JP2009046370A - Hydrogen generating device and hydrogen generating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen generating device and a hydrogen generating method sufficiently maintaining the reactivity of a hydrogen generating agent even if a conservation period is prolonged. <P>SOLUTION: In the hydrogen generating device provided with the hydrogen generating agent 1 containing hydrogenated metal particles activated by removing metal hydroxide on the surface and a dehumidifying agent 2 in a reaction vessel 10 having a hydrogen discharge passage 12 and a moisture supply passage 11, the inside of the reaction vessel 10 is maintained in the state that the air does not flow in. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hydrogen generation apparatus and a hydrogen generation method for generating hydrogen gas by supplying moisture (including water vapor), and is particularly useful as a technique for supplying hydrogen to a fuel cell.

  Conventionally, hydrogen generators that supply water to generate hydrogen gas include those mainly composed of metals such as iron and aluminum, and those mainly composed of metal hydrides such as magnesium hydride. (For example, refer to Patent Document 1).

  In particular, as a hydrogen generator mainly composed of a metal hydride, a hydrogen generator containing magnesium hydride produced by adding a catalyst metal particle to magnesium particles and then performing a hydrogenation treatment is known. (For example, refer to Patent Document 2).

  On the other hand, in Patent Document 3 below, for the purpose of improving the reaction rate of magnesium hydride and the like, nanocrystals are obtained by pulverizing magnesium hydride particles with a ball mill prior to reacting magnesium hydride with moisture. A method for generating a state is disclosed.

  However, according to the study by the present inventors, a surface layer of magnesium hydroxide is generated on the surface of magnesium hydride particles by reaction with moisture in the air, and even if distortion or deformation occurs, It has been found that sufficient activation cannot be achieved when the magnesium hydroxide layer remains.

  In addition, even when using magnesium hydride that has been activated in advance, if it is left in the atmosphere or stored in a container that is normally used, a hydroxide film will form over time, and a sufficient reaction will occur during use. It was found that no sex was obtained. When a resin container is used, it is also clear that a hydroxide film is formed over time on magnesium hydride due to moisture in the resin and moisture that permeates the resin even if the sealed state is maintained. It was.

JP 2003-313001 A Japanese Patent Laid-Open No. 2003-314792 Special Table 2000-527281

  Accordingly, an object of the present invention is to provide a hydrogen generator and a hydrogen generation method that can sufficiently maintain the reactivity of the hydrogen generating agent even when the storage period is prolonged.

  Based on the above findings, the present inventors have intensively researched and found that the above object can be achieved by putting a dehumidifying agent in a reaction vessel to make it sealed, and the present invention has been completed. .

  That is, the hydrogen generator of the present invention includes a hydrogen generating agent containing metal hydride particles activated by removing metal hydroxide on the surface in a reaction vessel having a hydrogen discharge path and a water supply path. And a dehumidifying agent, so that the outside air does not flow into the reaction vessel.

  According to the hydrogen generator of the present invention, since the hydrogen generator contains metal hydride particles activated by removing metal hydroxide on the surface, the reactivity of the hydrogen generator is increased and a dehumidifier is added. Since it is provided in the reaction vessel so that the outside air does not flow in, the reactivity of the hydrogen generating agent can be sufficiently maintained even when the storage period is extended. Further, even when moisture absorption or moisture permeation from the reaction vessel itself occurs, the reactivity of the hydrogen generating agent can be maintained for a longer period.

  Magnesium hydride removes the metal hydroxide on the surface, so that the reactivity is greatly improved and the effect of activation is easily obtained. Conversely, an inert surface layer is formed by reaction with moisture in the atmosphere. It is likely to occur. Therefore, the present invention is particularly effective when magnesium hydride is used among metal hydrides.

  On the other hand, the hydrogen generating method of the present invention comprises a hydrogen generating agent containing metal hydride particles activated by removing metal hydroxide on the surface in a reaction vessel having a hydrogen discharge path and a water supply path. Then, using a hydrogen generator equipped with a dehumidifying agent, after storing in a state where no outside air flows into the reaction vessel, water is supplied from the moisture supply path to generate hydrogen by reaction with the hydrogen generator. And taking out from the hydrogen discharge path.

  According to the hydrogen generation method of the present invention, since the hydrogen generator contains metal hydride particles activated by removing metal hydroxide on the surface, the reactivity of the hydrogen generator is increased and a dehumidifier is added. Since it is prepared in the reaction vessel so that outside air does not flow in, the reactivity of the hydrogen generating agent can be sufficiently maintained even when the storage period is extended, and hydrogen is efficiently generated when moisture is supplied. be able to. Further, even when moisture absorption or moisture permeation from the reaction vessel itself occurs, the reactivity of the hydrogen generating agent can be maintained for a longer period.

  In the above, it is preferable to include a step of previously activating magnesium hydride particles using a ball mill. By using a ball mill, the hydroxide on the particle surface of magnesium hydride can be effectively removed, and the reactivity is greatly improved and the activation effect is easily obtained.

  As shown in FIG. 1, the hydrogen generator of the present invention includes a hydrogen generating agent 1 and a dehumidifying agent 2 in a reaction vessel 10 having a hydrogen discharge passage 12 and a moisture supply passage 11. The hydrogen generator 1 in the present invention contains metal hydride particles activated by removing metal hydroxide on the surface.

  Examples of the metal hydride include magnesium hydride, lithium hydride, calcium hydride, sodium hydride, lithium aluminum hydride, and the like. Magnesium hydride is preferred for the reasons described above.

A metal hydride generates hydrogen gas by reaction with water (hydrolysis or the like). For example, in the case of magnesium hydride, the following reaction is considered to occur.
MgH ₂ + 2H ₂ O → Mg (OH) ₂ + 2H ₂ (1)
This reaction is an exothermic reaction, and by keeping the system warm, the reaction can proceed with the temperature raised.

  It has been found that metal hydride particles have metal hydroxide formed on the surface by reaction with moisture in the air. For example, the surface of magnesium hydride particles has a surface layer of magnesium hydroxide. Hereinafter, the case of magnesium hydride will be described as an example.

  In the case of magnesium hydride, in a general storage method, a surface layer of magnesium hydroxide is formed on the surface of magnesium hydride particles by reaction with moisture in the air (same as the above reaction formula (1)). No hydrogen generation occurs even when reacted with water at room temperature. As a result of analyzing commercially available magnesium hydride, it was found that a surface layer of magnesium hydroxide having a thickness of about 50 nm was formed (see FIG. 4).

  The thickness of the surface layer of magnesium hydroxide as described above varies depending on the moisture in the atmosphere in the storage state, but is generally considered to be 10 to 100 nm. Even if this thickness is somewhat large, the effect of the present invention is sufficiently obtained.

  The average particle size of the metal hydride such as magnesium hydride is preferably 5 to 500 μm, more preferably 10 to 200 μm, and still more preferably 20 to 100 μm, from the viewpoint of increasing the reaction rate of hydrogen generation and the contact area with water. .

  The content of metal hydride such as magnesium hydride particles is preferably 80% by weight or more, more preferably 90% by weight or more, and 95% by weight or more in the hydrogen generator. Further preferred. When the content of the metal hydride is less than 80% by weight, the overall reaction rate tends to decrease and the amount of hydrogen generation per raw material weight tends to decrease.

  As the metal hydride particles such as magnesium hydride, particles activated by removing metal hydroxide on the surface in advance are used. The activation can be performed by, for example, a chemical treatment with a weak acid or a reduction treatment by heating. However, the magnesium hydride particles having a coating layer are mechanically deformed or the coating layer is removed. Therefore, it is preferable to perform a pulverization process or a pressure process.

  Examples of the pulverization and pressure treatment methods include a method of generating compressive force and / or shear force on magnesium hydride particles, and a method of scraping the surface. Specifically, a method using a pulverizer such as a ball mill, a roller mill, a high-speed rotating mill, a medium agitating mill, an airflow pulverizer, a compaction shear mill, a pulverizing method using a mortar, a method using various pressing devices, etc. Can be mentioned. Among these, a method using a pulverizer is preferable, and a method using a ball mill such as a planetary ball mill or a stirring ball mill is particularly preferable.

  The method using a ball mill can generate a uniform compressive force and / or shear force depending on the size of particles such as magnesium hydride, and can easily control the degree of mechanical deformation depending on the processing time. This is preferable.

  Specifically, from the viewpoint of further increasing the reaction rate at room temperature, it is preferable to perform treatment for 20 minutes or more using a ball mill, and from the viewpoint of further increasing the reaction rate at room temperature (without heat retention), 30 minutes or more. More preferably, the treatment is performed.

  The ratio of the average particle diameter before and after the treatment by pulverization using a ball mill or the like is preferably 10 to 50%, preferably 15 to 35% with respect to the average particle diameter before the treatment, from the viewpoint of further increasing the reaction rate at room temperature. Is more preferable. Therefore, the average particle diameter after the treatment with a metal hydride such as magnesium hydride is preferably 1 to 100 μm, more preferably 2 to 50 μm, and still more preferably 5 to 20 μm.

  The ball mill may be either a dry process or a wet process, but a dry process is preferred from the viewpoint of ease of processing, reactivity of the pulverized product, and the like. As balls used for the ball mill, ceramic balls such as zirconia are preferably used.

  The diameter of the ball is preferably 0.5 to 10 mm, more preferably 1 to 5 mm, from the viewpoint of further increasing the reaction rate at room temperature. The amount of metal hydride particles such as magnesium hydride is preferably 2 to 50 parts by weight and more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the ball.

  The hydrogen generator in the present invention contains particles of metal hydride activated as described above, and further contains a metal such as aluminum, an alkaline inorganic compound, and aggregation suppressing particles as necessary. be able to.

  As a metal contained as needed, the metal which reacts with water and generate | occur | produces hydrogen, such as an aluminum particle, an iron particle, and a magnesium particle, is preferable. Of these, aluminum particles are preferable. It is also possible to add a metal catalyst such as titanium, silicon, cerium, iron, calcium.

  When a metal such as aluminum is used in combination, a fine particle is preferable, an average particle size of 100 μm or less is preferable, an average particle size of 1 to 50 μm is more preferable, and an average particle size of 1 to 10 μm is preferable. Is more preferable. When the average particle size is less than 1 μm, production becomes difficult, secondary agglomeration occurs, and due to sintering, the surface area is significantly reduced at the time of temperature rise, and hydrogen generation tends to be reduced.

  As an aluminum particle, what was manufactured by the atomizing method is preferable. Moreover, what removed the oxide film on the surface is preferable. As such aluminum particles, various commercially available particles can be used.

  The metal content is preferably 1 to 10% by weight in the total hydrogen generator. When the metal content exceeds 10% by weight, the overall reaction rate decreases and the amount of hydrogen generated per raw material weight tends to decrease.

  When the alkaline inorganic compound is contained, examples of the alkaline inorganic compound include oxides, hydroxides and carbonates of alkali metals and alkaline earth metals. The alkaline inorganic compound is preferably at least one selected from the group consisting of calcium oxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, borax, sodium carbonate, and calcium carbonate, and particularly preferably calcium oxide. .

  The content of the alkaline inorganic compound is 0.1 to 10% by weight, preferably 0.2 to 5% by weight, and more preferably 0.5 to 3% by weight in the total hydrogen generator.

  When the aggregation-suppressing particles are contained, fine particles that are inert to the hydrogen generation reaction can be used as the aggregation-suppressing particles, but the aggregation-suppressing particles are made of carbon black, silica, cerium oxide, aluminum oxide, and titanium oxide. It is preferable that it is 1 or more types chosen from the group which consists of. Among these, carbon black is particularly preferable in terms of enhancing the aggregation suppressing effect.

  The content of the aggregation suppressing particles is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight in the total hydrogen generator. When the content of the aggregation suppressing particles exceeds 30% by weight, the content of magnesium hydride or the like is relatively decreased, and the total amount of hydrogen gas generated tends to be insufficient.

  As carbon black, for example, any of channel black, thermal black, acetylene black, ketjen black, fanes black and the like can be used. As carbon black, there are those subjected to hydrophilic treatment, etc., but in the present invention, untreated hydrophobic carbon black is preferably used in order to enhance the aggregation suppressing effect. Moreover, it is also possible to carry | support calcium oxide using these. The primary average particle size of carbon black is preferably 0.01 to 0.5 μm.

  In the present invention, it is also possible to add activated carbon, zeolite or the like. Active charcoal includes coconut shell charcoal, wood dust charcoal, peat charcoal, etc., but activated carbon also acts as a water retention agent. The activated carbon preferably has an iodine adsorption performance of 800 to 1200 mg / g.

  It is also possible to add an inorganic electrolyte. As the inorganic electrolyte, alkali metal, alkaline earth metal, heavy metal chloride, and alkali metal sulfate are preferable. For example, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ferric chloride, sodium sulfate, and the like. Is used.

  The hydrogen generating agent of the present invention may be a powdery mixture, but may be consolidated by a pressure press to form a consolidated product such as a pellet or a tablet. By performing such consolidation, the amount of hydrogen generated per unit volume can be increased.

  The dehumidifying agent in the present invention may be any as long as it can dehumidify the inside of a reaction vessel equipped with a hydrogen generating agent, and a commercially available solid or liquid dehumidifying agent can be used. Moreover, when using a solid dehumidifier, a powder, a granular material, a tablet, etc. can be used.

  As the dehumidifying agent, for example, calcium chloride, glycerin, bauxite, silica gel, zeolite, iron oxide and the like can be used. Among these, a solid dehumidifying agent is preferable from the viewpoint that it can be easily disposed in a state in which the reaction of the hydrogen generating agent is difficult to inhibit.

The amount of the dehumidifying agent is preferably determined according to the volume of the reaction vessel, the filling density of the hydrogen generating agent, and the type of the hygroscopic agent. For example, when using zeolite, the space in the reaction vessel (hydrogen generation) It is preferable to use 0.1 to 1 g, more preferably 0.2 to 0.5 g, per 1 cm ³ of the volume (including the filling gap of the agent). With such a use amount, the humidity in the sealed reaction vessel can be maintained at 5 RH% or less for a long period (for example, 12 months or more).

  The position where the dehumidifying agent is provided is an upper space of the hydrogen generating agent 1 in the reaction vessel 10 and is in direct contact with the supplied water, as shown in FIG. The position not to be preferred.

  In addition, as shown in FIG. 2, the reaction vessel 10 is partitioned by a hydrophobic or water-repellent porous membrane 3, the hydrogen generating agent 1 is disposed in one space, and one end of the moisture supply path 11 is provided, It is more preferable to provide the hygroscopic agent 2 in the space. Thus, by partitioning with the hydrophobic or water-repellent porous film 3, only moisture in the gas phase is removed by the moisture absorbent 2, and moisture supplied at the time of moisture supply is not easily affected by the moisture absorbent 2. Thus, the hydrogen generation reaction can be suitably performed.

  Examples of the hydrophobic or water-repellent porous membrane 3 include polyolefin-based porous membranes and fluororesin-based porous membranes, but they are used for reaction as much as possible without attaching the supplied water to the membrane surface. From this viewpoint, a fluororesin-based porous film having water repellency is preferable.

  In order to make the permeation of water uniform in the reaction vessel 10, a non-woven fabric made of a hydrophilic material may be provided on the upper surface of the hydrogen generating agent 1. Note that a porous support material 4 such as a nonwoven fabric, filter paper, or a porous membrane may be provided around or around the hydrogen generating agent 1 to promote water permeation and hydrogen gas circulation.

  As shown in FIG. 1, the hydrogen generator of the present invention includes a hydrogen generating agent 1 and a dehumidifying agent 2 in a reaction vessel 10 having a hydrogen discharge passage 12 and a water supply passage 11, and also in the reaction vessel 10. Outside air does not flow in.

  In order to prevent the outside air from flowing into the reaction vessel 10, for example, a method of providing check valves 11 a and 12 a in the hydrogen discharge path 12 and the water supply path 11, or valves that are closed when no differential pressure occurs. And a method of providing a flow path forming portion that is opened for the first time when hydrogen is generated (during use).

In particular, the check valve 11a provided in the moisture supply passage 11 is preferably closed when moisture is not supplied. As such a check valve that can be miniaturized, a so-called duck pill valve is used. Is preferred. This is a check valve provided with a beak-shaped elastic member that opens when the pressure on the primary side is greater than the pressure on the secondary side and closes when the pressure on the primary side is small. Then, moisture is supplied, which reacts with the hydrogen generating agent 1 to generate hydrogen gas, which can be discharged from the hydrogen discharge path 12. That is, in the hydrogen generation method of the present invention, hydrogen containing metal hydride particles activated by removing metal hydroxide on the surface in a reaction vessel 10 having a hydrogen discharge path 12 and a water supply path 11. Using a hydrogen generator comprising a generating agent 1 and a dehumidifying agent 2, the hydrogen generating device 1 is stored in a state in which outside air does not flow into the reaction vessel 10, and then water is supplied from the water supply passage 11 to store the hydrogen generating agent 1. Hydrogen is generated by the reaction with, and taken out from the hydrogen discharge path 12.

  Water can be supplied in liquid or gas (water vapor). Specifically, for example, when hydrogen gas is supplied to a fuel cell of a portable electronic device, water may be supplied into the reaction vessel 10 via the water supply path 11 with a syringe pump or a micro pump. In addition, a supply device that presses the syringe using the elastic restoring force of the spring, a supply device that presses the syringe using the expansion force of the compressed gas, and a valve that uses the expansion force of the compressed gas For example, a supply device that presses water in the container with the generated gas. Among these, from the viewpoint of being able to be downsized, requiring no power, and obtaining a stable flow rate, the water in the container is pressed by the gas discharged through a valve or the like using the expansion force of the compressed gas. A feeding device is preferred.

  Further, the generated hydrogen gas may be supplied to the fuel cell via the hydrogen discharge path 12.

  The reaction for generating hydrogen does not require any particular heating and can be performed at room temperature (25 ° C.). However, by keeping the temperature, the temperature rises due to the reaction heat, and the reaction rate is improved.

  When supplying water to the hydrogen generating agent, the whole amount may be supplied at once. However, when hydrogen gas is generated in a stable generating amount, 0.5 to 5.0 ml / h per 1 g of the hydrogen generating agent. It is preferable to supply water at a supply rate.

  The hydrogen generation method of the present invention preferably includes a step of previously activating the magnesium hydride particles using a ball mill. Such an activation process can employ the method described above.

  Examples and the like specifically showing the configuration and effects of the present invention will be described below. In addition, the evaluation item in an Example etc. measured as follows.

(1) Hydrogen generation flow rate After the generated hydrogen gas was dried through a silica gel dryer, the total amount of hydrogen generation was measured with a mass flow meter (manufactured by KOT-LOC).

(2) Average particle diameter The sample to be measured was dispersed in isopropyl alcohol with ultrasonic waves (100 W) for 3 minutes to prepare a dispersion liquid sample. This sample is put in a batch cell (a solvent is used for blank measurement), and a particle size distribution is measured at a refractive index of 2.20-0.00i using a laser diffraction particle size distribution measuring device (SALD-2200, manufactured by Shimadzu Corporation). The average value was calculated from the particle size distribution.

(3) Reaction rate The ratio of the total amount of hydrogen generated actually is expressed as a percentage of the theoretical amount of hydrogen generated when magnesium hydride particles and metal particles all react with water.

Experimental Example 1 (Analysis of surface layer)
Using commercially available magnesium hydride particles (purity 98%, Wako Pure Chemical Industries, Ltd., average particle diameter of about 40 μm), after opening the container, a sample was prepared while avoiding a hygroscopic environment, and a transmission electron microscope was used. Observation of the cross section and analysis by electron diffraction were performed.

  FIG. 3 is a cross-sectional photograph (50,000 times) taken with a transmission electron microscope, and points A to J indicate positions where analysis by electron diffraction is performed. FIG. 4 is a cross-sectional photograph (magnified 500,000) with a transmission electron microscope at a higher magnification, and a surface layer having a thickness of about 50 nm is present.

  5 is a chart showing the diffraction intensity of surface X-rays at point A in FIG. 3, and FIG. 6 shows a microelectron beam diffraction pattern at point I in FIG. From the position and intensity of diffraction points on the (021) plane and (10-1) plane in FIG. 6, it was found that the component of the surface layer was magnesium hydroxide. This result also coincides with the result of the surface X-ray diffraction intensity chart of FIG.

  On the other hand, FIG. 7 shows a micro electron diffraction pattern at a point J in FIG. From the positions and intensities of diffraction points on the (002) plane and (200) plane in FIG. 7, it was found that the component of the surface layer was magnesium hydride.

  From the above results, it was found that a surface layer made of magnesium hydroxide and having a thickness of about 50 nm was present on the surface of commercially available magnesium hydride particles.

Experimental example 2 (Examination of ball mill processing time)
Commercially available magnesium hydride particles (purity 98%, Wako Pure Chemical Industries, Ltd., average particle diameter of about 40 μm) are used as raw materials, zirconia balls (diameter 5 mm, 10 times use of raw materials), and planetary pot mill (manufactured by Ito Seisakusho). , P4) for 2 minutes to 2 hours. Moreover, as a comparative sample, an untreated product and a product pulverized in a mortar for 10 minutes were prepared.

  When the average particle size of the magnesium hydride particles having a treatment time of 20 minutes or more was measured, it was about 10 μm, and the particle size was about 25% smaller than that of the untreated product.

  Using 1.2 g of each sample, there was no incubation at room temperature (only beaker was used), there was incubation at room temperature (beaker was kept with styrofoam), and it was heated with an 80 ° C water bath. While supplying water at a rate of 3 ml / h with a syringe pump, hydrogen was generated and the amount of hydrogen generated was measured. The reaction rate and the stability of hydrogen generation were evaluated. The results are shown in Table 1.

  As shown in the results of Table 1, in the untreated product, hydrogen was not generated at room temperature (reaction rate 0%), and hydrogen was generated only when heated to 80 ° C. This result was the same even when the powder was pulverized in a mortar for 10 minutes or with magnesium hydride particles having a treatment time of 2 to 15 minutes. In contrast, magnesium hydride particles with a treatment time of 20 minutes or more generate hydrogen at room temperature (with heat retention), and with the treatment time of 30 minutes or more, hydrogen is generated even at room temperature (without heat retention). did. It has been found that the treatment time is preferably within 1 hour from the viewpoint of the stability of hydrogen generation.

Example 1
In Experimental Example 2, using magnesium hydride particles obtained by activation with a mill for 30 minutes, 1 g of the particles was charged in a reaction vessel (made of polycarbonate resin) having a packing density of about 50% by volume and a volume of 2 cm ^3. Filled in. At this time, the volume of the upper space was about 1 cm ³ . Furthermore, 0.5 g of a granular hygroscopic agent (manufactured by Mitsubishi Gas Chemical Company, RP agent) was placed in the inner container provided in the upper space in the reaction container, and then completely sealed so that no outside air would flow into the reaction container. .

  A plurality of such hydrogen generators were easily stored in a sealed state for 1 month and 3 months, and then hydrogen was generated under the same conditions as in Experimental Example 2 (with heat retention). All had a reaction rate of 93%. The time from when the water reached the hydrogen generating agent to the start of hydrogen generation was 1 second, and no change due to storage was confirmed.

Comparative Example 1
In Example 1, magnesium hydride particles were filled in a reaction vessel and sealed under exactly the same conditions as in Example 1 except that no hygroscopic agent was used. A plurality of such hydrogen generators were easily stored in a sealed state for one week, and then hydrogen was generated under the same conditions as in Experimental Example 2 (with heat retention). As a result, the reaction rate was 90%, the time from when the water reached the hydrogen generator until the start of hydrogen generation was 5 seconds, and the deterioration of reactivity due to storage was confirmed.

Comparative Example 2
In Example 1, magnesium hydride particles were filled in a reaction vessel and sealed under exactly the same conditions as in Example 1 except that no hygroscopic agent was used. A plurality of such hydrogen generators were easily stored in a sealed state for one month, and then hydrogen was generated under the same conditions as in Experimental Example 2 (with heat retention). As a result, the reaction rate was 85%, the time from when water reached the hydrogen generator until the start of hydrogen generation was 60 seconds, and the deterioration of reactivity due to storage was confirmed.

The longitudinal cross-sectional view which shows an example of the hydrogen generator of this invention The longitudinal cross-sectional view which shows the other example of the hydrogen generator of this invention Cross-sectional photograph of commercially available magnesium hydride particles by transmission electron microscope A cross-sectional photograph of a transmission electron microscope with a higher magnification observing the vicinity of the surface in FIG. Chart showing diffraction intensity of surface X-ray at point A in FIG. Microelectron diffraction pattern at point I in FIG. Micro electron diffraction pattern at point J in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hydrogen generator 2 Dehumidifier 10 Reaction container 11 Water supply path 12 Hydrogen discharge path

Claims (4)

  A reaction vessel having a hydrogen discharge passage and a water supply passage, comprising: a hydrogen generator containing metal hydride particles activated by removing metal hydroxide on the surface; and a dehumidifying agent, and the reaction vessel A hydrogen generator that does not allow outside air to flow inside.   The hydrogen generator according to claim 1, wherein the metal hydride is magnesium hydride.   A hydrogen generator comprising a hydrogen generator containing metal hydride particles activated by removing metal hydroxide on a surface and a dehumidifier in a reaction vessel having a hydrogen discharge channel and a water supply channel. And a hydrogen generation method in which after storing in a state in which outside air does not flow into the reaction vessel, water is supplied from the water supply path to generate hydrogen by reaction with the hydrogen generating agent and is taken out from the hydrogen discharge path .   4. The method for generating hydrogen according to claim 3, comprising a step of previously activating the particles of magnesium hydride using a ball mill.

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