Manufacturing method of hydrogen generating material

Abstract

To develop a manufacturing method of a hydrogen generating material that can function without trouble even under the fusion point of gallium.SOLUTION: Provided is a manufacturing method of providing fine cracks in a whole aluminum fine particle by hitting and grinding articles obtained by allowing a gallium alloy to act on aluminum in an oxygen-shielded reaction chamber. In a manufacturing method of a hydrogen generating material in which the fine particle having a non-spherical shape occupies the whole or at least more than half by weight of the hydrogen generating material to hold the gallium of a trace amount left in the crack, when allowing the gallium alloy comprising gallium added with at least one of indium and tin to act on aluminum, a heat cooling apparatus is added to add a step of heating and cooling operation in a range of 600°C to -30°C including the fusion point of the gallium alloy for repeating phase transition of the gallium alloy.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a hydrogen generating material. This invention relates to a method for producing a material for generating hydrogen from water, using an alloy as the main material. [Background technology]

[0002] The prices of crude oil and natural gas, which are the energy sources that support our lives, are expected to rise by February 2022. After Russia invaded Ukraine, prices soared due to supply instability around the world. Prices of ingredients have also remained at a high level, and each is settling at a high price.

[0003] Furthermore, from the perspective of protecting the global environment, the traditional energy policy centered on fossil fuels is being reviewed. The development of new energy sources such as renewable energy is being accelerated all over the world. It does not emit any carbon dioxide, a greenhouse gas that worsens the environment, and only emits water when burned. Various research projects are being conducted around the world to produce hydrogen from non-emission water in order to realize a hydrogen society. do.

[0004] However, hydrogen production is not completely safe, and the mixture of hydrogen and oxygen is not ignited. The hydrogen detonation gas, a violent explosion that occurs when the mixture is heated, has a lower limit of 4.65% and an upper limit of 93.3%. When mixed with air, the explosive limit is 4.1 to 74.2%, which is the widest range of explosive limits after acetylene. For this reason, transporting hydrogen alone is extremely dangerous, and Due to the nature of hydrogen, various problems must be solved to realize a hydrogen society. .

[0005] In this context, the so-called hydrogen transport technology, which synthesizes ammonia using hydrogen and nitrogen from the air, is being developed. Efforts are also being made to utilize hydrogen as a carrier. Development of catalysts for synthesizing nia from hydrogen and nitrogen, and conversely, catalysts for decomposing ammonia into hydrogen and nitrogen Development of more efficient catalysts is also underway, and efforts are underway to realize a hydrogen society. We are making progress little by little.

[0006] Meanwhile, research is also underway to generate hydrogen from water on-site. The most common and simplest method is to generate hydrogen by electrolysis of water, which is also taught in junior high school science. However, this requires electrolytes, electrodes, batteries, etc. It is not possible for anyone to generate hydrogen easily anywhere at any time.

[0007] In addition, to simply heat water to break it down into hydrogen and oxygen, a high temperature of approximately 4,000°C or higher is required. To obtain the necessary energy from the sun, it would require a large parabolic mirror or other device. In reality, there are no container wall materials that can withstand such high temperatures. However, the drawback is that it can only be operated during the day when sunlight is available.

[0008] However, when considering the global environment, there is no better way to generate hydrogen than from water. Therefore, the ultimate energy source is hydrogen, which is obtained by decomposing water at low temperatures and used in fuel cells, There is a demand for technology that can be used in hydrogen vehicles and other applications.

[0009] The invention of the present inventor in Patent Document 1 makes it possible to generate hydrogen from water very easily. However, at room temperature below the melting point of gallium, which is about 29.76°C, gallium is a solid. In this case, aluminum cannot be immersed in gallium, so a high temperature above the melting point of gallium is required. The disadvantage is that the aluminum must be heated to a temperature where it is immersed in gallium. This requires thermal energy to heat the gallium. Therefore, there is a demand for a more user-friendly method for producing a hydrogen generating material using gallium. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Patent No. 5429595 Summary of the Invention [Problem to be solved by the invention]

[0011] The object of the present invention is to provide a method for producing a hydrogen generating material that functions without problems even below the melting point of gallium. The goal is to develop [Means for solving the problem]

[0012] To solve this problem, the present invention provides a method for forming fine cracks throughout the fine particles obtained by crushing aluminum. A method for producing a hydrogen generating material, comprising the steps of: adding the above-mentioned compound to aluminum in a reaction chamber that is sealed off from oxygen; Gallium alloys containing at least one of indium and tin are used. The hydrogen generating material is subjected to impact pulverization, and all or at least half by weight of the non-spherical fine particles are removed. In the method for producing a hydrogen generating material, the gallium is added with indium in a ratio of When a gallium alloy containing at least one of gallium and tin is applied to aluminum, A thermal cooling device is added, and the gallium alloy is heated and cooled within a range of 600°C to -30°C, which includes the melting point of the gallium alloy. A hydrogen generating material characterized by adding a step of repeating the phase transition of the gallium alloy by cooling. This is a method for producing the material. [Effects of the Invention]

[0013] The method for producing a hydrogen generating material of the present invention has the following effects. 1 In the case of gallium alloys, the lower the melting point, the better, even in the low temperature range below the melting point of gallium. The gallium alloy has a high fluidity at room temperature, making it more likely to crack the aluminum. Therefore, the hydrogen generating material can be produced effectively. 2 The volume of liquid gallium is approximately 3.4% smaller than that of solid gallium, and gallium alloys are also approximately 3.4% smaller in liquid than solid gallium. Because the volume of the body is small, the phase change between liquid and solid can be repeated using a heating and cooling device. This heating and cooling device allows the cracks in the aluminum to grow larger, resulting in a high-quality hydrogen generating material. A Peltier element can be used as the heating element, but a heating device and a cooling device may be separate. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic diagram showing a method for producing a hydrogen generating material according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] Furthermore, in the method for producing a hydrogen generating material, preferably, Gallium alloys containing at least one of indium and tin are made into aluminum. When using it, A heating and cooling device is added and the temperature is raised within the range of 600°C to -30°C, which includes the melting point of the gallium alloy. A manufacturing method characterized by adding a step of repeating the phase transition of the gallium alloy by cooling. is also desirable. [Example]

[0016] FIG. 1 is a schematic diagram showing a method for producing a hydrogen-producing material according to one embodiment of the present invention. In Figure 1, 1 is aluminum, 2 is a crack, 3 is a gallium alloy, 4 is a container, and 5 is a ball. Mill grinder, 6 is a lid, 7 is a ceramic ball, 8 is hydrogen generating material particles, 9 is a motor, 10 is an anoxic chamber, and 11 is a heating and cooling device.

[0017] The entire process is carried out in an oxygen-free chamber 10. The upper left diagram in Figure 1 shows the aluminum 1 material. It is a material, and preferably, the oxide on the surface is removed in advance and then gallium is used as shown in the lower left figure. The specimen was immersed in liquid gallium alloy 3 at a temperature above the melting point of gallium alloy 3 for a certain period of time, and then pulled out. It is placed in the ball mill 5 shown in the figure together with ceramic balls 7 and rotated by a motor 9. The particles are then pulverized to obtain non-spherical hydrogen generating material particles 8. In this embodiment, the particles are pulverized in a ball mill. We are using machine 5, but as long as it can impact crush the embrittled aluminum 1, we are using machine 6. The type of material does not matter. This allows the entire hydrogen generating material, or at least its weight, to be More than half of the particles 8 of the hydrogen generating material are non-spherical.

[0018] In this embodiment, the weight ratio of the gallium alloy 3 of gallium, indium and tin is As in Example 1, the composition is 66.5% gallium, 20.5% indium, and 13% tin. is also a eutectic metal, and its melting point is 11°C. In other words, this gallium alloy 3 has a melting point of 1 It is a liquid at temperatures above 1°C, which is much lower than the melting point of gallium, 29.76°C. This means that the hydrogen generating material can be made of gallium alone. This has a great advantage over conventional manufacturing methods. There is a process in which aluminum 1 is immersed in gallium alloy 3, but if it is immersed in gallium only, In order to be in a solid state, the temperature must be above the melting point of gallium, 29.76°C. This would be a serious situation where the aluminum 1 could not be immersed. Gallium alloy 3 is liquid at temperatures above 11°C, which is comparable to the melting point of gallium, 29.76°C. In comparison, there is a temperature difference of more than 18°C, which means there is more room.

[0019] When producing aluminum particles with cracks 2, if they are crushed using an impact crusher, The particles that generated microcracks throughout the grains were not spherical, and the embrittlement caused by the gallium alloy 3 Since the material is crushed in a state with countless cracks2, it is easy to create fine particles of various shapes. Moreover, non-spherical particles have a larger surface area than spherical particles, The number of cracks that form inside the particles from the surface also increases proportionally. This results in more voids between the particles, making the material bulky.

[0020] Also, a gallium alloy 3 containing at least one of indium and tin in gallium is used as an aluminum alloy. When the gallium alloy 3 is heated, a heating / cooling device 11 is used to heat the gallium alloy 3 to a temperature of 6000 K. A step of repeating the phase transition of the gallium alloy 3 by heating and cooling within a range of 00°C to -30°C. When adding, the gallium alloy 3 can go back and forth between the solid and liquid phases, To achieve this with very little energy, we need to use the melting point of gallium alloy 3 as a boundary, for example. Repeated heating and cooling of + / - 10°C can cause the phase transition of gallium alloy 3. For this purpose, a Peltier element can be used as the heating / cooling device 11. Alternatively, heating and cooling may be performed by simply using both a heating device and a cooling device. The phase transition of the aluminum alloy 3 causes a change in the phase of the aluminum alloy 1. Of course, the melting point of the gallium alloy 3 is the boundary. For heating and cooling at -10°C, the greater the temperature difference, the greater the impact on aluminum 1. The speed at which crack 2 occurs increases, but the energy required also increases. The temperature range to be set depends on the production plan of the hydrogen generating material of the present invention. The product obtained through this process is impact-pulverized to remove all of the aluminum fine particles. A hydrogen generating material obtained by a manufacturing method in which fine cracks 2 are formed in a body, In the material, the non-spherical fine particles account for all or at least half by weight, and the gallium and the precursor At least the gallium of the indium and the tin is held in the cracks 2. A characteristic hydrogen generating material is obtained. [Industrial Applicability]

[0021] Gallium alloy 3 in which at least one of indium and tin is added to gallium instead of gallium; Then, aluminum 1 was immersed in gallium alloy 3 without any problems even at room temperature below the melting point of gallium. A hydrogen generating material can be obtained by the above-mentioned manufacturing method. can be produced in large quantities. [Explanation of symbols]

[0022] 1. Aluminum 2. Cracks 3 Gallium alloy 4 containers 5. Ball mill grinder 6 Lid 7 ceramic balls 8. Hydrogen generating material particles 9 motors 10. Anoxic chamber 11 Heating and cooling device

Claims

1. A hydrogen generating material is obtained by a manufacturing method in which aluminum is reacted with gallium and then impact-pulverized in a reaction chamber that is shielded from oxygen, thereby forming fine cracks throughout the aluminum fine particles, wherein the non-spherical fine particles account for all or at least half by weight of the hydrogen generating material, and a trace amount of gallium is left behind in the cracks. Instead of the gallium-treated one, The gallium is reacted with a gallium alloy to which at least one of indium and tin is added, Instead of retaining the gallium, A hydrogen generating material characterized in that it contains at least gallium among the gallium, the indium, and the tin.

2. 2. The hydrogen generating material according to claim 1, wherein the gallium, indium, and tin The weight ratio of the gallium alloy is: In the case of an alloy of gallium, indium and tin, Gallium:Indium:Tin = (50-96): (2-50): (2-50), In the case of an alloy of gallium and indium, Gallium:Indium = (50-96): (4-50), In the case of an alloy of gallium and tin, Gallium:Indium = (50-96): (4-50) A hydrogen generating material characterized by being within the range.

3. A method for producing a hydrogen generating material in which fine cracks are formed throughout fine particles obtained by pulverizing aluminum, the method comprising the steps of: impact-pulverizing aluminum treated with gallium in a reaction chamber that is isolated from oxygen; and obtaining non-spherical fine particles in all or at least half by weight of the hydrogen generating material; Instead of the gallium-treated one, A method for producing a hydrogen generating material is characterized in that the gallium is reacted with a gallium alloy to which at least one of indium and tin is added.

4. 4. The method for producing a hydrogen generating material according to claim 3, When a gallium alloy containing at least one of indium and tin is applied to aluminum, a step of repeatedly heating and cooling the gallium alloy in a range of 600°C to -30°C, which includes the melting point of the gallium alloy, by using a heating and cooling device; A step of adding a heating device and heating the gallium alloy within a range of room temperature to 600°C; adding an ultrasonic generator and applying ultrasonic waves to the gallium alloy; A method for producing a hydrogen generating material, comprising the steps of:

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