Hydrogen generating device

Abstract

A hydrogen generation device 1 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 22. In addition, the hydrogen collection device 31 collects hydrogen generated by a reaction between the hydrogen carrier on the surface 41a and the liquid. A by-product collection device (61) collects by-products generated by a reaction between the hydrogen carrier on the surface (41a) and the liquid. A heating device 51 heats the conveyor belt 41. As a result, it is possible to obtain a hydrogen generation device (1) that easily promotes a reaction between a hydrogen carrier and an aqueous 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 liquid 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, there are cases where additives such as reaction promoters are used to enable the hydrolysis of hydrogen carriers such as sodium borohydride to proceed stably. In the case of generating hydrogen by hydrolysis of sodium borohydride, by-products such as sodium metaborate are produced. This by-product can be restored to a hydrogen carrier such as sodium borohydride, but in the case where additives such as reaction promoters remain in the by-product, more effort is required to restore the by-product to a hydrogen carrier. Therefore, a structure that can promote the reaction between the hydrogen carrier and the aqueous liquid even without adding additives or reducing the amount of additives added is desired.

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

[0006] The hydrogen generation device of the present invention includes: a conveyor belt, a coating device configured to coat a solid hydrogen carrier on the surface of the conveyor belt, a discharging device configured to discharge an aqueous liquid onto the hydrogen carrier coated on the surface of the conveyor belt, a hydrogen collection device configured to collect hydrogen generated by the reaction between the hydrogen carrier and the liquid on the surface of the conveyor belt, a by-product collection device configured to collect by-products generated by the reaction between the hydrogen carrier and the liquid on the surface of the conveyor belt, and a heating device configured to heat the conveyor belt. Advantageous Effects of the Invention

[0007] 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 liquid. Brief Description of the Drawings

[0008] Figure 1 is a schematic structural cross-sectional view of the hydrogen generation device according to the first embodiment. Figure 2 is a control block diagram of the hydrogen generation device according to the first embodiment. Figure 3 It is a schematic structural cross-sectional view showing an enlarged view of a heating portion of a conveyor belt in a hydrogen generation device according to a first embodiment. Figure 4 It is a schematic structural cross-sectional view showing an enlarged view of a heating portion of a conveyor belt in a hydrogen generation device according to a second embodiment. Figure 5 It is a schematic structural cross-sectional view showing an enlarged view of a heating portion of a conveyor belt in a hydrogen generation device according to a third embodiment. Figure 6 It is a schematic structural cross-sectional view showing an enlarged view of a heating portion of a conveyor belt in a hydrogen generation device according to a fourth embodiment. Detailed Description <First Embodiment>

[0009] The following will be described with reference to Figures 1 to 3 The first embodiment will be described. First, as an energy source alternative to 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 at a high pressure such as 70 MPa (700 times the atmospheric pressure).

[0010] The problem with hydrogen serving as an energy source is its low energy density. The volumetric energy density of hydrogen is about 1 / 3000 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.

[0011] Therefore, various materials have been considered as materials (i.e., hydrogen carriers) that can carry hydrogen at a higher energy density than a hydrogen tank. For example, ammonia, methylcyclohexane, etc. are known as hydrogen carriers, and during use, the hydrogen carrier rather than hydrogen itself is transported and hydrogen is extracted from the hydrogen carrier.

[0012] 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 hydrolysis of 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.

[0013] 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]

[0014] 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 serving as a coating device, a liquid discharge device 22 serving as a discharge device, a hydrogen collection device 31, and a by-product collection device 61.

[0015] The conveyor belt 41 rotates in the direction of the arrow in Figure 1 The powder coating device 12 receives the supply of the hydrogen carrier from the hydrogen carrier storage tank 11 storing the hydrogen carrier in powder form, 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 discharge device 22 is provided 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.

[0016] In the rotation direction of the conveyor belt 41, the hydrogen collection device 31 is provided downstream of the liquid discharge device 22, and collects hydrogen generated from 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 by-products generated from 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 products other than hydrogen generated from the reaction between the hydrogen carrier and the liquid. In addition, the hydrogen generation device 1 of the present embodiment further includes a heating device 51 for heating the conveyor belt 41.

[0017] The hydrogen generation device 1 can perform a series of steps on the conveyor belt 41, such as generating hydrogen through the reaction between a hydrogen carrier and an 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.

[0018] The operation of the hydrogen generation device 1 is as follows. First, the conveyor belt 41 starts to move, and the heating device 51 starts heating at the same time. When the conveying speed of the conveyor belt 41 stabilizes 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 discharge device 22, the liquid is discharged from the liquid discharge device 22, the reaction between the hydrogen carrier and the liquid starts, and the generated hydrogen is collected by the hydrogen collection device 31.

[0019] 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]

[0020] 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.

[0021] In addition, the hydrogen carrier of this embodiment is preferably a solid such as powder or granule, 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 preferred. 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 the contact area with the aqueous liquid.

[0022] 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. The sodium borohydride after the reaction 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)

[0023] It is known that this reaction (chemical formula (1)) is promoted by a Raney catalyst, which is formed from a metal such as nickel, cobalt or copper and an acidic solution such as citric acid or acetic acid. [Aqueous liquid]

[0024] 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. Additionally, two or more aqueous liquids can be prepared. By preparing two or more aqueous liquids, the hydrogen generation rate can be adjusted.

[0025] 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.

[0026] A surfactant can be added to the aqueous liquid. By using a 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.

[0027] The aqueous liquid can contain water-soluble acidic substances. 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 less 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.

[0028] The aqueous liquid can include water-soluble basic substances. 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.

[0029] The aqueous liquid may include a buffer solution. The function of the buffer solution is to inhibit pH fluctuations 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.

[0030] In addition to the above components, if necessary, the aqueous liquid may further contain various additives such as defoaming agents, pH adjusters, viscosity adjusters, rust inhibitors, preservatives, antifungal agents, antioxidants, and anti-reducing agents. [Conveyor belt]

[0031] 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.

[0032] In any case, the conveyor belt 41 is arranged such that the stretched surface stretched by two rollers (the driving roller 42 and the driven roller 43 in the present embodiment), that is, the above surface 41a is oriented in a substantially horizontal direction. In addition, the surface 41a is an 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.

[0033] 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. In addition, a heating device 51 for heating the conveyor belt 41 from the inner peripheral surface side is provided on the inner side of the conveyor belt 41.

[0034] From the viewpoint of never causing static electricity, the conveyor belt 41 is preferably given electrical conductivity and can be formed of metal or resin. In the case of metal, aluminum, iron, copper, Ni, stainless steel (SUS), etc. can be used. Further, in the case of resin, from the viewpoint of heat resistance, a resin having a high glass transition temperature is preferred, for example, an engineering plastic having high heat resistance and high durability is preferred, such as polyimide, polyamideimide, and polyetheretherketone. Further, in the case where the resin does not have electrical conductivity, it is preferred that the resin contains an antistatic agent such as carbon black to impart electrical conductivity. Further, 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 the present embodiment, an endless belt formed of a resin (which is a carbon-containing polyimide) having electrical conductivity is used as the conveyor belt 41.

[0035] The conveying speed (rotation speed) of the conveyor belt 41 is a predetermined speed set for each hydrogen carrier and aqueous liquid used. Further, it is preferred that the conveying speed can be appropriately adjusted according to the required amount of hydrogen. Thus, 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, for example, by appropriately adjusting the conveying speed according to the amount of hydrogen measured by a flow rate sensor 32 (see Figure 2 ), etc., which measures the flow rate of hydrogen collected by the hydrogen collection device 31. [Powder coating device]

[0036] The powder coating device 12 is a device that receives the supply of a 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 preferred to set the thickness to 50 μm or more and 500 μm or less in order to improve the reactivity with the aqueous liquid.

[0037] Further, the hydrogen carrier storage tank 11 serving as a hydrogen carrier supply container stores a hydrogen carrier (hydrogen carrier for replenishment) for replenishing the storage portion of the powder coating device 12. The hydrogen carrier storage tank 11 can be attached to the powder coating device 12 and can be separated from it. That is, the hydrogen carrier storage tank 11 is replaceable. [Liquid discharging device]

[0038] The liquid discharging device 22 is a liquid coating device that receives the supply of an 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 discharging device 22 can adjust the amount of the aqueous liquid relative to the amount of the hydrogen carrier. The liquid discharging 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.

[0039] The non-contact liquid discharging device 22 has no particular problem as long as the liquid discharging device 22 is a device capable of coating the hydrogen carrier with the aqueous liquid, such as a spraying system, a shower system, or a dispenser system. Any of these systems can adjust the amount of liquid discharged. Additionally, as the contact-type liquid discharging device 22, an intaglio offset roller, a rod coater, a die coater, a doctor blade coater, a blade coater, etc. can be mentioned. Any of these systems can adjust the amount of liquid discharged.

[0040] Additionally, the liquid storage tank 21 serving as the liquid supply container stores the aqueous liquid to be supplied to the liquid discharging device 22. The liquid storage tank 21 can be attached to and detached from the liquid discharging device 22. That is, the liquid storage tank 21 is replaceable. [Hydrogen collection device]

[0041] A hydrogen collection device 31 is provided to collect hydrogen generated by the reaction between the hydrogen carrier and the 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 part 31a that collects the hydrogen generated on the conveyor belt 41 and a suction fan 31b that sucks the hydrogen collected by the collection part 31a. The hydrogen sucked by the suction fan 31b is supplied to a supply destination, such as a fuel cell, through a pipe 31c.

[0042] In a fuel cell, which is 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 can be mixed into the collected gas. Therefore, it is preferable to provide a mechanism for removing substances other than hydrogen in the 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]

[0043] 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.

[0044] The collection blade 61a is preferably adjacent to the outer peripheral surface of the stretched conveyor belt 41 that is stretched by the rollers of the conveyor belt 41. In the present embodiment, the roller is the drive roller 42. Additionally, the collection blade 61a is preferably adjacent to surfaces 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. Additionally, 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.

[0045] The material of the collection blade 61a is not particularly limited, and examples thereof include rubber blades formed of rubber and used for cleaning intermediate transfer belts in copiers and the like. It is formed of rubber such as silicone rubber or polyurethane rubber and is shaped 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. Additionally, there is no problem in using a blade formed of metal or glass in a spatula shape (i.e., a so-called spatula) as the collection blade 61a.

[0046] The blade holding member has a function of supporting the collection blade 61a and applying a certain pressure to the collection blade 61a by warping the blade holding member. Although its material is not particularly limited, metal is preferred because pressure is to be applied.

[0047] Additionally, the by-product collection box 62 that serves 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 and detached from the by-product collection device 61. That is, the by-product collection box 62 is replaceable. [Heating device]

[0048] The heating device 51 has a function of heating the conveyor belt 41 from the inner peripheral surface side to promote the reaction between the hydrogen carrier and the aqueous liquid and stably generate hydrogen. Therefore, in the hydrolysis reaction of the hydrogen carrier, hydrogen can be stably extracted without using a reaction promoter such as a catalyst.

[0049] Additionally, the system for heating the conveyor belt 41 by the heating device 51 is a system with high energy efficiency in terms of heating compared to systems such as heating the hydrogen carrier or heating the aqueous liquid because the range to be heated and the timing of heating can be performed only during the reaction between the hydrogen carrier and the aqueous liquid.

[0050] The heating device 51 may be a heating device that heats the conveyor belt 41 via a film or a belt, a heating device that directly transfers the heat of the heater to the conveyor belt 41, or a heating device that includes an induction heating system for the heater if the conveyor belt 41 is formed of metal. There is no particular limitation as long as heat can be quickly transferred to the conveyor belt 41 and the conveyor belt 41 can be quickly heated. In addition, there is no problem with a configuration in which a heater is provided on the outer peripheral surface side of the conveyor belt 41 and the hydrogen carrier and the aqueous liquid are directly heated. It should be noted that in the case of a configuration in which heating is performed from the outer peripheral surface side, from the viewpoint of safety, since contact between hydrogen and the heater should be avoided, a configuration in which heating is performed via a heating film or the like is preferable. The detailed configuration of the heating device 51 will be described later. [Central control device]

[0051] Figure 2 is a block diagram of 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 that stores programs, a communication interface, a signal transmission unit 114, and a signal reception unit 115. The controller 112 is constituted by 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 the programs stored in the storage 113.

[0052] The RAM 111 is the main memory in which the controller 112 operates. 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.

[0053] Information from the 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 on the engine unit 103 of the hydrogen generation device 1 through the signal reception unit 115. As information on 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 on 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.

[0054] 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 aqueous liquid in the liquid discharge device 22.

[0055] In addition, the controller 112 transmits the following signals via the signal transmission unit 114 as signals generated based on 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.

[0056] 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.

[0057] Specifically, the drive unit 11b of the hydrogen carrier storage tank 11 is, for example, a motor or a solenoid, and the motor or solenoid 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.

[0058] The drive unit 12b of the powder coating device 12 is, for example, a 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.

[0059] 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.

[0060] The drive unit 41b of the conveyor belt 41 is, for example, the motor described above. The controller 112 controls the driving of the drive unit 41b to drive and stop the conveyor belt 41 and further controls its driving speed. [Detailed Structure of Heating Device]

[0061] Next, the detailed structure of the heating device 51 of the present embodiment will be described by using Figure 3 As described above, the heating device 51 is provided inside the conveyor belt 41 and heats the conveyor belt 41 from the inside. The heating device 51 configured in this way includes a heating film 52, a heater 53, and a heater holding member 54. The heating film 52 is a tubular belt member adjacent to the conveyor belt 41 and is a film-like member in the present embodiment. The heating film 52 rotates due to being driven by the conveyor belt 41. The heater 53 is a heating member that heats the heating film 52 and heats the conveyor belt 41 via the heating film 52. The heater 53 is disposed in the internal space of the heating film 52 and is in contact with the inner peripheral surface of the heating film 52. The heater holding member 54 that serves as a holding member holds the heater 53 and also has a guiding function for guiding the rotation of the heating film 52.

[0062] From the viewpoint of instantaneously heating the conveyor belt 41, the heating film 52 preferably has a low heat capacity and high thermal conductivity. The material is not particularly limited and can be a metal or a resin. In the case of a metal, a thin film formed of aluminum, iron, copper, Ni, or an alloy thereof such as stainless steel (SUS) is preferred. Additionally, in the case of a resin, engineering plastics having high heat resistance and high durability are preferred, such as polyimide, polyamideimide, and polyetheretherketone. Additionally, a rubber layer can be provided on the heating film 52 to increase thermal conductivity. Additionally, a release layer formed of a fluororesin such as a perfluoroalkoxy alkane (PFA) tube can be provided on the outer peripheral surface of the heating film 52 to increase the slidability with the conveyor belt 41.

[0063] Although the heater 53 is also not particularly limited, considering the starting performance, it is preferable to use a ceramic heater, a halogen heater, etc. Regarding the heater capacity, the dimensions of the conveyor belt 41, the conveying speed, the thickness of the conveyor belt 41, etc. are designed by calculating the total heat capacity.

[0064] It should be noted that in order to raise the temperature of the conveyor belt 41 more quickly, a counter roller can be provided on the side opposite to the heating device 51 with the conveyor belt 41 disposed therebetween, and a heating clamping portion can be provided where the conveyor belt 41 is clamped by the heating film 52 and the opposing roller. It is preferable to set the position of the heating clamping portion to a position downstream of the liquid discharging device 22, a position where the liquid discharged from the liquid discharging device 22 does not end on the counter roller, and a position upstream of the hydrogen collecting range of the hydrogen collecting device 31 in the rotational direction of the conveyor belt 41. Alternatively, the position of the heating clamping portion can be set to a position within the hydrogen collecting range upstream of the center of this range.

[0065] In addition, a separating mechanism capable of making the heating device 51 adjacent to and separated from the conveyor belt 41 can be provided. Further, a configuration can be adopted in which the heating device 51 is separated from the conveyor belt 41, the heating film 52 is pre-heated, and the heating film 52 is brought into contact with the conveyor belt 41 during heating.

[0066] The heating device 51 is arranged to heat at least the region where the reaction between the hydrogen carrier and the liquid starts. In the present embodiment, the region (heating region) of the conveyor belt 41 heated by the heating device 51 is configured to include at least one region where the liquid is discharged onto the surface 41a of the conveyor belt 41 from the liquid discharging device 22. In particular, in the present embodiment, from the viewpoint of better efficiency of energy consumption related to heating, the heating device 51 is arranged at a position directly below the liquid discharging device 22, as Figure 3 shown. In other words, when the conveyor belt 41 is omitted and viewed in the vertical direction, the heating device 51 is configured to overlap with the liquid discharging device 22.

[0067] Regarding the heating temperature of the conveyor belt 41, the surface temperature on the outer peripheral surface side of the conveyor belt 41 in the heating region of the heating device 51 is preferably a temperature of 50°C or higher and lower than 100°C. For example, a temperature detection sensor for detecting the temperature of the inner peripheral surface or the outer peripheral surface of the conveyor belt 41 is provided, and the controller 112 (see Figure 2 ) controls the heater 53 based on the detection signal of the temperature detection sensor so that the temperature of the surface 41a of the conveyor belt 41 heated by the heating device 51 is a set temperature set within a range of 50°C or higher and lower than 100°C.

[0068] In the case where the surface temperature is lower than 50°C, there is a possibility that the reaction between the hydrogen carrier and the aqueous reaction liquid does not proceed, and thus sufficient hydrogen production amount cannot be obtained. In addition, in the case where the temperature is higher than 100°C, there is a greater possibility of the following problem: when the hydrogen carrier reacts with the aqueous liquid, evaporation of water itself also occurs, and a large amount of water vapor is mixed in the hydrogen collection device 31. The set temperature is appropriately set within a temperature range of 50°C or higher and lower than 100°C according to the type of the hydrogen carrier, the type of the liquid, etc. In addition, the set temperature can be changed according to the amount of hydrogen gas desired to be collected, etc.

[0069] In the present embodiment, an ODF type device commonly used in the fixing device of a copying machine is used as the heating device 51. The ODF type device includes the heating film 52, the heater 53, and the heater holding member 54 as described above. In the present embodiment, a film having a three-layer structure is used as the heating film 52, in which an elastic layer is formed on the outer peripheral surface of the polyimide base layer, and a release layer is formed on the outer peripheral surface of the elastic layer. A rod-shaped ceramic heater is used as the heater 53.

[0070] A heater 53 is provided to hold the heating film 52 together with the conveyor belt 41 while being held by a heater holding member 54. In other words, the heater 53 faces the inner peripheral surface of the conveyor belt 41, and the heating film 52 is located therebetween. It should be noted that other components such as heat transfer components may be provided between the heating film 52 and the heater 53.

[0071] In the case of this embodiment configured in this way, the conveyor belt 41 is heated by the heating device 51, so that the reaction between the hydrogen carrier and the aqueous liquid on the conveyor belt 41 can be easily promoted. In particular, in this embodiment, the area (heating area) where the conveyor belt 41 is heated by the heating device 51 is set to at least include the area where the liquid is discharged from the liquid discharging device 22 onto the surface 41a of the conveyor belt 41. Therefore, in the state where the liquid has been poured onto the hydrogen carrier, these are heated, so that the reaction between the hydrogen carrier and the liquid can be effectively promoted.

[0072] Therefore, according to the hydrogen generation device 1 of this embodiment, even when no additives such as reaction promoters are added, or even when the amount of additives added is reduced, the reaction between the hydrogen carrier and the aqueous liquid can be promoted. Therefore, the effort required to recover the by-products into the hydrogen carrier can be reduced. <Second Embodiment>

[0073] The second embodiment will be described by using Figure 4 The hydrogen generation device 1A of this embodiment is different from that of the first embodiment in the structure of the heating device for heating the conveyor belt 41. Other structures and functions are similar to those of the above-described first embodiment, so similar elements are denoted by the same reference numerals, and their descriptions and illustrations will be omitted or simplified, and the parts different from the first embodiment will be mainly described.

[0074] The heating device 51A of this embodiment includes a driving roller 56 and a driven roller 57 that serve as at least a pair of stretching roller members 55 of the stretching belt member 55, and is configured such that the area where the belt member 55 is stretched by the driving roller 56 and the driven roller 57 is adjacent to the conveyor belt 41. That is, the heating device 51A includes a belt member 55 having an annular shape, a driving roller 56, a driven roller 57, a heater 53A serving as a heating member, and a heater holding member 54A. The heater 53A is provided between the driving roller 56 and the driven roller 57 and is held by the heater holding member 54A.

[0075] In addition, in the present embodiment, a plurality of (three in the present embodiment) heaters 53A are arranged at constant intervals in the rotational direction of the conveyor belt 41 and are held by the heater holding member 54A. Also in the case of the present embodiment, each heater 53A is a rod-shaped ceramic heater. Further, in the present embodiment, the drive roller 56 is rotationally driven by a motor (not shown), and thus the belt member 55 is rotated in synchronization with the rotation of the conveyor belt 41.

[0076] In the case of the present embodiment configured in this way, the belt member 55 is stretched by the drive roller 56 and the driven roller 57, and thus the contact range of the belt member 55 with the conveyor belt 41 is configured to be wider than that in the structure of the first embodiment. Specifically, the region of the conveyor belt 41 heated by the heating device 51A is configured to include the region where the liquid is discharged from the liquid discharge device 22 onto the surface 41a of the conveyor belt 41 and the portion directly below a part of the hydrogen collection device 31. That is, since a plurality of heaters 53A include the portion directly below the liquid discharge device 22 and are arranged in the range from the portion directly below the liquid discharge device 22 to the position directly below the upstream portion of the hydrogen collection device 31 along the rotational direction of the conveyor belt 41, the conveyor belt 41 can be heated in a wide range.

[0077] By setting the wide heating region as described above, unreacted components of the hydrogen carrier can be eliminated or reduced, and moisture remaining after the reaction is more likely to evaporate. Therefore, hydrogen can be generated more effectively, and unreacted hydrogen carriers can be reduced for more effective use of the hydrogen carriers. <Third Embodiment>

[0078] The third embodiment will be described by using Figure 5 The hydrogen generation device 1B of the present embodiment is different from that of the second embodiment in the position of the heating device for heating the conveyor belt 41. Other structures and functions are similar to those of the second embodiment described above, and thus similar elements are denoted by the same reference numerals, and their descriptions and illustrations will be omitted or simplified, and the parts different from the second embodiment will be mainly described.

[0079] The structure of the heating device 51B in this embodiment is similar to that of the heating device 51A in the second embodiment. It should be noted that in this embodiment, the area of the conveyor belt 41 heated by the heating device 51B is configured to include the area where the hydrogen carrier from the powder coating device 12 is coated on the surface 41a of the conveyor belt 41. That is, a plurality of heaters 53A are arranged over the entire range from the position directly below the powder coating device 12 to the position directly below the liquid discharge device 22 along the rotation direction of the conveyor belt 41. In other words, the position where the conveyor belt 41 is heated by the heating device 51B starts from the position directly below the powder coating device 12. It should be noted that the area of the conveyor belt 41 heated by the heating device 51B can be set to extend in the rotation direction of the conveyor belt 41 to the range of the position directly below the upstream part of the hydrogen collection device 31.

[0080] As described above, in this embodiment, the area of the conveyor belt 41 heated by the heating device 51B starts from a position upstream of the position directly below the liquid discharge device 22 in the rotation direction of the conveyor belt 41. Therefore, before the liquid is discharged onto the hydrogen carrier, the hydrogen carrier can be heated, and the start of the reaction between the hydrogen carrier and the liquid can be improved. Therefore, the amount of hydrogen generated at the start of the reaction can be increased, and hydrogen can be effectively generated. <Fourth Embodiment>

[0081] The fourth embodiment will be described by using Figure 6 The hydrogen generation device 1C in this embodiment is different from that in the first embodiment in the structure of the heating device for heating the conveyor belt 41. Other structures and functions are similar to those in the first embodiment described above. Therefore, similar elements are denoted by the same reference numerals, and their descriptions and illustrations will be omitted or simplified, and the parts different from the first embodiment will be mainly described.

[0082] The heating device 51C in this embodiment includes a heater 53B that serves as a heating component for directly heating the conveyor belt 41. That is, different from each of the above embodiments, the heating device 51C adopts a system in which the conveyor belt 41 is directly heated by the heater 53B without passing through a belt member. In addition, on the side of the heater 53B opposite to the side where the conveyor belt 41 is provided, the heating device 51C further includes a reflector 58 equipped with a heat insulating material. The reflector 58 has a shape surrounding the heater 53B except for the side of the conveyor belt 41, and is configured to reflect the heat of the heater 53B provided inside thereof toward the conveyor belt 41.

[0083] In the present embodiment, a halogen heater is used as the heater 53B. Further, as the reflector 58, a metal plate formed of an aluminum alloy is used, and the outer side thereof is covered with a heat insulating material. The reflecting surface on the inner side of the reflector 58 is mirror-polished so that radiant heat from the heater 53B can be effectively transferred to the conveyor belt 41.

[0084] Also in the case of the present embodiment configured in this manner, the heating device 51C is provided directly below the liquid discharging device 22. It should be noted that a plurality of heaters 53B may be provided, and the reflector 58 may be provided so as to cover the plurality of heaters, such that a wide range of the conveyor belt 41 is heated, as in the second and third embodiments. Industrial Applicability

[0085] The hydrogen generation device according to the present invention can be preferably 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

[0086] 1, 1A, 1B, 1C: Hydrogen generation device 12: Powder coating device (coating device) 22: Liquid discharging device (discharging device) 31: Hydrogen collection device 41: Conveyor belt 41a: Surface 51, 51A, 51B, 51C: Heating device 52: Heating film (belt member) 53, 53A, 53B: Heater (heating member) 54, 54A: Heater holding member (holding member) 55: Belt member 56: Driving roller (tension roller) 57: Driven roller (tension roller) 61: By-product collection device

Claims

1. A hydrogen generation device, comprising: A conveyor belt; A coating device configured to coat a solid hydrogen carrier on the surface of the conveyor belt; An emission device configured to emit an aqueous liquid onto the hydrogen carrier coated on the surface of the conveyor belt; A hydrogen collection device configured to collect hydrogen generated by the reaction between the hydrogen carrier and the liquid on the surface of the conveyor belt; A by-product collection device configured to collect by-products generated by the reaction between the hydrogen carrier and the liquid on the surface of the conveyor belt; and A heating device configured to heat the conveyor belt.

2. The hydrogen generation device according to claim 1, wherein, The temperature of the surface of the conveyor belt heated by the heating device is equal to or higher than 50 °C and lower than 100 °C.

3. The hydrogen generation device according to claim 1, wherein, The heating device heats the conveyor belt from the inside of the conveyor belt.

4. The hydrogen generation device according to claim 1, wherein, The heating device heats at least the area where the reaction between the hydrogen carrier and the liquid starts.

5. The hydrogen generation device according to claim 4, wherein, The area of the conveyor belt heated by the heating device at least includes the area where the liquid is emitted onto the surface of the conveyor belt from the emission device.

6. The hydrogen generation device according to claim 5, wherein, The area of the conveyor belt heated by the heating device includes the area where the hydrogen carrier is coated on the surface of the conveyor belt by the coating device.

7. The hydrogen generation device according to claim 1, wherein, The heating device includes: a belt member configured to be adjacent to the conveyor belt, and a heating member configured to heat the belt member.

8. The hydrogen generation device according to claim 7, Among them, The belt member is a film-like member, and wherein, the heating device includes a holding member configured to hold the heating member and guide the rotation of the belt member.

9. The hydrogen generation device according to claim 7, wherein The heating device includes at least a pair of stretching rollers configured to stretch the belt member and make the area of the belt member stretched by the pair of stretching rollers adjacent to the conveyor belt.

10. The hydrogen generation device according to claim 9, wherein, The heating member is disposed between the pair of stretching rollers.

11. The hydrogen generation device according to claim 1, wherein, The heating device includes a heating member configured to directly heat the conveyor belt.

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