JP2010017700A - Method for using waste material of lightweight structural material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for using a waste material of a lightweight structural material without costing much. <P>SOLUTION: The method for using the waste material of a lightweight alloy includes: using ingots or fragments of a lightweight alloy waste which is primarily used as a lightweight structure material; putting the ingots or fragments in a high pressure container 2; breaking the oxide film on the surface by laser under hydrogen pressure to bring the alloy surface into contact with hydrogen; performing hydrogen occlusion by hydrogenation reaction to produce pulverized hydride particles; and thereafter, either packing a filter-type bag with the hydride particles or pressure-bonding the hydride particles or solidifying the hydride particles with a binder to use the particles as a functional material for metal reaction (hydrolysis) or ionization reaction (electrode active material) for secondary use in a siphon type or battery type hydrogen generation apparatus. After that, the remaining hydroxides are recovered for the third use. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to the effective use of waste materials of lightweight structural materials alloyed from a plurality of metals mainly composed of magnesium (Mg), which has the same strength as iron and the light weight of plastics. The cost of manufacturing lightweight structural materials can be reduced by increasing the utility value from the use of waste materials.

High-performance lightweight alloys such as duralumin have been useful in the industry, but secondary use, such as recycling of waste materials, has problems in recycling such as environmental impact.
On the other hand, lightweight alloys mainly using magnesium have recently found new functionality and are widely provided as structural materials. The secondary use of magnesium waste is also attracting attention because of its superiority that it is environmentally friendly as well as recycled.

Lightweight alloy wastes composed primarily of magnesium are generally convenient because they can be regenerated with much less power than aluminum alloys. However, since the power is input with a small amount, the regeneration cost is also increased.

On the other hand, in addition to hydrogenation devices, in the fields of hydrogen generation and magnesium batteries using metal reactions and ionization reactions of hydrogenated magnesium, they are provided as materials for next-generation energy.

As such literature materials, the following are known.
Patent Publication 2003-229134 Patent Publication 2006-97061 International Patent Publication WO / 2008/015844 International Patent Publication WO / 2006/011620

A fuel cell having a negative electrode formed by fixing these hydrogen storage materials to a conductive substrate, a positive electrode composed of an air electrode and an electrolyte, and using a metal hydride as a fuel source, or a reaction electrode having a metal as a reactant, In both cases of hydrogen generation using the oxidation reaction at the potential difference between the counter electrodes composed of a metal having a standard electrode potential nobler than that of the metal, from the metal distribution of the lightweight alloy as a structural material, from the hydrogen storage alloy species It is excluded and there is no use of hydrogen for waste materials.

In addition, in the siphon type or battery type hydrogen generation of magnesium or hydrogenated magnesium, the metal storage as a lightweight structural material is excluded from the hydrogen storage alloy species, and the waste material is not hydrogenated.

Since most of the metals used as lightweight structural materials are converted into hydroxides by the oxidation reaction in siphon-type or battery-type hydrogen generation, it is convenient because the waste materials can be used as they are for tertiary use. For example, in the case of a magnesium alloy after secondary use, the other metals included are often hydroxides and can be used tertiary for various industrial raw materials / catalysts, soil / seawater improvement materials, heat storage materials, etc. There is no adverse effect.

Also in the hydride production apparatus, the ultra-high temperature hydrogenation method using the laser of the temperature control unit uses particles pulverized in advance for the purpose of producing a hydrogen storage alloy. For this reason, hydrogenation using a lump or debris of a lightweight structural material of a new alloy type is not described without a verification example. In the method of repeating the degassing and hydrogenation pressure of the conventional method, there are also problems that are expensive and troublesome.

Therefore, the present invention is an object of the prior art, even in an alloy containing a metal as a lightweight structural material, in the siphon-type or battery-type hydrogen generation of the conventional apparatus without cost and labor after the primary use. The secondary use is efficient, and the tertiary use is possible at low cost and without any effort even after use. Another object of the present invention is to provide safe and clean storage and transportation of energy by using electric energy from natural or renewable energy once for metal production from the viewpoint of global environmental conservation.

Therefore, the present invention can reduce the manufacturing cost of the lightweight alloy by using the secondary and tertiary usages at a low cost even in the case of the alloy including and allocated the metal as the lightweight structural material, which is a problem of the prior art. It is to become. Another objective is to reduce the burden on the global environment by providing safe and clean energy storage and transport.

In the present invention, a lump or fragment of a lightweight alloy waste material primarily used as a lightweight structural material is placed in a high-pressure vessel, and the surface oxide film is destroyed by a laser under hydrogen pressure to bring the alloy surface into contact with hydrogen. After hydride particles are pulverized by the expansion of metal crystals by occlusion of hydrogen by the hydrogenation reaction, the hydride particles are packed in a filter bag, or packed with a pressure bonding or binder, Use as a functional material for metal reaction (hydrolysis) or ionization reaction (electrode active material) as a lightweight alloy waste material that is secondarily used in a siphon-type or battery-type hydrogen generator and then thirdarily used the remaining hydroxide. It is characterized by.

It is possible to reduce the cost of manufacturing lightweight structural materials by using a single part without any effort. In addition, there is an advantage that hydrogen energy can be safely used with a material that is harmless to the human body existing in nature. In the next generation society, a complete zero emission cycle will be possible, there will be no resource depletion, and it will be effective in preventing global warming.

The magnesium alloy composition of the existing lightweight alloy material is mostly magnesium (Mg), aluminum (Al), zinc (Zu), iron (Fe), copper (Cu), silicon (Si), nickel (Ni), It is an alloy mixed with a small amount of multiple metals such as beryllium (Be), put a lump or debris of waste material in a pressure vessel pressurized with hydrogen, and remove the oxide film on the surface of the alloy under hydrogen pressure, By directly contacting the alloy with hydrogen, the hydrogenation reaction is self-propelled and hydrogenation (hydrogen storage) can be easily performed.

The hydrogenation includes one or a plurality of processing vessel means provided with a flange and a jacket and a temperature control unit in a high-pressure vessel, hydrogen filling means in which a degassing device and a hydrogen storage / release device are arranged in the high-pressure vessel, and the high-pressure vessel And a heating / cooling means in which a heating device and a cooling device are arranged in the hydrogen storage / release device, respectively, and a processing apparatus comprising an electronic control means for automatically controlling the processing container means, the hydrogen filling means, and the heating / cooling means.

In addition to the laser radiation plug, a heating wire, a heating plug, etc. are selected and provided in the temperature control section of this device, and one end is heated at a high temperature by the material and ignited, thereby causing a hydrogenation reaction. A metal hydride fine powder containing metal crystals in the nanometer range can be easily obtained at low cost by a reaction utilizing self-heating.

Even in an alloy lump of lightweight structural material, it is possible to remove the oxide film on the surface by irradiation heating of ultra high temperature of 4000 ° C or more peculiar to laser, and perform hydrogenation (hydrogen occlusion) reaction by bringing hydrogen into contact with the alloy directly. Due to the hydrogen embrittlement effect that the alloy crystal expands, hydrogenated alloy particles can be easily obtained. Since this hydrogenated magnesium alloy has a high magnesium mixing rate, it can occlude 7 wt% or more of its own weight.

This hydrogenated magnesium alloy is transformed into magnesium hydroxide by injecting water or an aqueous solution into the hydrogen generation container in the hydrogen generator, so that the magnesium gas reacts with the hydrogen gas generated by the hydrolysis of magnesium and the magnesium reacts. As a result, hydrogen atoms fixed between the metal crystals are released, and a large amount of hydrogen gas can be obtained from both of the hydrogen gas generated by bonding two atoms together to generate hydrogen molecules.

In addition, when the hydride particles are packed in a filter bag and used as a siphon-type hydrogen generation device, two liquid containers are provided with a drop through a pipe, and the liquid below Hydrogen generation is automatically controlled by pushing up water or an aqueous solution (or electrolytic solution) into the upper liquid container using the siphon phenomenon caused by the pressure of hydrogen gas generated in the container.

In this case, water or an aqueous solution (or electrolyte) and hydrogen gas pass through the filter, and magnesium hydroxide is kept inside so that it can be filtered. If they are pulled up together, the labor of collection becomes easy.

In addition, this filter bag is used to pack the hydride directly into bath water, washing water, aquaculture water, etc., so that the hydrogen gas generated by hydrolysis is dissolved directly in water, reducing the potential and weak alkalinity. It can be used as a material for producing functional water given a Ph value.

In addition, in the case of a battery-type hydrogen generator, the produced magnesium alloy hydride particles are used as an active material for the negative electrode of the battery element, and the current generated by the battery element is controlled by the load device. The ionization and metal reaction of the active material can be controlled, and hydride fixed between crystal of metal and hydrogen gas from hydrolysis can be generated.

In addition, since the metal species to be hydrogenated include a lot of metals, the metal species are not limited to the metal species described, and many metals are also packed as hydride particles in a filter bag. In addition, the remaining hydroxide after being secondarily used in a siphon-type or battery-type hydrogen generator as a functional material for metal reaction (hydrolysis) or ionization reaction (electrode active material) after being pressed or bonded with a binder Can be recovered for tertiary use.

In addition, for the purpose of hydrogen purification, in the case of a hydrogen purification membrane, the hydrogenated particles of magnesium alloy can be molded into a pipe shape or a sheet shape, activated in advance, and then attached to the apparatus. Alternatively, it can be applied to a device for selectively adsorbing methane gas or the like for purification and storage.

Further, in the case of an apparatus that recovers hydrogenation exotherm and hydrogen release endotherm for the purpose of heat pump, the magnesium alloy hydrogenated particles are mixed with a binder and solidified, activated in advance, and then in the apparatus or in the apparatus. It can be installed inside or outside the pipe, or it can easily be solid-bonded inside or outside the pipe inside the device or inside the groove of the corrugated plate, requiring activation after installation on a large device. It does not need to be a container that is robust to pressure.

The magnesium alloy hydrogenated particles can be easily formed into a thin film by using water or an organic solvent for water-soluble or organic solvent-soluble polymer resins. In an apparatus that operates in a relatively low temperature range, for example, an emulsion type in which an aliphatic polyester resin or polyolefin resin, which is a water-soluble organic polymer resin obtained by polymerizing lactic acid by a chemical synthesis method, is dispersed in water is used. In addition, general organic polymer resins can also be used.

Specifically, when cracks occur on the surface of the film as it is installed in the device and the operation time elapses, the polymer function is self-healing due to low temperature thermoplasticity due to heat generation during operation, etc. it can.

In the application of these functionalities, in the case of magnesium alloy hydrogenated particles, even in the case of large hydrogen storage containers such as hydrogen containers and hydrogen storage facilities for the purpose of hydrogen storage, the same applies to various kinds of coated granular metals. When the hydrogenated particles and the solidified mixture of the binder are packed into the inside or outside of the pipe in the apparatus and installed, the coated magnesium alloy hydrogenated particles are activated in advance and then the binder. And then paste it into an organic solvent and solidify it and pack it inside or outside the pipe in the device, or if you paste it into the groove of the corrugated plate, Therefore, it is not necessary for the large device to be a container strong against pressure.

In addition, when a plastic polymer resin is used as the coating material and it is attached to the electrode foil of a battery such as a nickel metal hydride battery or a lithium metal battery, the active material is pulverized from the expansion and contraction due to insertion and extraction of hydrogen and lithium, and drops off. If a battery element composed of a negative electrode, a positive electrode, and a separation membrane is joined and covered and integrated with an insulating film, the functionality is enhanced and the battery life can be extended.

Magnesium alloy hydrogenated particles are known to be unable to sustain an oxidation reaction in normal temperature water, but if they are heated to 140 ° C or higher in a high-pressure environment, they can undergo a free-running oxidation reaction with water. In general, nigra (magnesium chloride / MgCl), which is useful for the human body, is used as an aqueous solution (electrolytic solution), and when exhaust heat or the like is used as a heating source, hydrolysis can be performed in a normal temperature and normal pressure range.

This reaction can be generated from a self-discharge phenomenon caused by a short circuit of a local battery of particles if a battery element is formed in the container using this phenomenon. The structure of the battery element is, for example, by mounting magnesium alloy hydride particles on the negative electrode active material, magnesium chloride (MgCl) aqueous solution (electrolyte) as the electrolyte, polymer solid electrolyte, and anode diffusion layer as Ni, Ti-based metals, alloys, powders of metal compounds, powdered activated carbon, graphite, and magnesium alloy hydrogenated fine powder mixed with fluororesin are attached to the electrode, and oxygen, nickel hydroxide, etc. If a battery having an active material is constructed, a plurality of ions including polyvalent ions can be received by a diffusion layer that can increase the unit area and promote the interfacial reaction, and function as a magnesium battery that also serves as a hydrolysis with reduced polarization resistance. it can.

If the battery is not a sealed battery, the electrolyte must be included in combination with a solid polymer electrolyte and non-woven fabric with a capillary action function in addition to the polymer solid electrolyte. Then, the hydrogen gas generated in the hydrogen generation container can be sent to the hydrogen consumer without flowing out from the open portion of the anode surface, and the container can be prevented from bursting. This can also be applied to the field of small batteries for portable devices such as plate batteries and button batteries.

Further, even when this is a sealed battery, the anode is mixed with active materials such as Ni, Ti-based metals, alloys, metal compound powders, and catalysts that can accept hydrogen and magnesium alloy ions. When the element is configured, the battery can function as a battery having a reduced polarization resistance by enlarging a unit area to promote an interface reaction and receiving a plurality of ions including polyvalent ions.

In addition, for example, when ionization of the hydrogenated particles of the magnesium alloy of the negative electrode is increased or decreased by energizing the load device with the electric power generated by the battery element of the container and changing the amount of current flowing through the load, The amount by which the metal crystals are modified into hydroxide from the surface side of the compound is also proportional. At this time, hydrogen atoms that have lost their fixing sites between the metal crystals generate hydrogen gas because two of the atoms combine to form hydrogen molecules. The amount of the generated hydrogen can be controlled by the electric current from the reaction of the load current amount.

In addition, when the cells of the container and the battery element are laminated, the hydrogen generation can be easily controlled even in a field using a hydrogen demanding apparatus having a high voltage and a large fluctuation in hydrogen consumption, such as a fuel cell vehicle.

When the container is configured as a secondary battery (charge / discharge) using oxygen (O) as an active material, the magnesium alloy powder is coated with a plastic polymer or metal and solidly mounted on the negative electrode, Alkaline aqueous solution or non-aqueous solution and the like, and the anode diffusion layer accepts each ion of hydrogen and magnesium alloy, to avoid polarization resistance, Ni, Ti-based metals, alloys, powders of metal compounds, powdered activated carbon and When a functional substance obtained by mixing graphite and a catalyst with a fluororesin is attached, charging / discharging can be performed.

In the case of this battery configuration, since the anode uses oxygen in the atmosphere as an active material, the amount of electricity that can be discharged is not limited on the positive electrode side, the electric capacity can be dramatically increased, and both electricity and hydrogen can be used for charging. Can be supplied and charged.

In addition to oxygen, thionyl chloride, and nickel hydroxide, the anode active material is a metal oxide or a transition metal oxide such as lithium cobaltate (LiCoO2), lithium nickelate (LiNiO2), or lithium manganate (LiMn2O4). When various materials are used for the electrolyte and the negative electrode functional material and the battery element is configured in the container, a composite battery avoiding polarization resistance due to a plurality of ions (hydrogen ions, metal ions, lithium ions, etc.) can be obtained.

Referring to the embodiment of FIG. 1, it is an overall system diagram of a magnesium alloy hydrogenation treatment apparatus 1, which includes a high-pressure vessel 2, a deaeration device 5, a hydrogen storage / release device 6, and a hydrogen or inert gas supply device 9. In addition to the heating device 7 and the cooling device 8, the solenoid valve 12, 13, 13 b, 14, 14 b, the pressure reducing control valve 11, the heat medium pump 18, 19, and a control device including each sensor, metal reduction, or metal Hydrogenation pulverization, activation of functional bodies, hydrogen filling of hydrogen storage containers, and the like are performed.

The high-pressure vessel 2 is a vessel corresponding to a high pressure of 30 kg / cm ² or more, and a heat medium jacket 4, a flange, a heating wire, an electric heating plug, a laser radiation plug and the like as needed are attached around the side surface. A temperature control unit is provided, and a flange lid 3 for opening and closing a metal, a hydrogen storage container or the like is provided so that the flange lid 3 can be opened and closed hydraulically or electrically.

In addition, the jacket 4 has the contents of the high-pressure vessel 2 by electronic control of the heating valves 7 and 14b connected to the heating medium and the cooling medium 8 connected by piping and the heating medium and the cooling medium to the piping. For example, the object is heated to about 80 ° C. in the deaeration process, and cooled to about 5 ° C. in the hydrogen pressurization process.

The gas socket is electronically controlled by solenoid valves 13 and 13b connected to the deaeration system 16 connected through piping and the degassing system 16 from the hydrogen storage / release device 6 and the piping of the hydrogen or inert gas system 17. As a result, the contents of the high-pressure vessel 2 are evacuated to about 3 Toor by the vacuum pump of the deaeration device 5 in the degassing process, and 30 kg / cm ² by the hydrogen storage / release device 6 in the hydrogen pressurization process. The above hydrogen pressurization is performed, and if it is metal reduction, unnecessary gas is diffused to the outside. The high-pressure vessel 2 configured as described above is operated with a single unit or a plurality of units.

In the hydrogen storage / release device 6, the heating valves 7 and 14b connected to the heating medium and the cooling medium 8 connected to the heating medium nozzles at both ends of the laminate are electronically controlled. Thus, if the contents of the high-pressure vessel 2 require hydrogen pressurization, the hydrogen storage material mounted in the apparatus is heated to about 80 ° C. and hydrogen pressurization is performed at a hydrogen release pressure of 30 kg / cm ² or more. If the contents of the high-pressure vessel 2 release hydrogen, the hydrogen storage material is cooled to about 5 ° C. to store hydrogen.

The hydrogen or inert gas replenishing device 9 replenishes hydrogen to the hydrogen storage / release device 6 or hydrogen or inert gas to the high-pressure vessel 2, and the high-pressure hydrogen or inert gas is supplied via the pressure regulating valve 11. Gas cylinders are arranged.

In the electronic control, power sources such as a heat medium pump, a solenoid valve, and a hydraulic equipment pump are electronically controlled as appropriate according to sensor values such as temperature and pressure and preset values.

By configuring the device in this way, magnesium alloy waste material is placed in a high-pressure vessel, high-pressure hydrogen is introduced, and the oxide film on the magnesium alloy waste material surface is destroyed by laser irradiation, so that the alloy and hydrogen are removed. It can be pulverized from the expansion of the metal crystal of the magnesium alloy waste material by utilizing the hydrogenation (hydrogen storage) reaction, and particularly a fine metal single crystal powder can be easily obtained. Alternatively, the metal can be reduced by a method of gasifying and cooling with a laser radiation plug of the processing apparatus. For metal reduction, for example, an electrode is provided in a high-pressure vessel, coarse particles such as magnesium oxide are put, laser irradiation is performed by a laser radiation plug, and magnesium oxide is heated to high temperature to gasify, and oxygen is diffused to the outside air to form magnesium. This gas can be smelted by reducing the metal with an electrode provided inside.

In this case, the laser source of the laser radiating plug is necessary depending on the light collected directly by the lens or the reflector, or by the electric power generated using light conversion, wind power conversion, biomass fuel, etc. Effective use of renewable energy is also realized by amplifying and using those that generate electromagnetic waves of wavelengths.

The main types of existing lightweight alloys are shown below.
The verification of the metal reaction (hydrolysis) and ionization reaction (electrode active material) of the magnesium hydride alloy will be described using the waste material of the magnesium alloy “AM50A” of this average composition.

The shortest free-running reaction experiment of hydrolysis of naturally occurring solutes with aqueous solution was tried. Two types of samples were used: Sample 1: Magnesium hydride alloy particles having a particle size of 200 μm or more and 1 g, Sample 2: Magnesium hydride alloy particles having a particle size of 50 μm or less, 1 g.

Three kinds of aqueous solutions were used: aqueous solution 1: water (H 2 O), aqueous solution 2: citric acid (C 6 H 8 O 7) 8% aqueous solution, aqueous solution 3: bittern (hexahydrate magnesium chloride MgCl 2 · 6H 2 O) 5% aqueous solution.

The experimental method was started by pouring 5 cc of each of three types of normal temperature (20 ° C.) aqueous solutions into a sample in a test tube. When the free-running reaction was slow, observation and measurement were performed while gradually heating the aqueous solution.

In the case of Sample 1, the aqueous solution 1: water (H 2 O) did not react at all, and a slight bubble was confirmed on the particle surface at 90 ° C. under heating. Aqueous solution 2: Citric acid (C6H8O7) 8% aqueous solution reacted vigorously and the reaction was completed in less than 2 minutes as the temperature rose. In aqueous solution 3: bittern (hexahydrate magnesium chloride MgCl 2 · 6H 2 O), the reaction was slow, and the reaction was accelerated with heating, and an increase in bubbles was confirmed at 90 ° C.

In the case of Sample 2, bubbles were confirmed in the aqueous solution 1: water (H 2 O), and the rise of bubbles was confirmed at 90 ° C. under heating. Aqueous solution 2: Citric acid (C6H8O7) 8% aqueous solution reacted vigorously and the reaction was completed in less than 1.5 minutes as the temperature rose. Aqueous solution 3: The reaction was fast, and it was confirmed that the bubbles increased sharply at 90 ° C. while the temperature rose due to self-heating with time.

The final collection amount of hydrogen gas was the same for each aqueous solution, and was Sample 1: 800 cc (magnesium weight ratio 8 wt%) and Sample 2: 1400 cc (magnesium weight ratio 14 wt%).

Next, an electromotive force experiment was attempted using a battery element in which air (oxygen) was used as the anode active material and magnesium hydride alloy particles were used as the anode. Disassemble the commercially available magnesium battery, remove the magnesium attached to the negative electrode, dissolve the magnesium hydride alloy powder and the water-soluble plastic polymer with an organic solvent, connect the electrode size frame and compress it. It was heated and solid bonded to the electrode foil.

Other separators, positive electrode current collectors and the like were assembled using single cells of product members, and a 5% aqueous solution of bittern (hexahydrate magnesium chloride MgCl 2 · 6H 2 O) was used as the electrolyte. In the positive electrode current collector of the product, a powdered activated carbon, graphite, a catalyst, etc. mixed with a fluororesin is applied to a copper foil and fired to form a net.

The reaction formula of the experiment and the measured value of the electromotive voltage are as follows: positive reaction formula: 2Mg → 2Mg ²⁺ + 4e ⁻ , negative reaction formula: O ₂ + 2H ₂ O + 4e ⁻ → 4OH ⁻ , total reaction formula: 2Mg + O ₂ + 2H ₂ O → 2Mg (OH ) ₂ ↓, the initial electromotive voltage is 2.7V.

It has been found that when magnesium hydride alloy particles are used for the negative electrode, a battery comparable to a lithium battery can be obtained. The theoretical electromotive force of air and magnesium is 2.7 V, but at the same time, it gradually decreases due to the polarization resistance caused by a plurality of ions due to the hydrolysis reaction (reaction formula: MgH2 + 2H ₂ O → Mg ²⁺ + 2OH ⁻ + 2H ₂ ↑). .

For this verification, priority was given to the hydrolysis reaction using an aqueous solution of a chlorinated compound as the electrolyte for the primary battery. However, when adopting a secondary battery using magnesium hydride alloy particles, the electrolyte was hydroxylated. An alkaline electrolyte such as potassium (KOH) or an organic solvent may be used.

The measured value of the hydrogen gas generation amount was about 650 cc / g (magnesium weight ratio 6 wt%). Since the amount of electricity and the reduction amount of magnesium are in a proportional relationship, Table 2 shows the numerical values obtained by using Faraday's law to calculate the relationship between the amount of electricity and the amount of waste magnesium alloy, and the relationship between the negative electrode area and current. A graph is shown.
Faraday's law is obtained by the theoretical quantity of electricity Q (unit is C or As) Q = Fmn / M. F is the Faraday constant, m is the mass of the active material, M is the formula weight of the active material, n is the number of electrons involved in the reaction, and the amount of electricity is proportional to the mass of the active material.

This will be described with reference to FIGS. Fig. 2 shows that a magnesium alloy or magnesium hydride alloy particles are packed into a bag 50 like a sausage by a crimping part 52 packed inside using a filter tube and crimped at both ends with a heating roller. It has been. FIG. 3 shows a siphon type hydrogen generator 100.

The siphon 101 has a reaction vessel 129 in the lower portion, a pack 50 in which particles of magnesium alloy or magnesium hydride alloy are placed in a container inside the vessel, and a liquid vessel 128 in the upper portion through a communication pipe. An aqueous solution (electrolytic solution) 121 is placed inside. A plurality of siphons are provided in parallel to form a siphon-type hydrogen generator 100.

In addition, a check valve 137 is provided in the communication pipe between the liquid container 128 and the reaction container 129 inside each siphon, and a check valve 138 is provided in the communication pipe between the bottom of the reaction container 129 and the top of the liquid container 128. In the upper part of the reaction vessel 129, a hydrogen pipe 112 connected to the hydrogen demand body 130 is provided, and a plurality of 101a, 101b, 101c similar to the siphon 101 are joined in parallel. The hydrogen demand body 130 indicates any equipment that requires hydrogen gas, such as a hydrogen purification device, a functional water production device, a hydrogen pump, a hydrogen burner, a hydrogen engine, and a fuel cell.

In the case of a magnesium alloy or a magnesium hydride alloy, when the aqueous solution (electrolyte) 121 is magnesium chloride (MgCl), no harmful substances are generated by the reaction, and the hydroxide is not mud but remains as coarse particles. Alternatively, other known aqueous solutions (electrolytic solutions) can be selected and used, and the reaction can be accelerated by heating with the exhaust heat of the hydrogen consumer.

In addition, magnesium hydride alloy generates a large amount of hydrogen gas from both hydrolysis and hydride, so the amount of water produced and recovered by the hydrogen consumer is also considered to be reduced to the atmosphere. Since an amount of water more than necessary for hydrolysis can be secured, it is not necessary to replenish water from the outside when the produced water is circulated again into the liquid container. In other words, when a moving body such as an airplane or an automobile is used, it is not necessary to mount a large amount of water at the time of departure, which is convenient as a lightweight device.

A series of operations in which the siphon type hydrogen generator is configured in this way is to stop the reaction by pushing up (outflowing) the aqueous solution (electrolyte) 121 with the pressure of hydrogen gas generated using the siphon phenomenon. When the hydrogen gas is used, the hydrogen consumer 130 consumes the generated hydrogen gas, and the pressure drops, causing the aqueous solution (electrolyte) 121 to fall (inflow), and the aqueous solution (electrolyte) 121 and the magnesium alloy or magnesium hydride. The hydrolysis reaction with the alloy is started, and hydrogen generation is controlled automatically without the need for an electronic control device.

In addition, when the reaction is completed, the remaining hydroxide can be drawn out together with the soot, and the hydroxide trapped inside the pack can be recovered, so that it does not take time for tertiary use.

Although the present invention has been described, the present invention is not limited to the above embodiment, and can be improved or modified within the scope of the purpose of the improvement or the idea of the present invention.

As described above, by using the secondary and tertiary uses without cost, it is possible to reduce the cost of manufacturing the lightweight structural material. In addition, there is an advantage that it can be stored and transported as a next-generation energy source by converting safe natural energy into a thing with an inexhaustible material harmless to the human body existing in nature. In addition, a clean zero emission cycle is possible, there is no depletion of resources, and it is effective in preventing global warming.

1 shows an overall conceptual diagram of one embodiment of the present invention. (Example 1) 1 illustrates one embodiment of the present invention. (Example 3)

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Processing apparatus 2 High pressure vessel 5 Deaeration apparatus 6 Hydrogen storage-release apparatus 7 Heating apparatus 50 Pack 52 Crimp part 100 Hydrogen generator 128 Liquid container 129 Reaction container

Claims (7)

Using a lump or debris of lightweight alloy waste primarily used as a lightweight structural material, put it in a high-pressure vessel, destroy the oxide film on the surface with a laser under hydrogen pressure, contact the alloy surface with hydrogen, and hydrogen by a hydrogenation reaction After pulverized hydride particles are produced by occlusion, the hydride particles are packed in a filter bag or packed with a pressure bonding or binding agent to form a metal reaction (hydrolysis) or ionization reaction. As a functional material of (electrode active material), after secondary use with a siphon-type or battery-type hydrogen generator, the remaining hydroxide is recovered and used as a third-use lightweight alloy waste material. The lightweight alloy material is mainly magnesium (Mg), aluminum (Al), zinc (Zu), iron (Fe), copper (Cu), silicon (Si), nickel (Ni), beryllium (Be), etc. The lightweight alloy waste material according to claim 1, wherein the light alloy waste material is a material alloyed with one or more of a plurality of types, and is a lump or shard or powder or powder solidified. In the siphon type hydrogen generation, two liquid containers having a drop through a pipe are provided, and light alloy or hydride particles are placed in the lower liquid container, and the pressure of the hydrogen gas generated in the container The waste material of the secondary alloy for secondary use according to claim 1, wherein water or an aqueous solution (or electrolytic solution) is pushed up into the upper liquid container by utilizing a siphon phenomenon caused by the above. In the battery-type hydrogen generation, light-weight alloy or hydride particles are used as an active material for the negative electrode of the battery element, and the current generated by the battery element is controlled by a load device to ionize the functional substance of the negative electrode and the metal The light-weight alloy for secondary use according to claim 1, 2 or 3, wherein the reaction is controlled to control the amount of hydrogen gas generated from hydrolysis and hydride fixed between metal crystals. Waste material. The hydrogenation reaction includes one or a plurality of processing vessel means provided with a flange and a jacket and a temperature control unit in a pressure vessel, hydrogen filling means in which a deaeration device and a hydrogen storage / release device are arranged in the pressure vessel, and the pressure resistance It is hydrogenated by a processing device comprising a heating / cooling means in which a heating device and a cooling device are arranged in a container and a hydrogen storage / release device, respectively, and an electronic control means for automatically controlling the processing container means, the hydrogen filling means, and the heating / cooling means. The hydride according to claim 1, 2, 3, 4 characterized by the above-mentioned. The hydride particles according to any one of claims 1, 2, 3, 4, and 5, wherein the hydride particles are used for any of the following purposes (1) to (6).
(1) A molded product, a coating material, a coating material, or an injecting agent, which is used as a catalyst for deodorization, environmental improvement, etc., and in which hydride particles are dispersed.
(2) For the purpose of producing functional water, the hydride particles are filled in a utilization device for the purposes of cleaning, medical treatment, beauty, aquaculture, and the like.
(3) For the purpose of storing and transporting natural energy, hydride particles are stored in a sealed container or bag in an inert and sealed manner.
(4) Substances used for purification or storage (adsorption / storage) or heat pump or hydrogen pressurization, etc.
(5) The purpose of the electrode of the secondary battery, which is formed integrally by joining battery elements with electrodes using functional substances.
(6) An object of a fuel cell or a water electrolysis apparatus, which is used for a battery element such as a membrane layer or an electrode of an MEA (membrane-electrode assembly). The hydride particles after secondary use are tertiaryly used as hydroxides as various industrial raw materials / catalysts, soil / seawater improvement materials, heat storage materials, and gastrointestinal drugs. 2. Hydride particles according to 2, 3, 4, 5, 6.