JP2009269789A - System for generating hydrogen and method for producing hydrogen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a system which can take out gaseous hydrogen safely and efficiently, and a method for producing hydrogen using the system. <P>SOLUTION: The system for generating hydrogen 1 includes: a cartridge 2 which holds a hydrogen generating agent such as an active aluminum micro particle or the like in a container 3; and a reaction liquid feeding section 5 and a reaction liquid feeding means which feed a reaction liquid to the cartridge 2, wherein the reaction liquid feeding means is a means to make the hydrogen generating agent such as the active aluminum micro particle or the like react with the reaction liquid from the bottom part of the cartridge container 3. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hydrogen generation apparatus that generates hydrogen and a hydrogen generation method using the apparatus, and more particularly to an apparatus for generating hydrogen gas to be supplied to a fuel cell and a method using the apparatus.

  Hydrogen tanks using hydrogen storage alloys and small fuel cells that use hydrogen gas as fuel are about to be put into practical use. How to manufacture hydrogen gas used in small fuel cells at low cost and safely is important. It has become a challenge.

Conventionally, a hydrogen gas generation method using aluminum fine particles with enhanced low-temperature reactivity by applying an activation treatment to aluminum fine particles obtained by pulverizing an aluminum alloy in water has been disclosed (Patent Document 1). reference).
Also disclosed is a hydrogen generator that can supply a reaction liquid to a reaction vessel by a driving mechanism and perform a supply start operation and a supply amount adjustment (see Patent Document 2).

However, it is difficult to control hydrogen generation and the reaction proceeds rapidly, or in the conventional hydrogen generation apparatus and method, the reaction stops soon after the start of hydrogen generation, and it is difficult to efficiently extract hydrogen gas. There was a problem that there was. In addition, since the end point of the hydrogen generation reaction cannot be confirmed, there is a problem such as a case where the remaining unreacted hydrogen generator reacts again later.
JP 2006-4504 A JP 2007-145664 A

  The present invention has been made to cope with such problems, and an object of the present invention is to provide a hydrogen generation apparatus that can efficiently and safely extract hydrogen gas and a hydrogen generation method using the apparatus.

Regarding the hydrogen generation reaction, it has been confirmed that when a large amount of reaction solution is added at once, the reaction rapidly proceeds and the hydrogen generation cannot be controlled and the reaction vessel is damaged. Therefore, it was confirmed that hydrogen was generated at an initial stage when a small amount was added, but the reaction would soon stop even though the hydrogen generator was unreacted. Therefore, when we studied the problem that the reaction would stop soon after the start of hydrogen generation, when a reaction liquid such as water was dropped from above the hydrogen generator such as aluminum powder to react and generate hydrogen gas, It turns out that an aluminum oxide layer, which is a by-product, is formed near the surface of the generator, and the reaction solution cannot penetrate into the unreacted hydrogen generator, and the reaction stops shortly after the start of dropping. It was. Moreover, since reaction was advanced from the surface layer of the filled hydrogen generating agent, it turned out that completion | finish of reaction with a hydrogen generating agent and a reaction liquid cannot be confirmed.
The present invention has been made based on such knowledge, and the hydrogen generator of the present invention includes a cartridge that contains a hydrogen generating agent in a container, a reaction liquid supply unit that supplies a reaction liquid to the cartridge, and a reaction liquid supply. Means for reacting the hydrogen generating agent with the reaction liquid from the bottom of the cartridge container.

The reaction liquid supply means may be any method as long as the hydrogen generating agent and the reaction liquid can be reacted from the bottom of the cartridge, and a hollow member and one end of the hollow member that supply and supply the reaction liquid directly from the bottom. And a pin-like body having a pin fitted with a gap communicating with the hollow interior, the tip of the pin being inserted to the vicinity of the bottom of the cartridge container, and the reaction liquid extending along the outer peripheral surface of the pin from the gap As a good example, a means for supplying the information can be given.
Further, the cartridge container is characterized in that an excessive reaction at the time of hydrogen generation is prevented by forming the periphery of the container or a part thereof with a material having excellent thermal conductivity.
The hydrogen generator of the present invention is used for a fuel cell device.

The hydrogen generation method of the present invention is a hydrogen generation method using the hydrogen generation apparatus,
A step of mounting a cartridge containing a hydrogen generating agent in the hydrogen generator; a step of inserting a rod-like body to the vicinity of the bottom of the cartridge container; and a reaction solution supplied by a reaction solution supply unit through the rod-like body. And a step of generating hydrogen by reacting the hydrogen generating agent with the reaction liquid from the bottom of the cartridge.
The reaction solution is water.

The hydrogen generator of the present invention generates hydrogen by reacting a hydrogen generating agent with a reaction solution from the bottom of a cartridge container. Since the hydrogen generator is immersed in the reaction solution from the bottom of the container and the reaction between the hydrogen generator and the reaction solution proceeds, quantitative hydrogen is generated according to the supply of the reaction solution without leaving an unreacted hydrogen generator. Hydrogen gas can be taken out efficiently.
Further, the hydrogen generating agent is immersed in the reaction solution from the bottom of the container, and the surface of the stored hydrogen generating agent is immersed in the reaction solution, so that the completion of the reaction can be confirmed. For this reason, an unreacted hydrogen generating agent does not remain, and a highly safe hydrogen generating apparatus can be obtained.
Further, since the hydrogen generating agent is accommodated in the cartridge container and reacted with the reaction liquid in the container, there is no possibility that the user accidentally touches the reaction part during the reaction.

  Moreover, since the hydrogen generation method of the present invention uses the hydrogen generation apparatus, hydrogen gas can be efficiently and safely taken out.

  The hydrogen generator of the present invention will be described with reference to the drawings. FIG. 1 is a perspective view showing an example of an embodiment of the hydrogen generator of the present invention, and FIG. 2 is a cross-sectional view taken along line AA in FIG.

  As shown in FIGS. 1 and 2, the hydrogen generator 1 of the present invention includes a cartridge 2 that contains a hydrogen generating agent 4 in a container 3, a reaction liquid supply unit 5 that supplies a reaction liquid to the cartridge 2, and a reaction. Liquid supply means. The reaction solution supply unit 5 includes a storage unit 6 for storing the reaction solution, a supply mechanism 7 such as a syringe pump or a syringe, and a reaction solution supply path 8. The cartridge 2 and the reaction liquid supply unit 5 are connected to the fixing plate 15 fixed to the lid cover 9 or the like covering the cartridge 2 by the reaction liquid supply path 8 by fixing the reaction liquid storage unit 6 with a fixing screw 16 or the like. Connected. The reaction liquid stored in the storage unit 6 passes through the supply path 8 by the supply mechanism 7 and is further supplied into the cartridge container 3 by the reaction liquid supply means.

  As shown in FIG. 2, the cartridge 2 contains a hydrogen generating agent 4 that generates hydrogen by reacting with a reaction liquid in a sealed container 3 made of resin and formed into a cylindrical shape. In the hydrogen generator 1, the resin container 3 is replaced and used for each use. Further, since the exothermic reaction between the hydrogen generating agent and the reaction liquid occurs inside the container 3, the cartridge 2 is formed around the container 3 or a part thereof with a material having excellent thermal conductivity. It is preferable to prevent excessive reaction. As a material excellent in thermal conductivity, it is preferable to cover with a cover 12 made of metal or the like, or cover an upper part with a cover plate 9 made of a brass plate 14 or a resin excellent in thermal conductivity.

Examples of the hydrogen generating agent 4 that can be used in the present invention include one or more metal particles selected from metals that react with a reaction solution such as water to generate hydrogen, such as Fe, Al, Mg, Zn, and Si. And metal particles in which these are partially oxidized. The hydrogen generator may be in the form of a powder, or may be granular or tableted.
A preferred hydrogen generator 4 is active aluminum fine particles.

The reaction liquid supply means is a means for reacting the hydrogen generating agent and the reaction liquid from the bottom of the container 3 of the cartridge containing the hydrogen generating agent 4.
As a preferred example of the reaction liquid supply means for supplying the reaction liquid to the bottom of the container 3 of the cartridge, the reaction liquid supplied from the reaction liquid storage section 6 through the supply path 8 is transmitted along the inserted rod-shaped body 10 to 3 is a method of supplying the hydrogen generating agent 4 accommodated in the inside.

As a specific example, as shown in FIG. 2, a rod-shaped body 10 is inserted from the upper part of the sealed cartridge container 3 and a reaction solution is supplied along the rod-shaped body.
As an example of the rod-shaped body 10, as shown in FIG. 2, there is a structure having a hollow member 10 a and a pin 10 b fitted at one end of the hollow member 10 a with a gap 10 c communicating with the hollow interior. Can be mentioned. The pin 10b is preferably of such a length that its tip reaches the vicinity of the bottom of the cartridge container 3. In the case of the rod-shaped body 10 having this structure, the reaction liquid supplied from the supply path 8 passes through the inside of the hollow member 10a through the connecting member 8a connected to the hollow member 10a, and oozes out of the pin 10b from the gap 10c. The reaction solution is supplied along the outer peripheral surface of the pin 10b.
Further, the hole 3 a is formed by inserting the rod-shaped body 10, and the generated hydrogen gas is released from the hole 3 a through the hydrogen supply path 11.

  In the case of the rod-shaped body 10 having the above structure, when the reaction liquid is transmitted along the outer peripheral surface of the pin 10b, the active aluminum fine particles as the hydrogen generating agent 4 in contact with the pin 10b react with the reaction liquid, so that the active aluminum fine particles are porous. Changes to aluminum oxide. As a result, a flow path for the reaction liquid is formed, and the reaction liquid reaches the bottom of the cartridge container 3 by gravity without diffusing around the pins 10b. The reaction liquid that has reached the bottom of the cartridge container 3 immerses aluminum fine particles from the bottom of the container 3.

As another example of the rod-shaped body 10, the hollow member 10a and the pin 10b may be integrated, and the whole may be hollow and may have a reaction liquid discharge hole at the bottom. In this case, the reaction liquid is supplied from the bottom of the container 3 through the hollow interior of the rod-shaped body 10.
Further, any mechanism that reacts the hydrogen generating agent and the reaction liquid from the bottom of the container 3 of the cartridge in which the hydrogen generating agent 4 is stored may be used. The reaction liquid supply path 8 is connected to the bottom of the container 3 of the cartridge. The structure etc. which send a reaction liquid from 3 bottom part may be sufficient.

  Hydrogen generated inside the cartridge container 3 is discharged from the hydrogen supply path 11 through the hole 3a of the cartridge formed when the rod-like body 10 is inserted, and stored in a tank or the like, or directly supplied to the fuel cell device. .

  Further, a safety valve 13 is attached to the hydrogen generator 1 of the present invention, and when the pressure rises abnormally due to hydrogen generation inside the cartridge 2, the safety valve 13 operates to lower the pressure inside the cartridge 2.

  The active aluminum fine particles that can be used in the present invention are aluminum or aluminum alloy having a thickness of 50 μm or less, which has micro cracks on the surface and inside of the aluminum fine particles and contains aluminum hydride in the cracks. Specific examples of such active aluminum fine particles include aluminum and aluminum alloys as disclosed in JP 2008-24590 A. This is due to the fact that aluminum or aluminum alloy materials are rubbed and crushed in water to form crystal lattice distortion and micro cracks to a certain depth from the surface, and by applying temperature or ultrasonic shock, Cracks are generated, and the amount of hydrogen gas produced is increased, and by continuing the cracks and destruction inside the material due to the volume expansion caused by the generated hydrogen, the cracks are self-proliferated to generate hydrogen. Can be autonomously continued.

  The reaction solution that can be used in the present invention may be any one that reacts with a hydrogen generator to generate hydrogen, and examples thereof include acidic aqueous solutions, alkaline aqueous solutions, and water. Among these, a preferable reaction solution is water because it reacts with the active aluminum fine particles to generate hydrogen and is easy to handle.

  As the supply mechanism 7 for supplying the reaction liquid, any means that can quantitatively supply the reaction liquid to the cartridge 2 by using a syringe pump or a dropper can be used. It is preferable to use a syringe pump.

The method for adhering the resin materials constituting the container 3 of the cartridge is not particularly limited, but it is more preferable if it can be adhered by a method that does not use an adhesive. As such a bonding method, for example, resin bonding means such as ultrasonic welding, laser welding, thermal welding, diffusion welding, impulse welding, and high-frequency welding can be used. Adhesion of the adhesive into the cartridge can be prevented by adhering the resin materials by welding without using an adhesive or the like.
Among the above-mentioned resin material bonding means, it has excellent bonding strength and airtightness between resin materials, as well as excellent dimensional accuracy and external shape. It can be welded in various resin materials, and the resin materials are firmly bonded to each other. Therefore, it is preferable to use ultrasonic welding or heat welding.

  Ultrasonic welding varies depending on the resin material, cartridge size, etc., but the ultrasonic vibration horn amplitude is 25-50 μm in the vertical direction and the frequency is 15-40 kHz to increase the welding strength and air density. Therefore, it is preferable. In particular, ultrasonic welding conditions with an amplitude of 50 μm in the vertical direction and a frequency of 40 kHz are preferable. In the case of thermal welding, although it varies depending on the size of the resin material and the cartridge, it is preferable that the temperature range is 80 to 150 ° C. and the welding time is within 5 seconds.

The hydrogen generation method of the present invention is to generate hydrogen using the hydrogen generator 1 described above. First, a cartridge 2 in which a hydrogen generating agent 4 such as active aluminum fine particles is accommodated is mounted in the hydrogen generator 1. As a specific example, the cartridge 2 is installed in a resin or metal cover 12 and covered with a brass plate 14 to which a safety valve 13 or a hydrogen supply path 11 is attached and a lid cover 9. Next, the rod-like body 10 is inserted from the hole 3 a provided in the lid cover 9 and the cartridge container 3 to the vicinity of the bottom of the cartridge container 3. The hollow member 10 a of the rod-like body 10 is connected to the connection member 8 a of the reaction liquid supply path 8 and further connected to the reaction supply unit 5.
By this apparatus 1, a reaction solution such as water is supplied from the storage unit 6 by the supply means 7 of the reaction solution supply unit 5, and is transferred to the bottom of the cartridge container 3 through the supply path 8 through the rod-like body 10 as described above. The hydrogen generating agent and the reaction liquid are reacted from the bottom of the cartridge to generate hydrogen.

Example 1
In the hydrogen generator 1 shown in FIG. 1, a reaction liquid supply mechanism 7 using a syringe pump was prepared. A cartridge container 3 containing 10 g of activated aluminum fine particles HD-14 (manufactured by Hydrodevice Co., Ltd.) is attached to the apparatus, and the amount of hydrogen generated by a graduated cylinder prepared in the water tank through the exhaust pipe from the hydrogen supply path 11 is measured. Prepared for quantification. The rod-shaped body 10 was inserted into the cartridge container 3. After 1.0 ml of water is sent as a reaction solution with a syringe pump, when the hydrogen generation rate is 9.0 ml / min or less, the solution is sent with a syringe pump at 0.1 ml / min for 300 minutes, and every minute according to the water supply. The amount of hydrogen generated was measured. The results are shown in FIG. After the reaction, the active aluminum fine particles in the cartridge container 3 were completely immersed in water.

Example 2
In the hydrogen generator 1 shown in FIG. 1, a reaction liquid supply mechanism 7 using a dropper was prepared. A cartridge container 3 containing 10 g of activated aluminum fine particles HD-14 (manufactured by Hydrodevice Co., Ltd.) is attached to the apparatus, and the amount of hydrogen generated by a graduated cylinder prepared in the water tank through the exhaust pipe from the hydrogen supply path 11 is measured. Prepared for quantification. When 1.0 ml of water is sent as a reaction solution with a dropper and the hydrogen generation rate is 9.0 ml / min or less, 1.0 ml is repeatedly sent with a dropper and the amount of hydrogen generation per minute according to the water supply is measured. did. The results are shown in FIG. After the reaction, the active aluminum fine particles in the cartridge container 3 were completely immersed in water.

  As shown in FIG. 3 and FIG. 4, it was confirmed that the total amount of generated hydrogen was almost the same regardless of whether the reaction liquid supply mechanism 7 was a syringe pump or a syringe. In particular, it was confirmed that substantially quantitative hydrogen generation can be stably supplied by quantitatively and continuously feeding water as a reaction solution using a syringe pump.

Comparative Example 1
In the hydrogen generator used in Example 1, a hole was provided in the upper part of the cartridge container 3 without inserting the rod-like body 10 into the cartridge container 3, and water was fed from this hole. Hydrogen generation was observed immediately after feeding, but hydrogen generation stopped after about 150 minutes.

  Since the hydrogen generator of the present invention can generate hydrogen by reacting all of the hydrogen generator such as active aluminum fine particles and the reaction liquid, the fuel cell device using this hydrogen generator is used for home appliances, personal computers. It can be suitably used as a fuel cell device used in portable electronic devices and the like.

It is a perspective view which shows an example of embodiment of the hydrogen generator of this invention. It is the sectional view on the AA line in FIG. It is a figure which shows the time-dependent change of the hydrogen generation amount at the time of using a syringe pump for reaction liquid supply. It is a figure which shows the time-dependent change of the hydrogen generation amount at the time of using a dropper system for reaction liquid supply.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hydrogen generator 2 Cartridge 3 Container 4 Hydrogen generating agent 5 Reaction liquid supply part 6 Reaction liquid storage part 7 Reaction liquid supply mechanism 8 Reaction liquid supply path 9 Lid cover 10 Rod-shaped body 11 Hydrogen supply path 12 Cover 13 Safety valve 14 Brass plate 15 Fixing plate 16 Fixing screw

Claims (6)

A hydrogen generator comprising a cartridge that contains a hydrogen generating agent in a container, a reaction liquid supply unit that supplies a reaction liquid to the cartridge, and a reaction liquid supply means,
The hydrogen generating apparatus according to claim 1, wherein the reaction liquid supply means is a means for reacting the hydrogen generating agent and the reaction liquid from the bottom of the cartridge container.   The reaction liquid supply means is a rod-shaped body having a hollow member and a pin fitted with a gap communicating with the hollow interior at one end of the hollow member, and the tip of the pin is near the bottom of the cartridge container The hydrogen generator according to claim 1, wherein the reaction liquid is supplied along the outer peripheral surface of the pin from the gap.   3. The cartridge container according to claim 1, wherein an excessive reaction at the time of hydrogen generation is prevented by forming the periphery of the container or a part thereof with a material having excellent thermal conductivity. Hydrogen generator.   4. The hydrogen generator according to claim 1, wherein the hydrogen generator is used in a fuel cell device. A hydrogen generation method using the hydrogen generator according to any one of claims 1 to 4,
Mounting the cartridge containing the hydrogen generating agent in the hydrogen generating device;
Inserting the rod-like body to the vicinity of the bottom of the cartridge container;
Supplying the reaction solution supplied by the reaction solution supply unit via the rod-shaped body;
And a step of generating hydrogen by reacting the hydrogen generating agent with a reaction solution from the bottom of the cartridge. 6. The method for generating hydrogen according to claim 5, wherein the reaction solution is water.

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