JP5124728B2 - Hydrogen generator, laser reduction device, energy conversion device, hydrogen generation method and power generation system - Google Patents

Description

  The present invention relates to a technique for recovering reaction energy from elements such as sodium, potassium, magnesium, aluminum, calcium, and zinc and generating hydrogen gas, and more particularly, hydrogen that reduces water to hydrogen using a metal. The present invention relates to a generation apparatus, and a laser reduction, energy conversion method, hydrogen generation, and power generation system that reduce a generated metal oxide or chemical substance using a laser.

  Hydrogen gas generates water even when it is oxidized by an oxidant, so it is attracting attention as clean combustion for fuel in fuel cells. In recent years, it has become a core energy infrastructure from the viewpoint of depletion of fossil combustion and global warming. It is necessary to switch the base from fossil fuel to clean energy. Until now, hydrogen has been generated by electrolysis of water, filled into a high-pressure vessel, and then transported to various places for use. For this reason, the weight increases in transportation, and since it is flammable, it requires careful handling, and it is not sufficient from the viewpoint of long-term storage.

  For this reason, it is considered that an apparatus and a method for generating hydrogen gas simply and with clean energy will be required in the future. In addition, hydrogen gas generation is not a method that uses a large amount of fossil fuels such as electrolysis of water, but generates hydrogen gas while making more effective use of renewable energy. It is thought that technology to make it necessary. Further, it is preferable to reuse the raw materials in the hydrogen generator and the method therefor as much as possible.

Conventionally, a method for thermally reducing oxide resources such as magnesium-containing oxides (magnesium oxide, dolomite) using an arc discharge at a high temperature of about 1000 ° C. is known. It is considered that hydrogen gas can be obtained even when added. However, considering that the purpose of obtaining hydrogen gas is to generate clean energy for reducing CO _{2 and the} like, the power for generating arc discharge is considered to cause an increase in environmental load in many cases. .

  Various hydrogen generators and methods therefor have been proposed. For example, in Japanese Patent Application Laid-Open No. 2003-313001 (Patent Document 1), in a hydrogen generation method for generating hydrogen by hydrolyzing a hydride within a sealable main body container, at least a part of the hydride and water is used. A hydrogen generation method in which water is separated by a member formed of a water-repellent water-permeable water-vapor-permeable material and hydrogen is generated by reacting water molecules permeating the water-repellent water-vapor-permeable material with a hydride. It is disclosed.

  Japanese Patent Laid-Open No. 2003-226502 (Patent Document 2) discloses a container for storing a hydrogen generating fuel made of aluminum and an alkali metal or an alkaline earth metal, and heating the hydrogen generating fuel stored in the container. There is disclosed a hydrogen generating apparatus that includes a heating means for melting and alloying and a water supply means for supplying water to the hydrogen generating fuel in the container, and recovering the hydrogen generated by the hydrogen recovery means.

  Japanese Patent Laid-Open No. 2002-69558 (Patent Document 3) uses a hydrogen generating fuel made of an alloy of aluminum and an alkali metal or an alkaline earth metal, and includes a cooling means for cooling the inside of the container. An apparatus and a hydrogen generation method using the apparatus are disclosed.

  Further, in JP-A-8-109001 (Patent Document 4), a reaction metal body is melted through a heat source, the molten molten reaction metal body is stored at the bottom of the container, and water is added to the molten reaction metal body. A hydrogen generation method is disclosed in which a thermochemical reaction is supplied to generate hydrogen, the obtained hydrogen is led out, and a metal oxide body is discharged out of the container through a discharge means.

  Japanese Patent Laid-Open No. 8-59201 (Patent Document 5) and Japanese Patent Laid-Open No. 7-109102 (Patent Document 6) use a reaction metal body that is provided in a container and that undergoes an electrothermal chemical reaction with water. A hydrogen generation method and an apparatus therefor are disclosed in which water is supplied from the upper part of the gas generator and hydrogen gas is generated by an electrothermal chemical reaction between a reaction metal body and water.

  Japanese Patent Application Laid-Open No. 2004-231466 (Patent Document 7) includes a hydrogen generating material that contains aluminum powder and calcium oxide powder in order to generate hydrogen from water, and the mixing ratio of the aluminum powder is 85% by mass or less. A hydrogen generation method and apparatus using the material are disclosed.

  In the hydrogen generator and the hydrogen generation method described above, a hydrogen generating material is used as a mixture in order to obtain a high-temperature state in which water can be reduced using a metal, and the mixture is heated. Or it aims at producing | generating hydrogen gas by using a high hydrogen atom content substance. At this time, the metal element generates hydrogen and then is oxidized to a metal oxide. However, if the metal oxide is discarded or used for other purposes, it generates hydrogen. For example, when aluminum is used, the total environmental cost including power consumption and use of fossil fuel for that purpose cannot always be said to be low.

  On the other hand, the oxidation and reduction of metal elements both proceed at a high temperature, other than using a wet electrochemical method. In this case, it is possible to generate metal element by oxidizing metal element with minimum apparatus cost, and simultaneously change the object to be processed, and reduce metal oxide to generate metal with the minimum apparatus structure change. If a hydrogen generator can be provided, it is considered that environmental costs including raw materials can be significantly reduced for hydrogen generation.

Furthermore, in recent years, environmental problems related to chemical substances are known. For example, reduction of nitrogen oxides NOx is required in terms of natural destruction and deterioration of structures due to acid rain generated by NOx. Carbon dioxide and CO ₂ must be reduced worldwide as a major cause of global warming. In addition, low-cost decomposition / conversion methods are required for specific chemical substances such as dioxins and environmental hormones.

  On the other hand, a laser device mainly generates electric light by converting electric energy into light (lamp lighting) or discharge form and exciting a laser medium. This method includes a plurality of energy conversion processes, and is known to have low energy efficiency (efficiency of several percent or less). The reason for this is that originally good quality electrical energy is converted into light through low-efficiency energy conversion. In addition, semiconductor laser-excited solid-state lasers have been proposed as an improvement of this point, and a photoelectric conversion efficiency of about 50% has been obtained, and its versatility is also increasing. It is thought to improve.

  On the other hand, solar pumped lasers that use sunlight as a light source are also known. If sunlight is used as an excitation light source, it can be used as a light source for laser oscillation without using an electricity-light conversion process that directly uses electricity generated by fossil fuels. For industrial equipment such as equipment, it is considered that the laser equipment can be used more easily, at lower cost, and with lower environmental load. In addition, power generation methods that do not depend on fossil fuels, such as wind power generation, tidal power generation, and geothermal power generation, are being put into practical use. For example, in recent years, although wind power generation has a characteristic that the power generation amount fluctuates significantly depending on conditions, the peak power generation amount can provide power exceeding 2000 kWh. I have the big problem of changing. By using a laser reduction device that uses a laser that oscillates with this electric power, energy can be stored in the form of magnesium, and energy can be supplied with reduced environmental load.

In addition, when performing laser reduction, it has been found that metal ions are generated in the initial process of decomposition of a metal oxide or the like. Since metal ions generated by laser reduction form a local plasma, they can be controlled by using existing magnetic confinement devices, and metal ions and negative ions are opposite to each other in a direction perpendicular to the magnetic field direction. Therefore, it is expected that energy conversion by photoelectric conversion becomes possible by taking it out of the system as a current.
JP 2003-313001 A Japanese Patent Laid-Open No. 2003-226502 JP 2002-69558 A JP-A-8-109001 JP-A-8-59201 JP-A-7-109102 JP 2004-231466 A

  When hydrogen is produced from water using the metal elements described above, an oxide is obtained as a by-product, and because of its high alkalinity, it has been difficult to treat and dispose of it. Furthermore, if the metal element oxide decomposes at a high temperature, it can be converted back to an alkali metal or alkaline earth metal. Therefore, if renewable energy can be used to create a high temperature environment, On the other hand, it can be said that hydrogen gas can be generated by a method with the least load.

  Conventional general-purpose lasers consume power and have low electrical-light energy conversion efficiency. On the other hand, solar-pumped lasers are only experimentally researched at universities and research institutions, and are applied to industrial applications. There was a problem that could not be done.

  The present invention has been made in view of the above prior art, and the present invention provides a hydrogen generator that efficiently uses renewable energy, recovers reaction energy, and generates hydrogen gas. With the goal.

  Another object of the present invention is to provide a laser reduction apparatus that can reduce the generated metal oxide to an alkali metal or alkaline earth element again using renewable energy. .

  Furthermore, an object of the present invention is to provide a hydrogen generation method using the above-described hydrogen generation apparatus and laser reduction apparatus.

Another object of the present invention is to provide a laser reduction device that can decompose oxygen-containing chemical substances such as NOx, CO ₂ , dioxins, and environmental hormones by reduction or convert them into other compounds.

  Furthermore, the present invention finds that metal cations are generated when laser reduction of alkali metal or alkaline earth metal is performed, and uses the generated charged particles to control the generated plasma by confining the magnetic field. An object of the present invention is to provide an energy conversion device and a power generation system.

  In the present invention, the metal element can be burned to obtain a water reducing ability at a high temperature, or the water can be reduced to hydrogen gas simply by contacting with water. Focusing on providing a metal element, the present invention has been achieved. In the present invention, an alkali metal element or an alkaline earth element is first combusted, and water is supplied in a state maintained at a high temperature. The supplied water generates hydrogen by the reduction action of the metal element, and recovers the generated hydrogen.

  Thereafter, the oxide obtained as a by-product is heated to a high temperature using a laser beam, and the oxide is thermally decomposed to regenerate the metal element again. The heating in the present invention is performed using a solar light excitation laser, and the use of energy derived from fossil fuel for heating can be minimized. The regenerated metal element is used again for the production of hydrogen.

In the present invention, a specific chemical substance such as an alkali metal, an alkaline earth metal, or NOx, CO ₂ is decomposed or converted efficiently and at low cost by using a laser light source such as a solar light pumped laser. It is possible to perform energy conversion using charged particles generated in

That is, according to the present invention,
A reaction vessel holding a metal element;
A water tank for supplying water to the reaction vessel;
A laser for heating the metal element by heating a portion where the metal element is in contact with the water;
A hydrogen extraction pipe for recovering hydrogen gas and reaction energy generated by the reaction between the metal element and the water;
Can be provided.

  In the present invention, the metal element can be selected from the group comprising sodium, potassium, magnesium, aluminum, calcium, zinc or mixtures thereof. The hydrogen generation device may include a hydrogen storage device that stores the recovered hydrogen gas, and the hydrogen storage device may include a hydrogen storage alloy.

According to a second configuration of the present invention, there is provided a laser reduction device for reducing a metal oxide to a metal using a laser beam,
A vacuum vessel containing a metal oxide and provided with an irradiation window;
There is provided a laser reduction device comprising: a laser that irradiates a laser beam inside the vacuum vessel through the irradiation window to reduce the metal oxide.

  In the present invention, the metal oxide can be selected from sodium oxide, potassium oxide, magnesium oxide, aluminum oxide, calcium oxide, zinc oxide or a mixture thereof. The laser can be a solar light pumped laser.

According to a third configuration of the present invention, there is provided a hydrogen generation method for generating hydrogen gas by reducing water with a metal, the method comprising:
A step of bringing a metal element into contact with water at a high temperature and reducing it to hydrogen gas to produce a metal oxide or a metal hydroxide;
Recovering the generated hydrogen gas;
And a step of regenerating the metal by laser reduction of the generated metal oxide or metal hydroxide.

  In the present invention, the metal can be selected from the group comprising sodium, potassium, magnesium, aluminum, calcium, zinc or mixtures thereof. The method may include a step of recovering the generated hydrogen gas, and the step of storing the recovered hydrogen gas may include a step of causing the hydrogen storage alloy to absorb the hydrogen gas. The laser reduction can reduce a metal oxide or a metal hydroxide using a solar light excitation laser.

In the fourth configuration of the present invention,
A laser reduction device for reducing oxygen-containing chemicals using a laser beam,
A vacuum vessel containing the chemical substance and provided with an irradiation window;
There is provided a laser reduction device comprising: a solar-excited laser that irradiates a laser beam inside the vacuum vessel through the irradiation window to reduce the chemical substance.

In the fifth configuration of the present invention,
An apparatus that performs energy conversion by laser reduction using a laser beam to reduce an oxygen-containing compound,
A container for containing the chemical substance;
A laser for generating plasma from the chemical substance;
A magnetic field generator for generating a magnetic field for deflecting the plasma;
A grid disposed in the vessel for extracting current from the plasma in the vessel;
There is provided an energy conversion device including a capacitor for accumulating charges generated by the plasma outside the container.

According to the sixth configuration of the present invention,
A reaction vessel for reacting metal elements;
A water tank for supplying water to the reaction vessel;
A feeder that supplies the molded body of the metal element into the reaction vessel so as to come into contact with the water;
A hydrogen extraction pipe for recovering hydrogen gas and reaction energy generated by the reaction between the metal element and the water;
And an activating means for activating the metal oxidation reaction in the reaction vessel. Further, according to the invention, a refrigerant jacket for cooling the reaction vessel is provided. A hydrogen generator can be provided. In this invention, it can isolate | separate from the said reaction container with a sieve, and can provide the collection | recovery container which collect | recovers the oxide powder of the said metal element.

  Furthermore, in the seventh configuration of the present invention, it is possible to provide a power generation system including the hydrogen generation device described in any one of the above.

Further, according to the eighth configuration of the present invention, a reaction vessel holding a metal-containing substance,
A water tank for supplying water to the reaction vessel;
A portion of the metal-containing material that comes into contact with the water to oxidize the metal-containing material to recover hydrogen gas and reaction energy generated by the reaction between the metal-containing material and the water;
An energy conversion device that performs energy conversion using the hydrogen gas from the hydrogen extraction pipe;
A reducing device that regenerates the metal-containing material by reducing an oxygen-containing compound produced by oxidation of the metal-containing material;
A recovery device for recovering the metal-containing material regenerated by the reduction device;
Can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the hydrogen generator which produces | generates hydrogen gas by using renewable energy efficiently can be provided.

  In addition, according to the present invention, it is possible to provide a laser reduction device that can reduce the generated metal oxide to metal again using renewable energy.

  Furthermore, according to this invention, the hydrogen production | generation method using the hydrogen production | generation apparatus and laser reduction apparatus which were mentioned above can be provided.

In addition, according to the present invention, chemical substances such as NOx and CO _{2 that} have a large environmental load are removed efficiently and for reduction without energy consumption accompanied by generation of NOx and CO _2. In addition, it is possible to provide a laser reduction device that enables the use of a material conversion device that uses a laser that decomposes a specific chemical substance including the above-mentioned harmful substances and the like, and to effectively use charged particles at the time of decomposition. Thus, an energy conversion device that enables photoelectric conversion can be provided.

  In addition, according to the present invention, it is possible to efficiently recycle a material that uses a great deal of energy to produce a metal-containing substance. It is possible to provide a hydrogen generation system with a small environmental load that can be consumed and the consumption of metal-containing substances can be minimized.

<Section 1: Hydrogen generator-first embodiment->
FIG. 1 is a diagram showing a schematic configuration of a hydrogen generator of the present invention. The hydrogen generator 10 of the present invention generally includes a reaction vessel 12, a hydrogen extraction pipe 14 for taking out generated hydrogen out of the system, and a water storage tank 16 for supplying water to the reaction vessel. An opening 20 is provided between the reaction vessel 12 and the water storage tank 16, and the valve 18 is closed when water is not supplied. When supplying water into the reaction vessel 12, the valve 18 is driven manually or by an electric actuator 22 to supply the water stored in the water storage tank 16 to the reaction vessel 12. In the lower part of the reaction vessel 12, a material 24 containing a metal element such as metal magnesium is accumulated. The metal in the present invention means sodium, potassium, magnesium, aluminum, calcium, zinc, or a mixture thereof. Further, in the present invention, it can contain an alkali metal element or an alkaline earth element more widely, and further, as a compound that can be decomposed by the present invention, NOx and CO ₂ , which are oxygen-containing chemical substances, dioxin And environmental hormones.

  Further, the embodiment shown in FIG. 1 will be described. A material 24 such as metallic magnesium is first ignited in the reaction vessel 12, burned in the presence of oxygen, and brought to a high temperature state. In the present invention, “high temperature” means a temperature at which normal temperature is not included and the material used in the present invention can reduce water. At this stage, the valve 18 is opened manually or by an electric actuator, and water is showered inside the reaction vessel 12. At this time, the magnesium metal is combusted at a high temperature in the specific embodiment of the present invention, and the magnesium heated to the high temperature reduces the supplied water to generate hydrogen gas. The generated hydrogen gas is taken out of the system through a hydrogen extraction pipe 14 disposed on the upper side of the reaction vessel 12, and the reaction energy is recovered by a heat exchanger (not shown) or the like. It is consumed directly by hydrogen consuming devices such as automobiles equipped with batteries. The recovered reaction energy can be reused for heating the reaction vessel 12 or the like. In the present invention, all or a part of the generated hydrogen gas can be stored in the hydrogen storage device 26 provided with a hydrogen storage alloy or the like, and the hydrogen gas can be discharged and used as necessary. In the present invention, it is not particularly necessary to heat the material to a high temperature when hydrogen is generated by reducing water at room temperature, such as metallic sodium or metallic lithium.

In the present invention, as the hydrogen storage alloy, for example, La _0.8 Nb _0.2 Ni _2.5 Co _2.4 Al _0.1 , La _0.8 Nb _0.2 Zr _0.03 Ni _3.8 Co _0.7 Al _0.5 , MmNi _3.65 Co _0.75 Mn _0.4 Al _0.3 , MmNi _2.5 Co _0.7 Al _0.8 , Mm _0.85 Zr _0.15 Ni _1.0 Al _0.8 V _0.2 (In the above general formula, Mm is misch metal, Ce (40-50%), La (20-40%), Pr, Nd
It is a mixture of rare earths with the main constituent element. ). In addition, in the present invention, a Laves phase (AB ₂ type) alloy, specifically, a Ti-Mn, Ti-Cr, or Zr-Mn alloy can be used as the hydrogen storage alloy. More specifically, (Ti _zx Zr _x V _4-y Ni _y ) _1-z Cr ₂ , ZrV _0.41 Ni _1.6 , ZrMn _0.6 Cr _0.2 Ni _{1.2 and the} like are not limited thereto. The magnesium after the reaction that generates hydrogen is converted into an oxide or hydroxide such as magnesium oxide or magnesium hydroxide, and accumulated in the reaction vessel 12. The accumulated magnesium oxide or magnesium hydroxide is then taken out of the reaction vessel 12 and can be used as a raw material for regenerating metal magnesium or the like.

<Section 2: Laser reduction device>
FIG. 2 is a diagram showing a laser reduction device used for the regeneration of metallic magnesium. The apparatus 30 shown in FIG. 2 generally includes a vacuum vessel 32, a line 34 for supplying metal oxides, and a line 36 for supplying iron silicide used for reduction in certain embodiments of the invention. And an optical system 38 including an irradiation window disposed in a vacuum vessel for introducing a laser beam to locally generate a high temperature. First, the metal oxide is heated in a kiln (not shown) to convert the hydroxide into an oxide, and then supplied into the vacuum vessel 32 through the line 34 and the hopper. In another embodiment of the present invention, a silicon (Si) element can be used alone, or a silicon element for reduction need not be used.

At the same time, after iron silicide is supplied through the line 36, the vacuum vessel 32 is depressurized, and then a laser beam is irradiated through the optical system 38 to cause a reduction reaction. In this case, in the present invention, flash lamp excitation, semiconductor laser excitation, etc., such as ruby, Nd ³⁺ : YAG, garnet, sapphire, emerald, alexandrite, etc., Cr ³⁺ , Co ²⁺ , Ce, Pr, Pm, Sm, Eu, Tb , Lanthanoid elements such as Dy, Ho, Er, Tm, Yb, and Lu, or ions thereof, or a laser medium using a laser medium doped with a transition metal element or a transition metal ion can be used. In another embodiment of the present invention, a catalyst may be used to promote the reduction. Furthermore, in the present invention, in order to irradiate the laser beam more efficiently, an optical scanning mechanism is provided in the optical system 38, and the target substance such as magnesium oxide can be irradiated as uniformly as possible.

  Further, in the present invention, a reduction reaction can be caused by using a sunlight-excited laser together with the laser described above or in place of the laser described above. FIG. 3 is a diagram showing a schematic configuration of the solar light pumped laser 40 of the present invention. The solar light excitation laser 40 of the present invention includes a laser medium 42, a storage device 44 for storing the laser medium 42, a total reflection mirror 46 disposed at one end of the laser medium 42, and a half And a mirror 48. The accommodation device 44 further includes an optical element 52 that condenses the sunlight 50 onto the laser medium 42, and optically excites the laser medium 42 to form an inverted distribution. The optical element 52 includes a reflection element, a lens element, and the like, and is cooled by a cooling liquid such as water held in the storage device 44, thereby enabling high-efficiency laser oscillation under efficient cooling. .

  The two ends of the storage device 44 shown in FIG. 3 are the material forming the end of the storage device 44, or the laser medium 42 and air when the laser medium 42 is directly exposed to the end of the storage device 44. The Brewster angle defined by is given. In the present invention, when it is not particularly necessary to provide a Brewster angle, an end portion having another angle can be used. The accommodation device 44 may be formed integrally with the laser medium 42 or may be fixed to the end surface of the accommodation device 44 using an appropriate flange, O-ring, or the like. Further, the end portion of the storage device 44 is coated with an antireflection film ARC to improve efficiency. In addition, when it is not necessary to use the antireflection film ARC in the present invention or when it cannot be structurally used, it is not necessary to provide the antireflection film ARC. The inside of the housing device 44 is filled with a cooling liquid such as water, and the laser medium 42 accompanying laser oscillation is cooled to prevent damage to the laser medium due to thermal shock. The shape of the storage device 44 can be circular, elliptical, parabolic, etc. in cross section. When using a storage device with a circular cross section, the position corresponding to the curvature of the storage device and the refractive index of the cooling refrigerant. A laser medium is disposed on the surface. When the accommodation device is elliptical, the laser medium can be arranged at one focal point and the sunlight can be condensed at the other focal point, and these shapes can be combined to condense on the laser medium. Can be made.

  In the present invention, the storage device 44 has a function of concentrating sunlight on the laser medium 42 and holds the cooling liquid inside, so that it receives cooling by the cooling liquid together with cooling of the laser medium. Can do. It is preferable to use water as the cooling liquid from the viewpoint of cost and operability, and the cooling refrigerant has a shape or lens capable of transmitting sunlight and concentrating sunlight on the laser medium at the same time. It can also be sealed or circulated in the containing device.

  In the present invention, a light emitting diode or a semiconductor laser that generates laser light having a wavelength corresponding to the laser wavelength can be used so that the laser can be appropriately triggered. Furthermore, for the purpose of triggering laser oscillation, it is possible to use a polarizing plate with a material that uses the optical Kerr effect that polarizes the polarization angle with an external electrical trigger, and a laser using a supersaturated dye. Oscillation can also be triggered in Q switch mode.

The laser medium is formed as an optically transparent rod having a diameter of several mm to several cm. Examples of the laser medium that can be used in the present invention include ruby (Cr ³⁺ : Al ₂ O ₃ ), YAG (Nd ³⁺ : Y ₃ Al ₅ O ₁₂ ), alexandrite (Cr ³⁺ : BeAl ₂ O ₄ ), Emerald (Cr ³⁺ : Be ₃ Al ₂ (SiO ₃ )) ₆ ), the general formula is given by A ₃ B ₂ C ₃ O ₁₂ , and an element selected from the group consisting of Ga or Al is used at site A The site B uses an element selected from the group consisting of Ga, Sc, and Lu, and the site C uses an element selected from the group consisting of Y, Gd, La, and Lu. ^Cr 3+, laser medium with the addition of ^{Nd 3+,} sapphire _{^{(Ti 3+: Al 2 O 3}} ), Co 2+: MgF 2, Cr 3+: ScBO 3, Nd 3+: GG _{(Gd 3 Ga 5 O 12)} , Cr, Nd: GSGG (Gd 3 (GaSc) 5 O 12) and the like can be mentioned, it is possible to form an absorption band with a suitable crystal field in the range of sunlight As long as any laser medium can be used. In the present invention, the laser medium 42 further includes other rare earth elements, for example, lanthanoid elements such as Ce, Pr, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, or the like. And laser media with different properties doped with transition metal elements or transition metal ions can be used.

  The total reflection mirror 46 uses a mirror using a metal coating such as Al deposition, a mirror including a coating that selectively reflects a laser oscillation wavelength by a dielectric multilayer coating, or a prism system using total reflection. The half mirror 48 can preferably be a mirror having a dielectric multi-layer coating and having a transmittance on the order of 10% to 90%. Also, for the optical element 52 that can be used in the present invention, any known coating such as a dielectric multilayer coating or a metal coating can be used.

  Referring to FIG. 2 again, the metal produced by heating and reduction is recovered by being cooled by a condenser 54 and then recovered by being cast by a casting device 56 and recovered as a bare metal 58. The Moreover, the iron silicide accumulated in the vacuum vessel 32 is also recovered, and after the soluble components are separated, it is recovered as slag. The recovered bare metal 58 can be supplied again to the hydrogen generator of the present invention, or can be used for other purposes. Further, in the present invention, it is not always necessary to use a catalyst such as iron silicide.

When reducing NOx, CO ₂ , dioxin, environmental hormones, etc. according to the present invention, for example, hydrogen gas generated by the hydrogen generator shown in FIG. 1 is introduced into the chamber to generate a reducing atmosphere. Then, a reduction reaction can be generated by irradiation with a solar light excitation laser, and decomposition or conversion into other chemical substances can be performed. In the present invention, when efficient reduction can be performed only with a laser beam, it is not always necessary to supply hydrogen gas.

<Section 3: Energy converter using laser reduction>
FIG. 4 is a diagram showing another embodiment of the energy conversion device of the present invention. In the energy conversion device 60 shown in FIG. 4, a grid 68 and an oxygen-containing chemical substance 74 are arranged in a toroidal container 62 formed in a toroidal shape. As the oxygen-containing chemical substance 74, MgO can be used in a specific embodiment of the present invention, but the present invention is not limited to MgO. The oxygen-containing chemical substance 74 is irradiated with the laser beam LB from the light transmissive window 76. The laser beam that can be used at this time can be generated using the laser described above. The laser beam LB is condensed onto an oxygen-containing chemical substance 74 through a condensing optical system 64 such as a lens, and decomposes the oxygen-containing chemical substance 74 to generate a plasma 78. The plasma 78, in certain embodiments of the present invention, includes Mg ⁺ and is formed with negative ions that provide a corresponding charge balance.

Further, a magnetic field is applied to the toroidal container 62 of the energy conversion device 60 along the circumferential direction of the toroidal container 62 so that the generated plasma 78 can be magnetically confined. For this reason, the charged particles in the plasma 78 drift at a speed given by (∇B / B) R _s U. In the above equation, B is the magnetic field strength, ∇B is the spatial gradient of the magnetic field, Rs is the Larmor radius (the turning radius in the magnetic field), and U is the turning speed of the charged particles. For this reason, in the configuration of FIG. 4, by causing the grid 66 to generate a potential, the positive and negative charged particles move while performing drift motions in opposite directions at the Larmor radius to generate a current. In the energy conversion device 60 shown in FIG. 4, this current is led out of the toroidal container 62 using a hermetic seal or the like and stored in the capacitor 70.

  The intensity of the magnetic field used in the present invention can be approximately 10 T or less, and the electric charge accumulated in the capacitor for a certain time is supplied to the load 72 to drive the load. For this reason, it is possible to convert chemical-light energy into electric energy by using charged particles generated when performing the laser reduction of the present invention. Further, the toroidal container 62 is formed with a recovery container 68 for recovering a metal that gives a cation, and collects a metal such as Mg, and at the same time, a gas generated from the anion passes through the exhaust line 80 to the outside of the toroidal container 62. Has been discharged.

  FIG. 5 is a schematic diagram showing a state of charged particles that drift between the grids 66. The grid 66 is grounded on the upper side, and the positive ions generated in the plasma 78 move downward while performing a Larmor radius drift motion, while the negative ions perform a Larmor radius drift motion while the upper side is grounded. To generate current between the grids. The grid 66 is formed as a suitable mesh and allows the discharge and passage of cations. In the present invention, an appropriate potential difference can be set for the grid 66.

FIG. 6 shows the emission spectrum of a cationic species observed in a plasma formed according to the present invention. In FIG. 6, an emission spectrum of Mg ⁺ (MgII, obtained for a plasma corresponding to about 10,000 K, formed by irradiating an MgO target with an Nd ³⁺ : YAG laser (pulse output 0.3 J, pulse width 5 ns). 448.1130 nm, 2P6 4f-2p6 3d, and MgI, 518.36042 nm, 3s4s-3s3p). As shown in FIG. 6, the emission of Mg ⁺ was clearly observed from the plasma confined in the toroidal container according to the present invention, and it was shown that charged particles can be generated in the plasma generated by laser irradiation.

<Section 4: Hydrogen Generator—Second Embodiment>
FIG. 7 is a diagram showing an essential configuration of the second embodiment of the hydrogen generator of the present invention. Hydrogen generating apparatus shown in FIG. 7 90, sodium (Na), potassium (K), magnesium (Mg), potassium (Ca), aluminum (Al), zinc (Zn) or of _H 2 O, such as those of any mixture It is common with the hydrogen generator shown in FIG. 1 and the like in that hydrogen is generated by oxidation, and conversely, H ₂ O is reduced to H ₂ . In particular, in the second embodiment shown in FIG. 7, instead of powdery material such as Mg, film-like, plate-like, flake-like, and slice-like materials are continuously introduced into the hydrogen generator, Is generated.

Referring to FIG. 7 in more detail, the hydrogen generator 90 shown in FIG. 7 includes a reaction vessel 92 and an introduction tube 94 that is inserted into the reaction vessel 92 and introduces H ₂ O into the reaction vessel 92. And a feeder 96 for introducing a material such as Mg. The reaction vessel 92 and the like can be formed from materials such as SUS304, SUS316, SUS321, SUS329, SUS309, SUS310, SUS317, SUS405, SUS347, SUS420, and SUS410, and include appropriate sealing means such as an O-ring and a metal seal. It can be used to ensure sealing from the outside. In the embodiment shown in FIG. 7, H ₂ O was led into the reaction vessel 92 in the state of high-temperature and high-pressure steam, and was formed in a film shape in the embodiment shown in FIG. Contact with Mg causes an oxidation reaction.

As a result of the oxidation reaction, MgO and H ₂ are formed. The generated H ₂ is led out of the reaction vessel 92 via the exhaust pipe 114 and supplied to the fuel cell directly or in order to accumulate in a hydrogen storage alloy or the like. On the other hand, the hydrogen generator 90 shown in FIG. 7 includes a sieve 108 that extends through the inside and is formed of meshes that are polymerized with each other. The sieve 108 is reciprocated in the left-right direction on the paper surface by a motor 110 or the like disposed outside the reaction vessel 92, and the generated bulk MgO is crushed to form a powder 112 having a predetermined particle size. Accumulate on the lower side.

  In addition, films, plates, flakes, slices, and the like of materials such as Mg are introduced into the reaction vessel 92 through the feeder 96, as long as the feeder 96 has a supply capability adapted to the shape of the film, flakes, and the like. Anything can be used. For example, when introducing Mg or the like into the reaction vessel 92 as a film or a plate, a die can be used as the feeder 96. In the present invention, materials such as films, plates, flakes, and sliced Mg may be separately stored in the supply chamber 98 so that Mg and the like are not oxidized by air before being introduced into the die. it can.

The inside of the storage chamber 98 is preferably replaced with a suitable inert gas such as N ₂ or Ar. The material that can be used in the present invention can be 0.1 to several mm thick when it is a film or a plate, and the major axis is several mm to several cm when it is a flake. Can do. In the present invention, it is possible to control the amount of H ₂ to be generated in addition to the calorific value by controlling the amount of H ₂ O to be supplied and the supply amount of the material film and the like. In addition, for the purpose of controlling the amount of heat generation, a material that has an endothermic oxidation or a heat generation amount smaller than that of Mg, such as zinc, may be mixed.

A material roll 104 and a conveying roller 102 are arranged inside the storage chamber 98, and the film-like or plate-like material 100 is transferred in response to the degree of oxidation / consumption of the material in the reaction vessel 92. The reaction vessel 92 is supplied. In yet another embodiment of the present invention, in order to rotate the material roll 104 and always provide a material having a fresh surface, a cutting blade is disposed in the storage chamber 98 and the rotational force of the material roll 104 is Can also be obtained using H ₂ or heat exhausted from the reaction vessel 92. The produced oxide powder 112 such as MgO is collected from a discharge port (not shown) periodically or whenever a predetermined amount is accumulated, and is provided for energy conversion by laser reduction.

  FIG. 8 is a diagram showing a more detailed configuration of the second embodiment of the hydrogen generator of the present invention. The hydrogen generator 120 illustrated in FIG. 8 includes a reaction vessel 124 and a heat exchange jacket 122 that surrounds the reaction vessel 124 and exchanges heat from the reaction vessel 124. A refrigerant (water) supply line 130 is connected to the heat exchange jacket 122 via a valve 128. The valve 128 can be, for example, a three-way valve, and can switch between a refrigerant supply mode and a heat exchange-water vapor supply mode by connecting the supply line 132 in response to the stop position. The front end of the supply line 132 is introduced into the reaction vessel 124, and water vapor (˜200 ° C.) generated by heat exchange is introduced into the reaction vessel 124.

  Further, in the embodiment shown in FIG. 8, a plate or film of a material such as Mg along the inner wall of the reaction vessel 124 is provided with an introduction slit (not shown) and a feed mechanism (not shown) provided in the upper part. It is supplied using. In the present invention, a plate, film, or flake of material can be introduced by any method in an arrangement that does not interfere with processing, and it is not always necessary to introduce the material along the inner wall. Not. On the other hand, a spark gap 134 made of tungsten (W) or the like is inserted into the reaction vessel 124 as an activating means for providing initial combustion that provides a temperature for sustaining the reaction. It is possible to cause combustion of the material.

  In still another embodiment of the present invention, instead of the spark gap 134, a YAG laser, a semiconductor laser, a solar light pumped laser, or the like can be used as the activating means. In addition, the present invention preferably uses a metal that is generated as an exothermic reaction of water at a high temperature. At this time, a material that generates a material having a small endothermic or exothermic amount during the water reduction reaction, such as zinc, It can also be used as a reaction control additive.

A cap 138 having fastening means is connected to the upper part of the reaction vessel 124. The cap 138 is extended with a discharge line 140 for discharging H ₂ generated from the cap 138 to the outside. The cap 138 is connected to the reaction vessel 124 using fastening means that can withstand high temperatures and high pressures. Although any means known so far can be used as such fastening means, specifically, a kakura type joint can be mentioned. A sieve 126 for pulverizing the generated oxide is formed on the lower side of the reaction vessel 124, and the pulverized oxide powder 146 is collected in a recovery vessel 142 formed on the lower side of the sieve 126. Accumulated in. In the present invention, the reaction container 124 and the recovery container 142 are connected using a flange, and for example, the powder material generated from the observation window formed in the recovery container 142 is monitored, After the predetermined charge has accumulated, the reaction container 124 and the recovery container 142 fastened by bolts and nuts can be separated to recover the powder.

The recovered oxide such as MgO is supplied again to the laser reduction method shown in FIG. 2 and can be used for regeneration of Mg and the like. Further, H ₂ generated by the hydrogen generator 120 of FIG. 8 can be directly used as fuel for the fuel cell. The produced H ₂ can be stored in a hydrogen storage alloy or the like and used as a fuel for a fuel cell in order to further improve handling. In yet another embodiment of the present invention, power can be generated by supplying excess steam to the steam turbine. The water cooled by the steam turbine may be circulated again to the supply line 130 and used as a heat exchange medium for the heat generated in the reaction vessel 124.

  In the present invention, water can be directly used as a medium for performing heat exchange of the reaction vessel 124. However, the cooling efficiency can be controlled by using a refrigerant such as an alternative chlorofluorocarbon or supercritical fluid separately from water as a cooling medium. And controllability of the reaction can be improved. As described above, the hydrogen generator 120 shown in FIG. 8 of the present invention can be applied not only as a hydrogen supply source but also to a pollution-free internal combustion engine, a pollution-free generator, etc. It becomes possible to reduce.

  The present invention can also be used for an urban emergency lifeline in the event of a disaster. In the event of a major earthquake, securing lifelines and extinguishing fires are important. In particular, if an M7 class earthquake occurs in large cities such as Tokyo, Osaka, Nagoya, and Fukuoka, 77% of damaged houses are estimated to be lost by fire. Has been. For this reason, in Tokyo and other places, water for disaster prevention is secured at 12,000 locations, but it is considered impossible for fire trucks to reach here during a disaster.

  The present invention can also be used as an emergency lifeline restoration device using a reaction between water, Mg having no spontaneous combustibility, and water. The present invention functions as an emergency lifeline restoration device as follows.

(1) Fire extinguishing: A gas turbine is started by heat generated by Mg and water and heat by hydrogen, and fire extinguishing activities are carried out in a local government by a pump from fire prevention water. Generally, if you use a gas turbine, rotary engine, reciprocating engine, Stirling engine, etc., in which hydrogen produced in the present invention is combusted in an amount of 35 cm square Mg, you will be able to secure 6-8 hours of power for a fire engine. become.

(2) Drinking water: The heat generated during the reaction between Mg and water can evaporate the water, thereby securing distilled water and providing drinking water. For example, by using fire prevention water, heat is generated in addition to hydrogen due to heat generated during the reaction of 35 cm square Mg, and by condensing the water vapor, 800 kg of safe drinking water can be generated.

(3) Electricity: Electricity is generated by using hydrogen as power for gas turbines, rotary engines, and reciprocating engines to ensure electricity. In this case, it is considered that 35 cm square Mg can secure electricity for one household for 1-2 weeks to about 1 month.

(4) Hot water: Heat of the condensation process of distilled water described above can be used regeneratively to boil fire-proof water and ensure hot water such as a bath. In the present invention, the merit of Mg is that it is not flammable like gasoline and heavy oil, so it can be stored near the ground surface and stored safely with a simple shielding process.・ It does not cause health and safety problems.

<Section 5: Reduction device using laser ablation>
FIG. 9 shows still another embodiment of the laser reduction device of the present invention. The laser reduction apparatus 150 illustrated in FIG. 9 includes a container 152 that includes a window 160 through which a laser beam is incident, and a nozzle 156 that injects an inert gas such as helium, argon, or nitrogen into the container 152. In the lower part of the container 152, massive, granular, and pellet-shaped MgO 148 is accumulated. Further, from the upper part of the container 152, the laser beam 162 is irradiated onto the MgO and is focused on an appropriate position of the MgO, and the MgO is melted by laser ablation.

On the other hand, a high-speed inert gas is injected from the nozzle 156 into the MgO 148 melted by the laser beam 162 and separated so as not to recombine Mg and O ₂ decomposed and generated as 2MgO → 2Mg + O _2. ing. The generated solid Mg adheres to the inner wall of the container 152 due to the pressure of the inert gas, and is recovered thereafter. On the other hand, the generated O ₂ is led out of the container 152 through an exhaust pipe and a valve arranged on the upper part of the container 152. In the laser reduction apparatus 150 of the present invention shown in FIG. 9, the laser beam 162 can be moved in the direction of the arrow A to increase the melting area of MgO and improve the efficiency. In the present invention, the inert gas can be injected into the container 152 after being heated to a high temperature so as not to be cooled by the injection of the inert gas.

  According to the present invention, hydrogen can be generated and stored as needed while giving a minimum load to the environment, so that a more versatile supply of hydrogen energy is possible. An extremely industrially valuable hydrogen generator, laser reduction device, energy converter, and hydrogen that can greatly change the infrastructure and make a significant contribution to global warming and depletion of fossil combustion. A generation method can be provided. The hydrogen produced by the present invention can be provided for a fuel cell, but the generated hydrogen can be directly applied as a fuel for an internal combustion engine, and should be appropriately used for providing an emergency lifeline. Can do.

Schematic of the hydrogen generator of the present invention. Schematic of the laser reduction device of the present invention. The schematic side view of the sunlight excitation laser used by this invention. Schematic of the energy conversion device of the present invention. The schematic of the drift motion of the charged particle in the energy conversion apparatus of this invention. The figure which showed the emission spectrum of the cation from the plasma produced | generated using the energy converter of this invention. The figure which showed the essential structure of the hydrogen generator of the 2nd Embodiment of this invention. The figure which showed the detailed structure of the hydrogen generator of the 2nd Embodiment of this invention. The figure which showed other embodiment of the laser reduction apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Hydrogen generator, 12 ... Reaction vessel, 14 ... Hydrogen extraction pipe, 16 ... Water tank, 18 ... Valve, 20 ... Opening, 22 ... Actuator, 24 ... Material, 26 ... Hydrogen storage device, 30 ... Laser reduction device, 32 ... Vacuum container, 34 ... Line, 36 ... Line, 38 ... Optical system, La ... Laser, 40 ... Solar excitation laser, 42 Laser medium, 44 ... Accommodating device, 46 ... Total reflection mirror, 48 ... Half mirror, 50 ... Sunlight, 52 ... Optical element, ARC ... Antireflection film, 54 ... Condenser, 56 ... Casting device, 58 ... Gold, 60 ... Energy conversion device, 62 ... Toroidal container, 64 ... Condensing optical system, 66 ... Grid 68 ... Recovery container, 70 ... Capacitor, 72 ... Load, 74 ... Target, 76 ... Light transmissive window, 78 ... Plasma, 80 ... Exhaust line, LB ... Laser light

Claims (7)

A reaction vessel holding a metal material ;
A supply line for intermittently supplying water vapor to the reaction vessel;
A spark gap or a laser, which is an activating means for causing an initial combustion of the metallic material and water and sustaining the reaction of the metallic material and water;
A discharge line for recovering hydrogen gas generated by the reaction between the metal material and the water vapor ;
A heat exchange jacket for exchanging heat from the reaction vessel to generate the water vapor;
The supply line supplies the water vapor generated by heat from the reaction vessel to the inside of the reaction vessel.
Hydrogen generator.   The hydrogen generator of claim 1, wherein the metal element is selected from the group comprising sodium, potassium, magnesium, aluminum, calcium, zinc or mixtures thereof. The hydrogen generator includes a hydrogen storage device that stores the recovered hydrogen gas,
The hydrogen generation device according to claim 1, wherein the hydrogen storage device includes a hydrogen storage alloy. A laser reduction device for reducing the metal oxide generated by the hydrogen generation device according to any one of claims 1 to 3 to a metal using a laser beam,
A line for supplying the metal oxide;
A second line for supplying iron silicide;
A vacuum vessel containing the metal oxide and the iron silicide and provided with an irradiation window;
A laser reduction apparatus comprising: a laser that irradiates a laser beam inside the vacuum vessel through the irradiation window under reduced pressure to reduce the metal oxide.   The laser reduction apparatus according to claim 4, wherein the metal oxide is selected from sodium oxide, potassium oxide, magnesium oxide, aluminum oxide, calcium oxide, zinc oxide, or a mixture thereof.   The laser reduction apparatus according to claim 4 or 5, wherein the laser is a solar light excitation laser. The hydrogen generator according to any one of claims 1 to 3,
An energy conversion device that performs energy conversion using the hydrogen gas generated by the hydrogen generation device;
The laser reduction device according to any one of claims 4 to 6,
A recovery device for recovering the metal material regenerated by the laser reduction device;
Regenerative hydrogen generator.

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