JP2005281716A - Electrolytic light-emitting device, electrode for electrolytic light-emitting device, hydrogen-gas-generating apparatus, power generator, cogeneration system, method for generating hydrogen gas, method for generating power and method for supplying energy - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolytic light-emitting device which can be applied to the production of hydrogen usable as an energy source; a hydrogen-gas-generating apparatus using the electrolytic light-emitting device; a method for generating hydrogen using the device; a power generator using hydrogen obtained by the apparatus; and a method for generating a power using the apparatus. <P>SOLUTION: The electrolytic light-emitting device comprises: a reaction vessel 1 of an electrolytic tank; an electrolytic solution 4 retained in the reaction vessel 1; a platinum anode 5 and the tip of a cathode terminal 2, which are placed so as to contact with the electrolytic solution 4 and contain a refractory metal; and a power source 18 and a control unit 17, which are electrolytic light-emitting reaction means. The electrolytic solution 4 contains 0.05 mol/liter or higher of an alkali metal carbonate as an electrolyte. The platinum anode 5 has a 10 times or larger surface area than the tip of the cathode terminal 2 has. The power source 18 and the control unit 17 cause an electrolytic luminescence reaction between the tip of the cathode terminal 2 and the platinum anode 5, through applying a voltage of 100 V or higher between them. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electroluminescence device, an electrode for an electroluminescence device, a hydrogen gas generation device, a power generation device, a cogeneration system, a hydrogen gas generation method, a power generation method, and an energy supply method, and more specifically, stabilizes an electroluminescence phenomenon. The present invention relates to an electroluminescent device, an electrode for an electroluminescent device, a hydrogen gas generator using the electroluminescent device, a power generation device, a cogeneration system, a hydrogen gas generation method, a power generation method, and an energy supply method.

Conventionally, a thermal energy extraction device using an electroluminescence phenomenon is known (see, for example, Patent Document 1).
JP 2001-108775 A

  Development of new energy sources different from conventional energy sources (power sources) such as the thermal energy extraction device using the electroluminescence phenomenon described above and the power generation device using this thermal energy extraction device has become a global environmental problem It is desired from the viewpoint of the response. More specific description will be given below.

1. Problems with conventional energy technologies (power generation technologies) (About the problems and problems of the main power generation methods currently used)
Currently, the electrical energy we use (hereinafter also referred to as energy) is mostly derived from fossil fuels such as oil and coal, although the proportion of nuclear energy has increased compared to before. However, when fossil fuel is used, the generation of carbon dioxide (CO ₂ ) is inevitable. Therefore, as the emergence of global environmental problems such as global warming has become prominent, the introduction of cleaner energy on a global scale is expected.

  For this reason, it is desired to develop and introduce a technology for enabling the use of coal resources with abundant resources such as high efficiency and low environmental load. In the future, it will be important to introduce cleaner energy on a global scale, such as renewable energy that is widely and abundant in the world, while reducing its dependence on fossil fuels.

  The power generation methods mainly used at present are nuclear power generation, thermal power generation, hydroelectric power generation, and various other types of power generation methods have been studied or put into practical use. Here, nuclear power generation uses nuclear fuel such as enriched uranium or plutonium, and first converts nuclear energy into thermal energy. The high-temperature steam generated by the heat energy is guided to the steam turbine, the generator is rotated, and as a result, electric energy is obtained. Thermal power generation burns gaseous fuel, liquid fuel, coal, and other combustible materials (including RDF (Refuse Derived Fuel)) to generate thermal energy first. High-temperature steam is generated by this thermal energy, the steam turbine is rotated by this high-temperature steam, and as a result, the generator is driven to obtain electric energy. Hydroelectric power generation is to obtain electric energy by driving a generator by turning a turbine according to a flow when water stored in a dam flows out of the dam. Examples of other power generation methods include geothermal power generation, wind power generation, solar cell power generation, thermal power generation, and fuel cell power generation.

  Among the above-described power generation methods, currently used power generation methods include nuclear power generation, thermal power generation, and hydropower generation. However, these power generation methods have the following problems.

  First, for nuclear power generation, expensive facilities are required to ensure safety against radiation. In addition, radioactive waste disposal and countermeasures are required. In addition, it is necessary to establish a nuclear fuel cycle from the viewpoint of effective use of uranium fuel resources, but at present this nuclear fuel cycle is not yet established. In addition, it cannot be said that the pull thermal plan using plutonium generated by reprocessing of spent nuclear fuel as fuel in light water reactors has made great progress. In addition, it is necessary to prevent problems such as leakage of radioactive materials and ensure safety. In addition, high maintenance costs are incurred to maintain the nuclear power plant. In addition, with the installation of nuclear power plants, there are concerns about the impact on the surrounding environment (environmental problems may occur). In addition, it is becoming difficult to secure a new construction site for constructing a new nuclear power plant.

In addition, thermal power generation has the following problems. In other words, when installing thermal power generation facilities, the location conditions are severely restricted by regulations such as exhaust gas. In addition, since it is necessary to perform desulfurization treatment and NO _X countermeasures on the exhaust gas, the capital investment is high. Moreover, in the case of thermal power generation using coal as fuel, there is a problem in the treatment of coal ash after combustion. In addition, there is a concern about the environmental load due to the discharge of warm wastewater (hot wastewater) generated by power generation to the surroundings. Moreover, in order to burn fossil fuels such as coal, carbon dioxide is released into the atmosphere, and as a result, carbon dioxide gas, which is said to cause global warming, is generated. Moreover, regarding power generation using RDF as fuel (RDF power generation), the power generation efficiency is not yet sufficiently high, and it is required to improve the power generation efficiency. In addition, in RDF power generation, there is a concern about the generation of dioxins.

  In hydropower generation, there are the following problems. In other words, since the conditions for the installation location of the hydroelectric power plant are severe, it has become difficult to actually install a new one. In addition, when constructing a dam for hydroelectric power generation, it is necessary to take measures against the environment. In addition, it is necessary to take measures such as compensation for residents such as settlements submerged by the construction of dams and securing new resettlement sites. In addition, in a dam for hydroelectric power generation, sand and mud accumulate in the dam due to operation for many years, and the capacity of the dam becomes smaller year by year. Therefore, maintenance such as periodically discharging sand accumulated in the dam becomes necessary, which increases the operating cost.

  As described above, there are various problems with the current main power generation methods. Further, the other power generation methods described above are considered to gradually spread in consideration of environmental loads and installation conditions. However, it seems that it cannot be used immediately as the main power generation method for supplying large-scale power like the current nuclear power generation and thermal power generation.

  Of the above-described power generation methods, fuel cell power generation has attracted attention in recent years. Fuel cell power generation has been developed and used as a power supply for spacecraft in the US space development program such as the Gemini, Apollo, and Space Shuttle projects. This is because the fuel cell has excellent characteristics such as high efficiency and high power density. Further, in recent years, a power generation system using a fuel cell for general power generation using light oil such as natural gas or naphtha or gas mainly composed of hydrogen obtained by reforming methanol or coal gas as a fuel, Researched and developed for commercialization. However, since such a system is still expensive and has a short life, research for solving the problems of low price and long life has been intensively conducted.

  A fuel cell is a power generation system that directly generates electricity through an electrochemical reaction between hydrogen and oxygen. Hydrogen, which is a fuel, is obtained, for example, by electrolyzing water or by reforming a fuel such as the natural gas described above.

  However, the method of producing hydrogen by electrolysis of water as described above has an economical problem as a method for securing energy fuel. Further, a method for obtaining hydrogen from fuel also requires a fuel reforming process, and the power generation cost of a power generation system using a fuel cell has not yet reached a commercialization level. That is, in a power generation system using a fuel cell, how to secure and supply hydrogen at a low cost is one major issue.

  Accordingly, the hydrogen production method will be briefly described below with respect to the present production method and the new production method.

(Hydrogen production technology using water electrolysis to date)
Conventionally, a system that decomposes water to produce hydrogen and oxygen and uses it as clean secondary energy has been studied. Water electrolysis has been industrially performed as a method for obtaining hydrogen as a chemical raw material. In Japan as well, until 1950s, large-scale water electrolyzers were operating in various parts of the country to produce hydrogen as a raw material for producing ammonia in the fertilizer industry. However, with the rise of petrochemistry, the method of producing hydrogen by steam reforming of hydrocarbons has become economically advantageous. For this reason, the method for producing hydrogen has shifted from the method for producing hydrogen by electrolysis of water to the method for producing hydrogen by steam reforming of the hydrocarbons described above. At present, hydrogen production by electrolysis of water on a large scale is rarely performed except in special areas where relatively low-cost electricity can be obtained by hydropower generation.

  In recent years, hydrogen energy systems have been proposed. And since hydrogen has been reconsidered as an energy medium in this way, interest in water electrolysis (water electrolysis), which can easily produce hydrogen from electric power, has come to regain interest. Water electrolysis is currently the only hydrogen production technology established industrially from non-fossil energy sources such as nuclear and solar energy. For this reason, new water electrolysis technology was developed in each country after the oil shock.

  Water electrolysis as a method for producing hydrogen, which is an energy medium, has the advantage that it is an industrially established technology as described above, but it uses hydrogen as a fuel (heat source) from high-quality energy (power) as electricity. ) Has the disadvantage of reducing the quality of energy (decreasing efficiency).

  Also, unlike the case of hydrogen production as a chemical raw material, in order to supply a large amount of hydrogen, the scale of the facility becomes extremely large, and in order to ensure economic validity, the energy for producing hydrogen Since high efficiency, that is, low value-added fuel is produced, it is necessary to be able to realize it at an economically reasonable level (that is, at low cost). Here, the water electrolyzer required a relatively large area. For this reason, in order to make a large-capacity facility at a low cost, it is necessary to develop the entire apparatus as a compact one. In order to reduce the size of the water electrolysis apparatus, it is conceivable to increase the amount of hydrogen generated per unit area by increasing the current per area of the electrode plate. However, increasing the current value per area of the electrode plate inevitably increases energy loss due to electrical resistance. As a result, there is a problem that the energy conversion efficiency decreases.

  In order to solve the above problems, the following three directions of technical development have been conventionally performed. That is, high temperature high pressure water electrolysis, solid polymer electrolyte (SPE) water electrolysis, and high temperature steam water electrolysis.

  In Japan, the Sunshine Project was started in 1974 by the Ministry of International Trade and Industry (now Ministry of Economy, Trade and Industry) Industrial Technology Institute. As part of this plan's hydrogen production technology development, an electrolytic cell was developed for high-temperature and high-pressure alkaline water electrolysis. This project lasted for 10 years, and an 80 kW pilot plant was constructed and operated and researched. However, since the supply and demand for oil has eased, the willingness to develop new energy has diminished and the immediate technical goals have been achieved. The large-scale development plan is over.

(About the method of decomposing water other than water electrolysis)
As a method of decomposing water into oxygen and hydrogen other than water electrolysis as described above, Direct pyrolysis, 2. 2. Radiolysis method, 3. thermochemical decomposition method; There are four photolysis methods.

The direct pyrolysis method is performed by continuing the heating of water at a temperature of about 2700 ° C. or higher. When water is heated under such conditions, the chemical reaction formula shown below,
H ₂ O → H ₂ + 1 / 2O ₂
The following reaction occurs. Thus, in the direct pyrolysis method, water is directly decomposed into oxygen and hydrogen.

  Here, the total energy required for decomposing water in the standard state and decomposing it into hydrogen and oxygen, which are gases in the standard state, is theoretically according to the following equation.

ΔH = ΔG + T · ΔS
Here, the total energy, that is, the change in enthalpy ΔH is composed of Gibbs free energy ΔG and thermal energy ΔQ. This thermal energy ΔQ is equal to T · ΔS. Here, T represents an absolute temperature, and ΔS represents an entropy change.

  Next, the radiolysis method is a method of applying Gibbs free energy with radiation. For example, when beta rays are used, the following reaction occurs.

CO ₂ + β → CO ⁻ + 1 / 2O ₂
CO ⁻ + H ₂ O → CO ₂ + H ₂ + e ⁻
In addition, since a beta ray is an electron (e < ^- >), it can be said that the reaction shown by the reaction formula mentioned above is a kind of electrolysis.

  The thermochemical decomposition method is a method in which chemical energy is applied as the Gibbs free energy ΔG in the total energy ΔH. For example, consider a case where certain chemical substances A and B are mixed in water. When this mixed liquid is heated, a chemical reaction occurs between the chemical substances A and B and water, and chemical energy is released. If such a reaction is written in chemical formula, it becomes as follows.

A + B + H ₂ O → AH ₂ + BO
AH ₂ → A + H ₂
BO → B + 1 / 2O ₂
Here, rather than decomposing water all at once, it is easier to decompose by dividing into three processes as in the chemical formula described above. This thermochemical decomposition can be said to be a complete recycling method in which the chemical substances A and B act as a catalyst and are not discharged or consumed themselves. For this reason, it attracted attention as an ideal water splitting method. There was a time when energy-related research laboratories around the world proposed a unique method and was called the thermochemical cycle method and was actively researched.

  However, even though the chemical reaction itself has definitely progressed, there have been chemical engineering problems such as product separation, heat transfer, product transport and storage, and chemical substances A and B. In particular, the chemical substance A can obtain a predetermined effect only when a highly corrosive substance such as halogen is used. As a result, there has been a problem regarding the material of the apparatus for carrying out such a thermochemical cycle method. For this reason, the thermochemical decomposition method described above has not been put into practical use, and research is still being conducted.

Next, in the photolysis method, a PN junction semiconductor is used. A pair of electrons and holes generated by light is separated inside the semiconductor by diffusion electrolysis formed by PN bonds. When this semiconductor is immersed in an electrolytic solution, diffusion electrolysis can be performed at the interface. And the decomposition | disassembly to the hydrogen and oxygen of water using this diffusion electrolysis is also possible. For example, in an apparatus in which a titanium oxide semiconductor (TiO ₂ ) and platinum (Pt) are used as electrodes and these electrodes are immersed in a potassium hydroxide (KOH) solution, ultraviolet rays are applied to the titanium oxide. Then, electrons and holes (P ⁺ ) are generated. And this is isolate | separated by diffusion electrolysis and a hole acts on a water molecule and raise | generates reaction as shown in the following Reaction Formula.

H ₂ O + 2P ⁺ → 2H ⁺ + 1 / 2O ₂
Such a reaction generates oxygen. Further, hydrogen ions (H ⁺ ) move through the solution and combine with electrons at the Pt electrode. As a result, the following reaction occurs.

2H ^{+ +} 2e ^- → H ₂
As a result, hydrogen is generated.

In this method, the semiconductor plays a very important role. As the semiconductor, in addition to TiO ₂ , SrTiO ₃ , Fe ₂ O ₃ , WO _{3 and the} like can be considered. Note that semiconductor conditions that can be used in such a photolysis method include a forbidden band width in the range of 1.5 to 2.5 eV and a sufficiently large photovoltaic power.

  The above has been considered as a method for decomposing water. However, with the exception of special cases, all of them have not yet been put into practical use mainly for economic reasons. The present invention has been made to solve the above-described problems, and an object of the present invention is to provide an electroluminescent device and an electrode for an electroluminescent device that can be applied to the production of hydrogen that can be used as an energy source, and To provide a hydrogen generation apparatus and a hydrogen generation method using this electroluminescent device, a power generation apparatus and a power generation method using hydrogen obtained by such an apparatus, a cogeneration system, and an energy supply method.

  An electroluminescent device according to the present invention includes an electrolytic cell, an electrolytic solution held inside the electrolytic cell, an anode and a cathode that are arranged in contact with the electrolytic solution, and contain a refractory metal, and an electroluminescent reaction Means. The electrolytic solution has an electrolyte concentration of 0.05 mol / liter or more. The anode has a surface area that is at least 10 times the surface area of the cathode. The electroluminescence reaction means causes an electroluminescence reaction by applying a voltage of 100 V or more to the cathode and the anode.

  In this way, the electroluminescence reaction can be generated continuously and stably. Therefore, the electroluminescence reaction can be industrially used stably, such as the use of hydrogen gas generation process utilizing the electroluminescence reaction.

  The electroluminescent device may include a concentration adjusting unit that adjusts an electrolyte concentration in the electrolytic solution.

  In this case, the electrolyte concentration of the electrolytic solution, which is one of the conditions for continuously generating the electroluminescence reaction, can be adjusted so as to satisfy the predetermined numerical range described above. As a result, the electroluminescence reaction can be stably generated over a long period of time.

  A hydrogen gas generator according to the present invention includes the above electroluminescent device and a gas extraction member. The gas extraction member is connected to the electrolytic cell of the electroluminescent device, and extracts hydrogen gas generated as a result of the electrolytic solution being decomposed by the electroluminescent reaction to the outside of the electrolytic cell. The hydrogen gas generator may further include an oxygen gas extraction member that extracts oxygen gas generated as a result of decomposition of the electrolytic solution by electroluminescence reaction to the outside of the electrolytic cell.

  In this way, since the electrolytic solution can be directly thermally decomposed by an electroluminescence reaction, more hydrogen gas can be generated than in the case of electrolyzing a normal electrolytic solution. In addition, since the electrolytic solution is directly pyrolyzed by electroluminescence reaction, when the oxygen gas extraction member is provided as described above, a larger amount of oxygen gas is contained than when the normal electrolytic solution is electrolyzed. Can be taken out.

  A power generation device according to the present invention includes the hydrogen gas generation device and a fuel cell. The fuel cell generates electricity using hydrogen gas taken out from the hydrogen gas generator as fuel. Further, when the oxygen gas can be taken out from the hydrogen gas generator, the power generation device may use the oxygen gas taken out from the hydrogen gas generator as a reaction gas of the fuel cell.

  In this case, since the hydrogen gas generated by the hydrogen gas generator is used as the fuel for the fuel cell, it is not necessary to accumulate hydrogen using a hydrogen storage alloy or the like for supplying the fuel cell. Further, in the fuel cell, hydrogen gas reacts with oxygen to become water, so that this water can also be reused for the electrolyte of the hydrogen gas generator.

  The power generation device may include an adjustment device that removes the liquid from the hydrogen gas extracted from the hydrogen gas generation device and adjusts the humidity of the hydrogen gas. When the oxygen gas can be taken out from the hydrogen gas generator, the adjusting device has a function of removing the liquid from the oxygen gas taken out from the hydrogen gas generator and adjusting the humidity of the oxygen gas. May be.

  In this case, since the humidity of the hydrogen gas (or oxygen gas and hydrogen gas) can be adjusted to a humidity suitable for the reaction in the fuel cell, the reaction in the fuel cell can be performed more efficiently. Can do. Therefore, the power generation efficiency in the fuel cell can be improved.

  In the above power generator, the hydrogen gas generator may include an oxygen gas extraction member that extracts oxygen gas generated as a result of decomposition of the electrolytic solution by electroluminescence reaction to the outside of the electrolytic cell. In the power generator, the hydrogen gas generator and the fuel cell may constitute a sealed circuit. That is, the power generation device includes a supply line for supplying hydrogen gas and oxygen gas extracted from the gas extraction member and oxygen gas extraction member of the hydrogen gas generation device to the fuel cell as fuel, and hydrogen generated as a result of power generation in the fuel cell. You may provide the recirculation | reflux pipe line for making the water produced | generated from gas and oxygen gas recirculate | reflux to the electrolytic cell of a hydrogen gas generator.

  In this case, since there is no need to supply reaction gas (fuel gas) such as hydrogen gas and oxygen gas used in the fuel cell from the outside, the range of selection of the installation location and usage environment of the power generation device can be expanded. .

  A cogeneration system according to the present invention includes the power generation device and a thermal energy extraction member that extracts thermal energy from the power generation device.

  If it does in this way, while taking out electrical energy from a power generator, exhaust heat accompanying generation of electricity or generation of hydrogen gas can be taken out as thermal energy. As a result, energy utilization efficiency can be improved.

  In the hydrogen gas generation method according to the present invention, a step of placing an electrolytic solution having an electrolyte concentration of 0.05 mol / liter or more in an electrolytic cell is performed. And the process of immersing a cathode and an anode in electrolyte solution is implemented. The cathode and anode each contain a refractory metal. The anode has a surface area that is at least 10 times the surface area of the cathode. A step of causing an electroluminescent reaction is performed by applying a voltage of 350 V or higher to the cathode and the anode. And the process which takes out the hydrogen gas which arises as a result of having decomposed | disassembled electrolyte solution by electroluminescent reaction out of an electrolytic vessel is implemented. The hydrogen gas generation method may include an oxygen gas extraction step of extracting oxygen gas generated as a result of the electrolytic solution being decomposed by the electroluminescence reaction to the outside of the electrolytic cell.

  In this way, water constituting the electrolytic solution can be directly pyrolyzed using an electroluminescence reaction, so that more hydrogen gas is generated than when electrolysis of a normal electrolytic solution is performed. Can do.

  In the hydrogen gas generation method, the step of causing the electroluminescence reaction may include adjusting the temperature of the electrolytic solution to be 70 ° C. or higher and 100 ° C. or lower.

  In this case, hydrogen gas can be stably generated by the electroluminescence reaction.

  In the hydrogen gas generation method, the voltage applied to the cathode and the anode in the step of causing the electroluminescence reaction may be a pulse voltage.

  In this case, the electroluminescence reaction can be continued while reducing electrode wear. Therefore, hydrogen gas can be generated stably.

  The power generation method according to the present invention includes a step of obtaining hydrogen gas by performing the hydrogen gas generation method, and a step of generating power with a fuel cell using the hydrogen gas as a fuel gas. In the power generation method, when oxygen gas can also be obtained by performing the hydrogen gas generation method, the oxygen gas may be used as a reaction gas for the fuel cell in the power generation step.

  In this case, since the hydrogen gas generated by the hydrogen gas generator is used as the fuel for the fuel cell, it is not necessary to accumulate hydrogen using a hydrogen storage alloy or the like for supplying the fuel cell. Further, in the fuel cell, hydrogen gas reacts with oxygen to become water, so that this water can be reused as the electrolyte of the hydrogen gas generator. In addition, when oxygen gas extracted from the hydrogen gas generator is used as the reaction gas of the fuel cell, it is not necessary to separately secure oxygen gas to be supplied to the fuel cell, so the hydrogen gas generator and the fuel cell are closed. A circuit can be configured.

  The power generation method may further include a step of removing the liquid from the hydrogen gas supplied to the fuel cell and adjusting the humidity of the hydrogen gas. In the above power generation method, when oxygen gas can also be obtained by performing the hydrogen gas power generation method, the method may further include a step of removing liquid from the oxygen gas and adjusting the humidity of the oxygen gas. Good.

  In this case, since the humidity of hydrogen gas (or hydrogen gas and oxygen gas) can be adjusted to a humidity suitable for the reaction in the fuel cell, the reaction in the fuel cell can be performed more efficiently. it can. Therefore, the power generation efficiency in the fuel cell can be improved.

  An energy supply method according to the present invention includes an electric energy supply step of supplying electric energy from a fuel cell to the outside by performing the power generation method, and electrolysis of thermal energy generated in accordance with the execution of the power generation method. And a thermal energy supply step of supplying the outside from at least one of the tank and the fuel cell.

  If it does in this way, while taking out electrical energy from a power generator, exhaust heat accompanying generation of electricity or generation of hydrogen gas can be taken out as thermal energy. As a result, energy utilization efficiency can be improved.

  An electrode for an electroluminescent device according to the present invention is an electrode for an electroluminescent device that is disposed so as to be in contact with an electrolytic solution and used to generate an electroluminescent reaction, and includes a cathode containing a refractory metal, An anode containing a melting point metal and having a surface area of 10 times or more the surface area of the cathode.

  By using such an electrode for an electroluminescence device, an electroluminescence reaction can be efficiently generated in the electroluminescence device.

  Thus, according to the present invention, the electroluminescence reaction can be utilized industrially stably. As a result, it is possible to realize the generation of hydrogen using the electroluminescence reaction, and the fuel cell power generation and cogeneration system using the generated hydrogen.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following drawings, the same or corresponding parts are denoted by the same reference numerals, and description thereof will not be repeated.

(Embodiment 1)
As a result of various studies, the inventor has completed a method for producing hydrogen using the electroluminescence phenomenon described below.

  Conventionally, when electrolyzing water, an electrolyte is dissolved in water to form an electrolytic solution, and a DC voltage of 1.7 V to 3.0 V is applied to an anode and a cathode immersed in the electrolytic solution. As a result of applying such a voltage, hydrogen is generated on the cathode side and oxygen is generated on the anode side.

  For such normal electrolysis, when a high-melting-point metal is used as the electrode material and the voltage applied to the electrode is set to 100 V or more and the current density is increased, the following state is obtained. That is, when electrolysis is continued in the electrolytic solution under the above-described conditions, the temperature of the electrolytic solution gradually increases. When a predetermined temperature and current density are reached, the reaction changes to a completely different reaction from that of normal electrolysis depending on the shape and arrangement of the electrodes.

  In normal electrolysis, hydrogen is generated from the cathode, and even if the current density is increased, only the amount of hydrogen generation is increased. On the other hand, when an anode having a sufficiently large surface area with respect to the surface area of the cathode is used and the voltage applied to the electrode is increased, the current density rapidly decreases when the voltage reaches a predetermined voltage, and the resistance of the electrolytic solution apparently appears. Will increase. Thereafter, a discharge reaction occurs from a part of the cathode, and a light emission phenomenon occurs from the vicinity of the cathode. This phenomenon has already been reported for more than 60 years as electroluminescence. However, the theoretical mechanism of this electroluminescence phenomenon has not been elucidated.

  As conditions for the electroluminescence phenomenon, the surface of the cathode is covered with the generated hydrogen bubbles, and by further increasing the current flowing through the electrode, a part of the cathode surface is locally heated and supplied. It is necessary that a part of the generated electric power is directly consumed for glow discharge in hydrogen bubbles. Then, when such glow discharge occurs, the cathode surface is covered not only with hydrogen but also with water vapor. This results in a uniform thin gas coating on the entire cathode surface. And discharge comes to occur continuously in this gas coat, and is stabilized. The discharge spectrum varies depending on the discharge voltage, the electrode metal, the temperature of the electrolytic solution, the surface state of the electrode, the type of the electrolytic solution, and the like.

  As a result of experiments conducted by the inventor, it has been found that the following conditions are necessary as conditions for causing the electroluminescence phenomenon continuously under normal pressure. That is: An aqueous solution containing 0.05 mol / liter or more of alkali metal carbonate is used as the electrolytic solution. 2. A cathode and an anode made of a refractory metal are immersed in the aqueous solution. 3. A DC voltage of 100 V or higher is applied to the electrode. 4). The value of the surface area of the anode is 10 times or more the value of the surface area of the cathode.

  If such conditions are satisfied, glow discharge can be continuously generated around the cathode. That is, the electroluminescence phenomenon can be continuously generated. The inventor has devised a device that supplies hydrogen by thermally decomposing water using a device (electroluminescent device) that can continuously generate such an electroluminescent phenomenon. The configuration will be described below with reference to FIG. FIG. 1 is a schematic view showing a hydrogen generator according to the present invention.

  As shown in FIG. 1, a hydrogen generator using an electroluminescent device according to the present invention includes a reaction vessel 1 that holds an electrolytic solution 4, a cathode terminal 2 inserted into the reaction vessel 1, and an anode terminal 3. And a power source 18 for supplying power to the cathode terminal 2 and the anode terminal 3. The power source 18 is connected to the cathode terminal 2 and the anode terminal 3 via a control device 17 and conductive wires 16a and 16b. The outer periphery of the cathode terminal 2 is covered with a covering material 10. In the cathode terminal 2, the covering material 10 is not disposed on the surface of the other end located on the opposite side of the one end connected to the conductive wire 16b. At the other end of the cathode terminal 2, the surface of the cathode terminal 2 is exposed. The other end of the exposed surface of the cathode terminal 2 acts as a cathode. A covering material 11 is also disposed on the outer periphery of the anode terminal 3. A mesh-shaped platinum anode 5 is connected to the other end portion of the anode terminal 3 which is located on the opposite side of the one end portion to which the conductive wire 16a is connected. The platinum anode 5 has an annular shape surrounding the cathode terminal 2. A cylindrical partition wall 6 surrounding the cathode terminal 2 is disposed inside the reaction vessel 1. The cathode terminal 2 is disposed inside the partition wall 6, and the platinum anode 5 is disposed outside the partition wall 6. That is, the partition wall 6 is positioned between the tip (cathode) of the cathode terminal 2 and the platinum anode 5 and is disposed so as to separate the cathode and the platinum anode 5.

  A heat exchanger vessel 15 is arranged so as to surround the reaction vessel 1. The reaction vessel 1 and the heat exchanger vessel 15 are connected and fixed by a strength member such as a support (not shown). The heat exchanger container 15 and the cathode terminal 2 and the anode terminal 3 are connected and fixed by a fixing member 14. The fixing member 14 also has a function as a sealing material for a connection portion between the heat exchanger container and the cathode terminal 2 and the anode terminal 3. Moreover, the connection part of the reaction container 1 and the cathode terminal 2 and the anode terminal 3 is also fixed and sealed with the sealing material.

  Between the reaction vessel 1 and the heat exchanger vessel 15, a heat exchange medium 23 (for example, a liquid such as water or a gas such as air or an inert gas) introduced from a circulation port (not shown) is disposed and circulated. ing.

  The control device 17 controls the frequency, voltage, current, and the like of power supplied from the power supply 18 so as to be changeable. A hydrogen-oxygen mixed gas take-out pipe 9 is connected so as to communicate with the inside of the reaction vessel 1 at a position adjacent to the cathode terminal 2 (position on the inner peripheral side of the partition wall 6). The hydrogen-oxygen mixed gas extraction pipe 9 is connected and fixed by a heat exchanger container 15 and a fixing member 14. The open end of the hydrogen-oxygen mixed gas take-out pipe 9 facing the reaction vessel 1 is in a state of maintaining a predetermined distance from the liquid surface 7 of the electrolytic solution 4 arranged in the reaction vessel 1.

  Further, at a position adjacent to the platinum anode 5, that is, on the outer peripheral side of the partition wall 6, an oxygen gas extraction pipe 8 is connected to the upper surface of the reaction container 1 so as to communicate with the inside of the reaction container 1. The oxygen gas take-out pipe 8 is arranged so that the opening end portion thereof is connected to the inside of the reaction vessel 1, and is connected and fixed via a heat exchanger vessel 15 and a fixing member 14. In FIG. 1, the hydrogen-oxygen mixed gas extraction pipe 9 is shown connected to the flow meter 19 and the mass analyzer 22 via the pipe line 20 for measurement. In addition, a valve 21 is installed in the pipe line 20 between the flow meter 19 and the mass analyzer 22. However, when the obtained hydrogen-oxygen mixed gas is used in a fuel cell or the like as will be described later, the hydrogen-oxygen mixed gas take-out pipe 9 and the oxygen gas take-out pipe 8 are connected to piping connected to other members such as the fuel cell. Will be.

  An electrolyte solution supply pipe 12 and an electrolyte solution discharge pipe 13 are connected to the side wall of the reaction container 1 so that the electrolyte solution 4 can flow into the reaction container 1. The electrolyte replenishment pipe 12 and the electrolyte discharge pipe 13 are connected and fixed by a heat exchanger container 15 and a fixing member 14, respectively. The electrolytic solution supply pipe 12 and the electrolytic solution discharge pipe 13 are connected to an electrolytic solution tank through a conduit and a pump (not shown). The pump described above is controlled by a control device (not shown) (for example, operating conditions such as on / off of the pump or the number of revolutions) so that the amount of the electrolytic solution 4 in the reaction vessel 1 is within a predetermined range.

  Using the above-described hydrogen generator, hydrogen can be generated by thermal decomposition of water using an electroluminescence phenomenon as described below.

  First, an aqueous solution in which an alkali metal carbonate is dissolved is prepared as an electrolytic solution. The concentration of the alkali metal carbonate is an arbitrary value of 0.05 mol / liter or more as described above. In this aqueous solution, a voltage of 350 V or higher is applied to the cathode terminal 2 and the anode terminal 3. As a result, glow discharge occurs at the tip portion (cathode portion) of the cathode terminal 2, and a so-called electroluminescence phenomenon occurs. In the vicinity where such glow discharge occurs, the temperature is 3500 ° C. or higher. Therefore, water is directly pyrolyzed in such a high temperature part. As a result, a large amount of hydrogen and oxygen that cannot be considered by ordinary electrolysis are generated. This is because the gas generated on the cathode terminal 2 side (the gas extracted by the hydrogen-oxygen mixed gas extraction tube 9) contains oxygen at a certain rate in addition to hydrogen. It can be seen that water is directly decomposed by heat due to the electroluminescence phenomenon (glow discharge) at the cathode part).

  According to the inventors' experiment, this phenomenon was confirmed even in the case of electrolysis using water vapor instead of the electrolyte solution 4. The amount of hydrogen generated by pyrolysis is changed by changing the conditions such as the magnitude of the voltage applied to the cathode terminal 2 and the anode terminal 3 described above and various applied pulse voltages. , More than the amount of hydrogen generated by normal electrolysis. More specifically, the apparatus according to the present invention generates 1.35 times more hydrogen and oxygen than the amount of hydrogen and oxygen generated by normal electrolysis.

  As a result of repeating the above experiments and researched by the inventor, it was found that the conditions for generating hydrogen by the electroluminescence phenomenon were as follows. That is: The voltage applied to the cathode terminal 2 and the anode terminal 3 is preferably 350 V or higher. 2. If the voltage applied to the cathode terminal 2 and the anode terminal 3 is a pulse voltage, the consumption of the electrode is reduced and electroluminescence is continuously generated. As a result, the amount of hydrogen generated by thermal decomposition can be increased. 3. The thermal decomposition reaction of water can be continued efficiently by variously changing and adjusting the pulse width of the pulse voltage described above from 0.1 seconds to 10 seconds and the pulse interval from 0.001 seconds to 5 seconds. 4). By maintaining the temperature of the electrolytic solution 4 in a temperature range of 70 ° C. or more and 100 ° C. or less, a more stable thermal decomposition reaction of water can be continuously caused. 5). Under the condition that the voltage applied to the anode terminal 3 and the cathode terminal 2 is 350 V or more, 99% or more of the applied voltage is applied to the end (cathode part) surface of the cathode terminal 2. As a result, voltage loss can be reduced. 6). When the electroluminescence reaction is continued under the high voltage condition as described above, a product in which the material constituting the cathode terminal 2 (metal material constituting the electrode) and hydrogen are reacted is formed. 7). Most of the heat generated by the electroluminescence reaction is used as energy for the thermal decomposition reaction of water. 8). It is considered that photons generated in the electroluminescence reaction under the high voltage under the above-described conditions are absorbed by the nuclei of the electrode metal and cause a multiphoton absorption phenomenon. 9. The atomic nucleus of the metal constituting the electrode (anode terminal 3) that has absorbed a large amount of photons is in an excited state. Such excited metal nuclei have a very low energy compared to the excited state caused by neutrons. As a result, it is considered that decomposition is extremely slower than the case of decomposition (fission) caused by the excited state by neutrons. 10. As described above, since the decomposition of nuclei is extremely slow, the nuclei generated as a result of the decomposition are stable nuclei. For this reason, almost no radioactive material is generated as a result of normal fission reactions. 11. It is considered that the electroluminescence phenomenon continues due to such low energy nuclear decomposition. That is, when viewed from the outside, it seems that excessive energy more than the input energy by electricity is generated in the portion where the electroluminescence phenomenon occurs, but in reality, the electron nucleus of the metal constituting the cathode terminal 2 is decomposed. It is thought that energy resulting from (a very slow safe fission reaction) is used.

(Embodiment 2)
FIG. 2 is a schematic diagram showing the configuration of an electroluminescence cogeneration system to which the hydrogen generator according to the present invention is applied. FIG. 3 is a schematic diagram for explaining a material balance and a heat balance in the electroluminescence cogeneration system shown in FIG. An electroluminescent cogeneration system according to the present invention will be described with reference to FIGS.

  As shown in FIG. 2, in the electroluminescence cogeneration system according to the present invention, after hydrogen and oxygen generated by an electroluminescence device 32 as a hydrogen generation device are subjected to humidity adjustment through a humidity controller / gas-liquid separator 33. Then, the fuel cell 31 is supplied and electric power is generated in the fuel cell 31. Water is generated from hydrogen gas and oxygen gas by a reaction that generates electricity in the fuel cell 31, and this water is returned to the electroluminescent device 32 and supplied via a pipe. Note that the liquid (water) separated from the hydrogen gas and the oxygen gas in the humidity controller / gas-liquid separator 33 is also supplied to the electroluminescence device 32 in the same manner.

  The electric power generated in the fuel cell 31 is supplied to the power distribution device 36 via the power conversion device 37. The power distribution device 36 supplies power necessary for causing the electroluminescence phenomenon to the electroluminescence device 32 via the power supply device 60 (see FIG. 3), and sends surplus power to the outside as power supply. . In this way, electric power can be supplied from the electroluminescence cogeneration system to the outside.

  Note that power from the external power source 34 is required before the electroluminescence phenomenon is first generated in the electroluminescence device 32. For this reason, the external power supply 34 is in a state of being connected to the power distribution device 36 via the watt-hour meter 35. When the electroluminescent phenomenon is first activated in the electroluminescent device, the electric power supplied from the external power source 34 to the power distribution device 36 via the watt hour meter 35 is supplied to the electroluminescent device 32 via the conductive wire. Will be.

  On the other hand, in the electroluminescent device 32 and the fuel cell 31, heat is generated in the course of the reaction. The generated heat is recovered by the water circulating in the pipe line 49 by the pump 41, and is used to raise the temperature of water as a heat medium accumulated in the hot water storage tank 40 (boiling hot water). A water supply source 38 is connected to the hot water storage tank 40 via a valve 39. In the hot water storage tank 40, hot water heated by heat from the exposed portion of the conduit 49 is supplied to the outside of the hot water storage tank 40 as hot water. Further, in the electroluminescence cogeneration system, as shown in the figure, a low-temperature water absorption refrigerator 43, a heat-dissipating heat exchanger 42, and a cooling tower 44 are arranged and connected by a predetermined pipe line.

  As will be described later, for example, cold water of about 7 ° C. can be supplied to the outside from the low-temperature water absorption refrigerator 43. In the electroluminescence cogeneration system, a hot water supply heat exchanger 47 connected to a pipe passing through the hot water storage tank 40 is installed. In this hot water supply heat exchanger 47, heat exchange is performed for supplying the heat energy of hot water in the hot water storage tank to the outside as hot water. In such a pipe for supplying cold water or hot water (hot water), pumps 45, 46, and 48 are installed to feed the medium in a predetermined direction.

  The electroluminescent cogeneration system shown in FIG. 2 will be briefly described below for each component.

  First, regarding the power supply device, when the electroluminescence device 32 is activated, an external power supply 34 is required as the power supply device. When a 100 V AC power source supplied by an electric power company is used as the external power source 34, it is supplied to the electroluminescence device 32 as DC electricity of about 250 V (more preferably 350 V or more) via a thyristor and a DC converter. Moreover, when using a battery as a power supply device used when starting the electroluminescent device 32, the DC current from the battery may be boosted to about 250 V, and then the boosted current may be supplied. Further, such a power supply device preferably incorporates a pulse generator and supplies a pulse voltage to the electroluminescence device 32. In this way, a stable electroluminescent reaction can be caused continuously. As a result, water electrolysis and thermal decomposition can be promoted stably.

  Then, if power generation is started in the fuel cell 31 using the hydrogen gas and oxygen gas supplied from the electroluminescent device 32, sufficient electric power to be supplied to the electroluminescent device 32 is secured as will be described later. Therefore, the external power supply 34 is shut off. When a battery is used as the external power source 34, the amount of power consumed when the above electroluminescent device 32 is activated may be charged with the power generated in the fuel cell 31.

  The electroluminescent device 32 functions as a hydrogen gas and oxygen gas generator in the electroluminescent cogeneration system shown in FIG. As the configuration of the electroluminescence device 32, for example, a device configuration as shown in FIG. 1 can be used. When the apparatus having the structure as shown in FIG. 1 is used, for example, the electrolytic solution 4 is held inside the sealed reaction vessel 1. The amount of the electrolytic solution 4 can be about 70% of the internal volume of the reaction vessel 1. The reaction vessel 1 is provided with a discharge pipe (such as a hydrogen-oxygen mixed gas take-out pipe 9) for taking out hydrogen gas and oxygen gas, and a return of water generated as a result of recombination of the hydrogen gas and oxygen gas in the fuel cell 31. A pipe (for example, a pipe connected to the electrolyte solution supply pipe 12) and a heat exchanger for recovering heat generated in the reaction vessel are provided. As this heat exchanger, as shown in FIG. 1, a heat exchanger vessel 15 surrounding the reaction vessel 1 is arranged, and heat exchange is performed in a gap between the reaction vessel 1 and the heat exchanger vessel 15. A technique of distributing the medium 23 can be used. Further, as a heat exchange method, a pipe for the heat exchanger is disposed so as to be immersed in the electrolyte solution 4 inside the reaction vessel 1 so that the heat exchange medium 23 flows through the pipe of the heat exchanger. It may be. In the electrolytic solution, as described with reference to FIG. 1, the cathode terminal 2 and the platinum anode 5 having a surface area of 10 times or more of the surface area of the tip (cathode part) acting as the cathode in the cathode terminal 2 are arranged. To do. The cathode terminal 2 and the anode terminal 3 are each applied with a power supply voltage supplied from a power distribution device 36 (see FIG. 2).

  The power distribution device 36 has a function of sending direct current electricity generated in the fuel cell 31 to the electrolytic light emission device 32 as direct current so that electrolysis with continuous electrolytic light emission is performed, and to the outside of the cogeneration system. It has a function of converting to 100V AC electricity and outputting.

  In the electroluminescence cogeneration system shown in FIG. 2, the heat generated in the electroluminescence device 32 is recovered by the heat exchanger in the electroluminescence device 32. Further, a heat exchanger installed in the fuel cell 31 (for example, a heat exchange medium installed so as to surround the fuel cell 31 is circulated) reaction heat generated when hydrogen and oxygen are recombined in the fuel cell 31. It is possible to collect by piping etc. that can be. In each heat exchanger, cooling water as a heat exchange medium is circulated through a pipe as shown by a pipe line 49 in FIG. The exhaust heat recovered by these heat exchangers is used to make hot water in the hot water storage tank 40.

  Moreover, the hot water held in such a hot water storage tank 40 is used as a heat source of the low-temperature water absorption refrigerator 43 that operates using low-temperature water (70 ° C. to 90 ° C.) as a heat source. In the low-temperature water absorption refrigerator 43, cold water at 5 ° C. to 9 ° C. can be produced by evaporating the refrigerant with an evaporator. And if such cold water is sent to a fan coil or an air handling unit, the living space can be cooled, for example.

  Here, the electroluminescence cogeneration system shown in FIG. 2 is a system in which hydrogen and oxygen generated by utilizing the electroluminescence phenomenon as described above are guided to the fuel cell 31 and used as fuel. Since hydrogen and oxygen are pure fuels, they pass through a humidity controller / gas-liquid separator 33 (also referred to as a gas-liquid separator / dryer) to an alkaline fuel cell or a carbonated carbonate fuel cell with good power generation efficiency. If this hydrogen gas or oxygen gas is supplied, it is theoretically possible to ensure a power generation efficiency of 83%.

  Here, one important factor for maintaining the power generation efficiency of the fuel cell with high efficiency is the moisture management of the electrolyte membrane in the fuel cell. This reason can be explained from the reaction principle in the fuel cell. That is, when hydrogen ions move from the anode to the cathode, the hydrogen ions and some water molecules are combined, and the hydrogen ions move together with the water molecules. For this reason, in order to maintain the power generation efficiency of the fuel cell with high efficiency, it is necessary that hydrogen gas and oxygen gas as fuel gas always contain appropriate moisture. And if there is too much water in hydrogen gas or oxygen gas, water will cover the three-phase interface (electrode catalyst, fuel gas, electrolyte membrane interface) that is the reaction field, and reduce the power generation performance of the fuel cell. become. As described above, in the fuel cell, it is important to keep the moisture content (humid state) in the fuel gas constant and maintain the power generation efficiency.

When the power generation efficiency in the fuel cell is 83%, as shown in FIG. 3, the power generation amount in the fuel cell 31 using 4.62 Nm ³ / h hydrogen gas generated from the electroluminescence device 32 as the fuel is 11.5 kW. / H. Of this electric power, 10 kw / h is supplied to the electroluminescent device 32. As a result, the power initially supplied to the electroluminescence device 32 is not necessary. At the same time, 1.5 kW / h of the power generated by the fuel cell 31 can be supplied to the outside. As a result, the electroluminescence cogeneration system can supply surplus power to the outside while technically maintaining the electroluminescence phenomenon. In other words, it can be seen that the system can use energy that could not be used until now.

  Further, as shown in FIG. 3, the water recombined in the fuel cell can be returned to the electroluminescent device 32 via the drain recovery 61. As a result, it is possible to supplement the decrease in the electrolytic solution due to the decomposition of water in the electrolytic solution into hydrogen and oxygen. As a result, water can be reused between the electroluminescence device and the fuel cell, and a closed cycle can be achieved.

  In the electroluminescent cogeneration system shown in FIG. 2, as already described, since heat is generated from the electroluminescent device 32 and the fuel cell 31, the generated heat is recovered as hot water and supplied as hot water as described above ( It is possible to use heat energy, such as hot water supply, or by leading to a fan coil, an air handling unit or a floor heating coil. In addition, by using this hot water as a heat source for the low-temperature water absorption refrigerator 43 to produce cold water at 5 ° C. to 9 ° C., it can be led to a fan coil or an air handling unit and used for cooling.

As shown in FIG. 3, when the initial power input amount that is initially input to cause electroluminescence in the electroluminescence device 32 is 10 kw / h, hydrogen is 4.62 Nm ³ / h in the electroluminescence device 32. Occur. Further, at this time, the amount of heat generated by the electroluminescence device 32 (the amount of heat of the exhaust heat recovery 62) is 2249 kcal / h as shown in FIG. 3, and cooling water (for example, shown in FIG. In addition, it can be recovered as hot water at 90 ° C. using cooling water flowing through the heat exchanger vessel 15. Further, 4.62 Nm ³ / h hydrogen (hydrogen gas) and 2.31 Nm ³ / h oxygen (oxygen gas) generated in the electroluminescence device 32 are sent to the alkaline or carbonate molten salt fuel cell 31. It is done.

  In the fuel cell 31, power is generated by recombination of hydrogen and oxygen. If the power generation efficiency in the fuel cell 31 is 83%, 11.5 kw / h electric power, 5.75 kg / h water, and 4236 kcal / h heat are generated from the hydrogen and oxygen described above. This heat can be recovered as 90 ° C. hot water using cooling water circulating in the fuel cell 31 (cooling water circulating in the pipe line 49). The amount of heat recovered in this way (the amount of heat of the exhaust heat recovery 63) is 6472 kcal / h in total. When this heat is recovered as hot water, hot water of about 80 ° C. to 85 ° C. can be stored in the hot water storage tank 40 (hot water supply tank).

Moreover, if these heats are sent to the fan coil, the air handling unit, or the floor heating coil installed in the residential room as described above, they can be used for heating. Further, in summer, when the entire amount of hot water is used as a heat source for the generator of the low-temperature water absorption refrigerator, cold water of 7 ° C. can be obtained with an efficiency of about 0.6 to 0.7. Then, the cooling operation can be performed by sending the cold water to the fan coil or the air handling unit used at the time of heating. In addition, the refrigerating capacity of such a low-temperature water absorption refrigerator is 3883 kcal / h to 4530 kcal / h, and a room of 26 m ² to 30 m ² can be cooled. Then, by supplying hot water at night and using these heats for cooling and heating during the day, a cogeneration system capable of efficient power generation, hot water supply, cooling and heating can be obtained. In addition, as shown in FIG. 3, the heat radiation from the low-temperature water absorption refrigerator 43 to the cooling water is 10355 kcal / h.

  Here, the numerical values of the material balance and the heat balance of the electroluminescence cogeneration system shown in FIG. 3 will be described.

First, consider the energy balance of the fuel cell. The reaction in the fuel cell is a hydrogen combustion reaction. Combustion is generally an exothermic reaction between fuel and oxygen, and reaction heat in a combustion process that generates stable oxides H ₂ O, CO ₂ , CO, etc. is called combustion heat. Usually, the absolute value of the combustion heat per 1 kg of fuel or 1 Nm ^{3 is referred} to as the calorific value of the fuel. When the combustion gas comprises of H ₂ O, in a state after the combustion, H ₂ O results in a difference in H ₂ O vaporization latent heat of the heating value depending on whether a liquid or a gas. The amount of heat generated when H ₂ O condenses and contains latent heat is referred to as total heat generation or higher heat generation. On the other hand, the calorific value when H ₂ O remains steam and does not contain latent heat is referred to as the true calorific value or the lower calorific value.

  The energy corresponding to the reduction amount (−ΔH) of the change in the enthalpy of the fuel combustion reaction in the fuel cell is the total available energy. The maximum energy that can be used in the electrochemical reaction is energy corresponding to a reduction amount (−ΔG) of a free energy change due to the reaction. Here, the amount of decrease in free energy change is expressed by the following equation.

-ΔG = nFE
Here, E represents the maximum voltage of the battery, F represents Faraday constant: 9.65 × 10 ⁴ A · s (Coulomb), and n represents the number of reaction electrons. On the other hand, the amount of decrease in enthalpy change is expressed by the following equation.

−ΔH = −ΔG−TΔS
Therefore, energy corresponding to (−TΔS) in the above-described formula cannot be used. And the chemical reaction formula shown below 2H ₂ + O ₂ = 2H ₂ O
The entropy change (ΔS) of the fuel cell reaction at is negative. Therefore, the amount corresponding to (−TΔS) is released out of the system as heat. When the partial pressures of hydrogen, oxygen, and water vapor are all 1 atm, (−ΔH) of the reaction in the fuel cell is approximately 250 kJ · mol ⁻¹ . Thus, (- ΔG) is, 224kJ · mol ^-1 next at 200 ° C., a 178kJ · mol ^-1 when the temperature is 1000 ° C..

  Therefore, the theoretically required energy conversion efficiency (ΔG / ΔH) is 89.6% when the temperature is 200 ° C., and 71.2% when the temperature is 1000 ° C. Actually, it includes irreversible energy loss consumed by polarization caused by delay of electrode reaction and resistance of electrodes and electrolytes. These increase if the current density of the discharge is increased. Further, such energy loss decreases as the battery operating temperature is increased. At present, the conversion efficiency into electric energy is about 40% to a maximum of 83%. All other energy is released out of the system as heat.

Next, the amount of power generated by the fuel cell when hydrogen gas 4.62 Nm ³ / h is used will be examined. The amount of hydrogen gas is the amount of hydrogen gas generated in the electroluminescent device 32 (see FIG. 3) (experimentally determined amount), which is 3.4 Nm ³ / h by electrolysis, and the thermal decomposition reaction. It is considered that 1.22 Nm ³ / h is generated. After hydrogen, which is a fuel, reacts in the fuel cell 31, the generated water is in a water vapor state. Therefore, the lower heating value is used as the heating value. The lower heating value of hydrogen is 2570 kcal / Nm ³ . Therefore, the energy available for fuel cell power generation is
^{2570kcal / Nm 3 × 4.26Nm 3 /} h = 11873kcal / h
It becomes. If the power generation efficiency of the fuel cell 31 is 83%, the power generation amount is expressed by the following equation.

11873 kcal / h x 0.83 = 9855 kcal / h
Here, since 1 kw / h = 860 kcal / kwh, the power generation amount in the fuel cell power generation is expressed by the following equation.

9855 kcal / h ÷ 860 kcal / kwh = 11.5 kw / h
Next, the amount of exhaust heat due to water vapor loss is examined. Energy that could not be used for power generation can be used for heat. Therefore, the amount of heat (the amount of exhaust heat due to water vapor loss) is calculated. Since the total calorific value of hydrogen is 3050 kcal / Nm ³ , the calorific value is expressed by the following equation.

^{3050kcal / Nm 3 × 4.62Nm 3 /} h = 14091kcal / h
And when subtracting the energy used for power generation from the value obtained by the above formula,
14091 kcal / h-11873 kcal / h = 2218 kcal / h
It becomes. The amount of heat of 2218 kcal / h is energy that can be used as exhaust heat for air conditioning or hot water supply.

  Next, the amount of exhaust heat from the difference in power generation efficiency is examined. Here, the energy supplied from the fuel hydrogen to the fuel cell 31 is 11873 kcal / h as described above. The amount of heat exhausted from the fuel cell 31 with a power generation efficiency of 83% is expressed by the following equation.

11873 kcal / h × (1.00−0.83) = 2018 kcal / h
Next, the total amount of exhaust heat from the fuel cell 31 is examined. The total exhaust heat amount of the fuel cell 31 from the above-described water vapor loss and power generation efficiency difference is expressed by the following equation.

2218 kcal / h + 2018 kcal / h = 4236 kcal / h
Then, considering the total amount of heat exhausted from the electroluminescence device 32 and the fuel cell 31, the total heat generation amount is represented by the following equation.

2249 kcal / h + 4236 kcal / h = 6472 kcal / h
The exhaust heat as described above can be used by using the low-temperature water absorption refrigerator 43 as described above. For example, by using the above-described exhaust heat as a heat source and using a low-temperature water absorption refrigerator using water as a refrigerant and a lithium bromide aqueous solution as an absorption solution, 7 ° C. cold water for cooling can be produced. Further, by supplying hot water of 70 ° C. to 90 ° C. as a heat source, 7 ° C. cold water can be made with an efficiency of a coefficient of performance of 0.6 to 0.7.

(Embodiment 3)
An energy supply system (power generation system) such as a cogeneration system using the above-described electroluminescence phenomenon can be applied to various fields. Here, it is considered that hydrogen energy is a pillar of energy that can greatly contribute to the prevention of global warming and can be replaced with a new location of nuclear power. It is also said that the 21st century is an era of hydrogen. Fuel cells that use hydrogen as a fuel for chemical power generation are being studied for use in automobiles and other transportation systems, and their practical application is imminent. It seems that the era of the spread of such fuel cells as a clean energy source to replace gasoline engines and diesel engines is approaching.

And the electric power generation system by this invention can be utilized also as motive power sources of such moving bodies, such as a motor vehicle. Here, the development status of such an automobile (also called a hydrogen-using automobile) will be briefly described. Currently developed hydrogen-powered vehicles are equipped with infrastructure such as fuel cell performance, size, weight, cost, fuel storage tank system for hydrogen, and regional arrangement of refueling stations (hydrogen stations). It is a problem. In 2002, two hydrogen stations, one-tenth of a 300 Nm ³ / h commercial machine, were put into operation. One is a station in which hydrogen is generated by natural gas reforming and stored in a hydrogen storage alloy, and the other is a station in which hydrogen from solid polymer water electrolysis is stored in a hydrogen storage alloy. And in 2003, a running test by a fuel cell vehicle will be carried out on public roads using this hydrogen station.

  Thus, if it is conventional technology, the final appearance of the fuel cell vehicle is expected to be a hydrogen supply type. In a station using only pressurized hydrogen having a hydrogen mass of 100 kg or less, the target time for storing hydrogen in the storage alloy of the automobile is set to be within 10 minutes. However, since this time currently takes about 30 minutes, how to reduce this time is an issue.

  Moreover, since the hydrogen storage alloy tank mounted in a motor vehicle becomes a powder, there is a problem of how to design a cooling device or the like in the tank.

  Here, as for the hydrogen storage alloy, Toyota Motor has succeeded in storing 2 mass% of hydrogen at a mass of 100 kg. At 2% by mass, the car can travel 250 km. However, it is preferable that the automobile can travel about 450 to 500 km with one filling of hydrogen. Therefore, in order to realize such a travel distance, the key is how much the hydrogen storage capacity of the hydrogen storage alloy can be increased.

  Here, the hydrogen storage alloy mounted on the fuel cell vehicle causes an exothermic reaction when storing hydrogen. Moreover, when releasing hydrogen, it is necessary to set it as the temperature conditions of 80 degrees C or less. However, magnesium hydrogen storage alloy can store up to about 70% by mass of hydrogen, but a temperature of 350 ° C. is required to release hydrogen. Because of such high temperatures, it is difficult to put hydrogen storage alloys using magnesium into practical use. In consideration of safety, an alloy capable of releasing hydrogen at room temperature is required.

  Since there are various issues regarding how to store hydrogen in this way, in fact, whether a hydrogen storage alloy is mounted on a fuel cell vehicle as a hydrogen-using vehicle, and the hydrogen source The specific direction, such as whether to use ethanol reforming, gasoline reforming, or to use a high-pressure tank as a tank in which a hydrogen storage alloy is placed, has not yet been determined.

  Here, a system in which the electroluminescence device according to the present invention is mounted on a hydrogen-utilizing vehicle is considered. If an electroluminescent device according to the present invention (for example, a hydrogen generator as shown in FIG. 1) is mounted on an automobile, hydrogen and oxygen are generated and supplied to a fuel cell, a hydrogen storage tank is not necessary. There is no need for a hydrogen station. When starting the electroluminescence device, for example, it may be started using a battery in the same manner as in the current automobile, and supply of hydrogen and oxygen may be started. When the automobile is running, if the battery is charged with surplus electricity, it can be used in exactly the same way as the current automobile. In this case, hydrogen and oxygen may be stored for a time required for the electroluminescent device to exhibit 100% capacity. Or if a large battery is mounted like a hybrid car, an electroluminescence device can be started immediately. The heat generated from the electroluminescent device and the fuel cell can be used for drying hydrogen and oxygen, and then used for heating as in the current automobile, or can be released from the radiator to the atmosphere.

  In addition to using the electroluminescent device according to the present invention in a hydrogen-using vehicle as described above, it is also conceivable to apply the electroluminescent device (hydrogen generating device) according to the present invention to other transportation facilities. That is, it is conceivable that a power generation system combining an electroluminescent device (hydrogen generator) and a fuel cell according to the present invention is mounted on a transportation system such as a ship or a long-distance train that travels in a section that is not electrified. . In such a case, there is no need to consider refueling, and a clean and environmentally friendly transportation system that does not emit exhaust gas can be realized. In addition, it is possible to electrify a section that is not electrified without installing a transmission line. For this reason, there is no need to transfer current over a long distance, so there is no power transmission loss, and there is no need to significantly reduce capital investment, accidents in the winter of power transmission lines, maintenance, or the like.

  As another application example of a system that combines an electroluminescence device (hydrogen generator) and a fuel cell, for example, a small-scale power generation facility can be compared with a conventional system by installing this system in a building or general home. Thus, it can be installed inexpensively and in large quantities. As a result, the need for large-scale power plant construction is reduced. Further, in this case, it is possible to construct a system with very little power transmission loss.

  In addition, since such a small-scale power generation facility can be realized, various applications such as power supply in remote islands, power supply for unmanned lighthouses, power supply for traffic signals, and power supply in remote areas can be considered.

  As a material constituting the cathode of the electroluminescent device according to the present invention, refractory metals such as niobium (Nb), molybdenum (Mo), tantalum (Ta), tungsten (W) can be used. Metals are also available. For example, as a material constituting the cathode, a transition metal such as titanium (Ti) or zirconium (Zr), or an iron-based metal such as pure iron (Fe), nickel (Ni), or stainless steel can be used.

  In order to verify the effect of the present invention, the following experiment was conducted. First, an experimental apparatus configured as shown in FIG. 1 was prepared. Here, a reaction vessel having a diameter of 10 cm, a height of 17 cm, and a volume of 1000 cc was prepared as a reaction vessel. Pyrex (registered trademark) was used as a material constituting the reaction vessel. A fluororesin synthetic lid was used as the lid of the reaction vessel. The diameter of this lid is 7 cm. Three lids made of platinum, a cooling water inlet and outlet, and a hole with a diameter of 2 cm were formed in the lid. A collection tube made of Pyrex (registered trademark) for collecting hydrogen and having a diameter of 5 cm and a length of 12 cm was attached to the hole downward. The upper part of the collection tube was covered with another fluororesin rubber. And the hole was made in this lid | cover and the glass connection part of the inlet_port | entrance of a water-cooled condenser was attached.

  The mixed gas of hydrogen and oxygen gas and water vapor discharged from the reaction vessel is passed through the water-cooled condenser through the glass connecting portion described above. When passing through this water-cooled condenser, the mixed gas is cooled and removed by condensing only water. A Tygon (registered trademark) tube is connected to the outlet of the water-cooled condenser, and the tube is connected to a hydrogen flow rate detector (flow meter 19). As a hydrogen flow rate detector, a model 3100 system of Kofloc (registered trademark) was used, and an apparatus of model number: CR-700 was used as a measuring device. The form of the measuring instrument part is a Heated tube thermal flow meter type. The minimum detection amount is 0.01 cc / min. The normal measurement value range is 1000 cc / min to 10 cc / min. The measurement accuracy of this flow meter is 1% or more.

  A fluororesin cooling tube was spirally wound around the hydrogen collection tube in the reaction vessel. And the platinum anode 5 (platinum net electrode) which is an anode was arrange | positioned circularly outside the hydrogen collection pipe | tube. In addition, platinum temperature detectors for measuring the water temperature are respectively attached to the inlet and the outlet of the cooling pipe. Furthermore, the temperature in the reaction vessel is measured at three locations where the distance (depth) from the lid is changed. The solution in the reaction vessel is stirred by a magnetic stirrer. The amount of heat generated with respect to the input power is measured by collecting data from all the measuring instruments described above every 5 seconds and continuously measuring the data.

As the cathode electrode, a tungsten electrode having a thickness of 1.5 mm and a length of 15 cm was used. This tungsten electrode has a tip portion (cathode portion) inserted into the reaction vessel exposed 2 cm, and the other portion (upper portion) is covered with a shrinkable fluororesin. Further, the electrolytic solution held in the reaction vessel at a grade of K ₂ CO _3, and prepared a light aqueous solution having a concentration of 0.2 M. As the power source 18, a Takasago (registered trademark) model number EH1500H was used, and as a measuring device, a Yokogawa (registered trademark) model number PZ4000 was used. The input voltage, current, and power were measured every 5 seconds. The power sampling time was 40 μs, the data length was 100 k, that is, 100,000 points were measured in 4 seconds. Then, an integrated value such as voltage and current every 40 μs was input as power data. The measurement accuracy at this time is 0.1%.

  The temperature in the reaction vessel was measured using a platinum temperature sensor (model number PLAMIC Pt-100Ω) manufactured by Nethsin (registered trademark) having an outer diameter of 1.5 mm. The measurement accuracy of this sensor is 0.01% or more. As cooling water for cooling the reaction vessel, water from tap water was passed through a Tygon (registered trademark) tube (tube), and the tube was immersed in a thermostatic bath to a constant temperature. And the liquid quantity was measured with the turbine meter. This turbine meter has a flow rate measurement accuracy of 0.01%. Data collection was performed with an Agilent® data logger (model number 34970A). The temperature was measured at three points in the reaction vessel and at one point in the temperature-controlled room, and data such as the amount of cooling water, the inlet temperature, the outlet temperature, the input voltage, the input current, the power, and the amount of generated hydrogen were measured. These data were finally captured every 5 seconds by the computer.

Here, the theoretical electrolysis electric energy of hydrogen in the electrolysis of water is 2.94 kwh / Nm ^3, which is apparent from Faraday's law as shown below. That is, when a direct current voltage is applied to water, the following reaction occurs and it is decomposed into hydrogen and oxygen. Since pure water has poor conductivity, a sulfated alkali hydroxide solution is used as the electrolyte.

(Cathode) 2H ₂ O + 2e ⁻ → 2OH ⁻ + H ₂
(Anode) 2OH ⁻ → H ₂ O + 2e ⁻ + 1 / 2O ₂
Overall 2H ₂ O → H ₂ + 1 / 2O ₂ + H ₂ O
In the reaction described above, two molecules of water on the anode side are lost and hydrogen is generated. On the anode side, one molecule of water is generated simultaneously with the generation of oxygen. As a result, one molecule of water was decomposed and one molecule of water moved from the hydrogen side (cathode side) to the oxygen side (anode side).

  The theoretical electrolysis voltage of this reaction is shown by the following equation.

E _r = E ₀ -RT / 2FlnP / P ₀
Here, E _r is the theoretical electrolysis voltage, E ₀ is the standard theoretical electrolysis voltage, and P ₀ and P are the water vapor tensions of pure water and electrolyte, respectively. E ₀ is given by ΔG ₀ / 2F, and is 1.226 V under the conditions of 25 ° C. and atmospheric pressure of 1 atm. The theoretical electrolysis voltage in this case is 1.229 V, which is slightly higher than the voltage for dividing pure water at the same temperature. The amount of electricity required to produce 1 m ³ of hydrogen is 2393 Ah from Faraday's law. And since this reaction proceeds quantitatively in practice, the minimum electric energy required is 2.94 Wh / m ³ .

In the system used for the experiment, in the electrolysis accompanied by thermal decomposition using the electroluminescence phenomenon, the hydrogen generation amount is 4.62 Nm ³ / h with respect to the power input amount of 10 kw / h, and the theoretical electrolysis hydrogen generation. A generation amount exceeding 1.35 times the amount was confirmed. In addition, it was confirmed that oxygen was generated from the anode, which could not be generated by ordinary electrolysis. This shows that thermal decomposition occurs near the cathode at high temperatures.

The measurement results of the above-described experiment are shown in FIG. FIG. 4 is a graph showing experimental results for confirming the effects of the present invention. In the graph shown in FIG. 4, the horizontal axis represents time (unit: S), and the vertical axis represents input power (unit: kw) and hydrogen generation amount (unit: kw). As can be seen from FIG. 4, the input power was about 450 W at the start of discharge, but then decreased with the consumption of the electrode, and after 1000 seconds, it was 100 W. On the other hand, the amount of hydrogen generated is 0.462 per 1 kW, that is, 4.62 Nm ³ / h per 10 kW / h. Further, when the amount of heat generated from the electroluminescence device was measured while the electroluminescence phenomenon continued, a value of 2249 kcal / h was measured.

In such experiments, we also measured and studied the generation of neutrons from the electroluminescence device. In the electroluminescent device, it is considered that the metal electrode undergoes very slow metal nucleolysis, and the number of neutrons generated at this time is about 1 / cm ² · sec. This is thought to be due to the fact that the neutrons measured in nature are 0.5 to 0.6 / cm ² · sec, and the regulation value according to the Basic Law for Nuclear Energy is 10 ¹⁶ / cm ² · sec. Is a low level, and it turns out that there is no problem. As neutron shielding means, paraffin is optimal, and if it is protected with paraffin having a thickness of about 10 cm in an experiment, sufficient safety can be ensured.

  To summarize the characteristic configuration of the electroluminescent device constituting the hydrogen gas generator as an example of the electroluminescent device according to the present invention described above, the electroluminescent device shown in FIG. And an electrolyte solution 4 held inside the reaction vessel 1, a platinum anode 5 as an anode containing a refractory metal, and a tip of a cathode terminal 2 as a cathode (which is arranged in contact with the electrolyte solution 4 ( The cathode terminal 2 is immersed in the electrolytic solution 4 and exposed without being covered with the covering material 10), and a power source 18 and a control device 17 as electroluminescence reaction means. The electrolytic solution 4 has an alkali metal carbonate concentration of 0.05 mol / liter or more as an electrolyte. The platinum anode 5 has a surface area that is 10 times or more the surface area of the tip of the cathode terminal 2. The power source 18 and the control device 17 cause an electroluminescence reaction by applying a voltage of 100 V or more to the tip of the cathode terminal 2 and the platinum anode 5. In addition, the voltage applied to the front-end | tip part of the cathode terminal 2 and the platinum anode 5 becomes like this. More preferably, it is 350V or more.

  In this way, the electroluminescence reaction can be generated continuously and stably. Therefore, the electroluminescent reaction can be industrially used stably, such as for the hydrogen gas generation process using the electroluminescent reaction.

  The electroluminescent device includes an electrolytic solution supply pipe 12, an electrolytic solution discharge pipe 13, a conduit, a pump, and an electrolytic solution tank as a concentration adjusting unit that adjusts an electrolyte concentration (concentration of alkali metal carbonate) in the electrolytic solution 4. It may be.

  In this case, the electrolyte concentration (concentration of the alkali metal carbonate) of the electrolytic solution 4 which is one of the conditions for continuously generating the electroluminescence reaction is adjusted so as to satisfy the predetermined numerical range described above. Can do. As a result, the electroluminescence reaction can be stably generated over a long period of time.

  A hydrogen gas generator according to the present invention includes the above electroluminescent device and a hydrogen-oxygen mixed gas extraction pipe 9 as a gas extraction member. The hydrogen-oxygen mixed gas extraction pipe 9 is connected to the reaction vessel 1 as an electrolytic tank of the electroluminescence device, and takes out hydrogen gas generated as a result of the decomposition of the electrolytic solution 4 by the electroluminescence reaction to the outside of the reaction vessel 1. It is. The hydrogen gas generator further includes an oxygen gas extraction pipe 8 as an oxygen gas extraction member for extracting oxygen gas generated as a result of decomposition of the electrolytic solution 4 by electroluminescence reaction to the outside of the reaction vessel 1 as an electrolytic cell. May be.

  In this way, water constituting the electrolyte solution 4 can be directly thermally decomposed by electroluminescence reaction, so that more hydrogen gas can be generated than when electrolysis of a normal electrolyte solution is performed. Can do. Further, since the electrolytic solution 4 is directly pyrolyzed by electroluminescence reaction, more oxygen gas is provided by providing the oxygen gas take-out pipe 8 as described above than when electrolyzing the normal electrolytic solution 4. Can also be taken out.

  The power generator according to the present invention includes a hydrogen gas generator (electrolytic light emitting device 32 shown in FIG. 2) as shown in FIG. 1 and a fuel cell 31 shown in FIG. The fuel cell 31 generates power using the hydrogen gas extracted from the electroluminescence device 32 as fuel. Moreover, when oxygen gas can be taken out from the hydrogen gas generator, the power generator may use the oxygen gas taken out from the hydrogen gas generator as a reaction gas (fuel gas) of the fuel cell 31.

  In this way, since hydrogen gas generated by the hydrogen gas generator (electroluminescence device 32) is used as fuel for the fuel cell 31, hydrogen is stored using a hydrogen storage alloy or the like for supplying to the fuel cell 31. There is no need to keep it. In the fuel cell 31, the hydrogen gas reacts with oxygen to become water, so that this water can be reused as the electrolytic solution of the electroluminescence device 32.

  The power generator removes liquid from the hydrogen gas taken out from the hydrogen gas generator (electrolytic light emitting device 32) and also adjusts the humidity of the hydrogen gas as a humidity controller / gas-liquid separator 33 (see FIG. 2). When oxygen gas can be taken out from the hydrogen gas generator, the humidity controller / gas-liquid separator 33 removes liquid from the oxygen gas taken out from the hydrogen gas generator (electroluminescence device 32), It may have a function of adjusting the humidity of the oxygen gas. In this case, since the humidity of the hydrogen gas (or oxygen gas and hydrogen gas) can be adjusted to a humidity suitable for the reaction in the fuel cell 31, the reaction in the fuel cell 31 is more efficiently performed. Can be done. Therefore, the power generation efficiency in the fuel cell 31 can be improved.

  In the above power generator, the hydrogen gas generator (electroluminescent device) serves as an oxygen gas extraction member that extracts oxygen gas generated as a result of decomposition of the electrolytic solution 4 by electroluminescence reaction to the outside of the reaction vessel 1 as an electrolytic cell. An oxygen gas extraction pipe 8 may be included. In the power generation device, a hydrogen gas generator (electrolytic light emitting device 32) and a fuel cell 31 are connected to the fuel cell 31 via a sealed circuit (in FIG. 2, from the electrolytic light emitting device 32 via a humidity controller / gas-liquid separator 33). A circulation constituted by a gas and oxygen gas supply pipe, a pipe for refluxing water from the fuel cell 31 to the electroluminescent device 32, the electroluminescent device 32, the humidity controller / gas-liquid separator 33, and the fuel cell 31. Pipe line). That is, the power generation apparatus uses hydrogen gas and oxygen gas extracted from the gas extraction member (hydrogen-oxygen mixed gas extraction tube 9) and the oxygen gas extraction member (oxygen gas extraction tube 8) of the hydrogen gas generator as fuel. A supply line (hydrogen and oxygen gas supply pipes connected to the fuel cell 31 from the electroluminescence device 32 via the humidity controller / gas-liquid separator 33) to be supplied to the battery 31, and hydrogen generated as a result of power generation in the fuel cell 31 A reflux line (pipe for refluxing water from the fuel cell 31 to the electroluminescence device 32) for refluxing water generated from the gas and oxygen gas to the reaction vessel 1 of the hydrogen gas generator (electroluminescence device 32); May be provided.

  In this case, since there is no need to supply a reaction gas (fuel gas) such as hydrogen gas or oxygen gas used in the fuel cell 31 from the outside to the power generation device, the range of selection of the installation location and use environment of the power generation device can be expanded. it can.

  The electroluminescence cogeneration system shown in FIG. 2 as a cogeneration system according to the present invention includes the power generator, a heat exchanger container 15 as a thermal energy extraction member that extracts thermal energy from the power generator, a pipe line 49, The hot water storage tank 40, the heat exchanger 42 for heat radiation, the low-temperature water absorption refrigerator 43, the cooling tower 44, the heat exchanger 47 for hot water supply, etc. are provided.

  If it does in this way, while taking out electric energy from fuel cell 31 which constitutes a power generator, exhaust heat accompanying generation of electricity or generation of hydrogen gas can be taken out as thermal energy. As a result, energy utilization efficiency can be improved.

  In the hydrogen gas generation method according to the present invention, an electrolytic solution 4 having an electrolyte concentration (alkali metal carbonate concentration) of 0.05 mol / liter or more is disposed in a reaction vessel 1 (see FIG. 1) as an electrolytic cell. Perform the process. And the process of immersing the cathode terminal 2 front-end | tip part as a cathode, and the platinum anode 5 as an anode in the electrolyte solution 4 is implemented. The tip of the cathode terminal 2 and the platinum anode 5 each contain a refractory metal. The platinum anode 5 has a surface area that is 10 times or more the surface area of the tip of the cathode terminal 2. A step of causing an electroluminescence reaction is performed by applying a voltage of 350 V or more to the tip of the cathode terminal 2 and the platinum anode 5. And the process which takes out the hydrogen gas which arises as a result of having decomposed | disassembled the water which comprises the electrolyte solution 4 by an electroluminescent reaction out of the reaction container 1 as an electrolytic vessel through the hydrogen oxygen mixed gas extraction pipe | tube 9 is implemented. In the hydrogen gas generation method, an oxygen gas extraction step of extracting oxygen gas generated as a result of the decomposition of the electrolytic solution 4 by electroluminescence reaction to the outside of the reaction vessel 1 through the oxygen gas extraction pipe 8 may be performed. Good.

  In this way, water constituting the electrolytic solution 4 can be directly thermally decomposed using electroluminescence reaction, so that more hydrogen gas is generated than when the electrolytic solution 4 is electrolyzed. Can be made.

  In the hydrogen gas generation method, the step of causing the electroluminescence reaction may include adjusting the temperature of the electrolytic solution 4 to be 70 ° C. or higher and 100 ° C. or lower. In this case, hydrogen gas can be stably generated by the electroluminescence reaction.

  In the hydrogen gas generation method, the voltage applied to the tip of the cathode terminal 2 and the platinum anode 5 in the step of causing the electroluminescence reaction may be a pulse voltage. In this case, the electroluminescence reaction can be continued while reducing the wear of the electrodes such as the tip of the cathode terminal 2 and the platinum anode 5. Therefore, hydrogen gas can be generated stably.

  The power generation method according to the present invention includes a step of obtaining hydrogen gas by performing the hydrogen gas generation method, and a step of generating power by the fuel cell 31 using the hydrogen gas as a fuel gas. In the power generation method, when oxygen gas can be obtained by performing the hydrogen gas generation method, the oxygen gas may be used as a reaction gas for the fuel cell 31 in the power generation step. In this way, the hydrogen gas (or hydrogen gas and oxygen gas) generated by the electroluminescence device 32 (see FIG. 2) as the hydrogen gas generator is used as the fuel for the fuel cell 31, so that it is supplied to the fuel cell 31. There is no need to store hydrogen using a hydrogen storage alloy or the like. In the fuel cell 31, the hydrogen gas reacts with oxygen to become water, so that this water can be reused as the electrolytic solution of the electroluminescence device 32. In addition, when the oxygen gas extracted from the electroluminescence device 32 is used as the reaction gas of the fuel cell 31, it is not necessary to separately secure the oxygen gas to be supplied to the fuel cell 31, so that the electroluminescence device 32 and the fuel cell 31 are used. It becomes possible to constitute a closed circuit.

  The power generation method further includes a step of removing a liquid such as water from the hydrogen gas supplied to the fuel cell 31 using the humidity controller / gas-liquid separator 33 and adjusting the humidity of the hydrogen gas. Also good. In the power generation method, when oxygen gas can also be obtained by performing the hydrogen gas power generation method, the liquid is removed from the oxygen gas using the humidity controller / gas-liquid separator 33, and the oxygen gas A step of adjusting the humidity may be further provided. In this case, since the humidity of the hydrogen gas (or hydrogen gas and oxygen gas) supplied from the electroluminescent device 32 to the fuel cell 31 can be adjusted to a humidity suitable for the reaction in the fuel cell 31, The reaction in the fuel cell 31 can be performed more efficiently. Therefore, the power generation efficiency in the fuel cell 31 can be improved.

  The energy supply method according to the present invention includes an electric energy supply step of supplying electric energy from the fuel cell 31 to the outside by executing the power generation method, and thermal energy generated in accordance with the execution of the power generation method. From at least one of the reaction vessel 1 (see FIG. 1) as an electrolytic cell and the fuel cell 31 (see FIG. 2), the heat exchanger vessel 15 (see FIG. 1), the pipe line 49, the hot water storage tank 40, and the like are used. And a heat energy supply step for supplying to the outside. If it does in this way, while taking out electrical energy from the power generator containing fuel cell 31, exhaust heat accompanying generation of electricity or generation of hydrogen gas can be taken out as thermal energy. As a result, energy utilization efficiency can be improved.

  An electrode for an electroluminescence device according to the present invention is an electrode for an electroluminescence device which is disposed so as to be in contact with the electrolyte solution 4 and used for generating an electroluminescence reaction, and serves as a cathode containing a refractory metal. The tip of the cathode terminal 2 (the tip that is immersed in the electrolyte solution 4 and exposed without being covered with the coating material 10 in the cathode terminal 2), and the surface area of the tip of the cathode terminal 2 is 10 And a platinum anode 5 as an anode having a surface area more than doubled.

  By using such an electrode for an electroluminescence device, an electroluminescence reaction can be efficiently generated in the electroluminescence device 32.

  The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the embodiments and examples described above but by the scope of claims for patent, and is intended to include all modifications within the meaning and scope equivalent to the scope of claims for patent.

It is a schematic diagram which shows the hydrogen generator by this invention. It is a schematic diagram which shows the structure of the electroluminescent cogeneration system to which the hydrogen generator by this invention is applied. It is a schematic diagram for demonstrating the material balance and heat balance in the electroluminescence cogeneration system shown in FIG. It is a graph which shows the experimental result for confirming the effect of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Reaction container, 2 Cathode terminal, 3 Anode terminal, 4 Electrolyte, 5 Platinum anode, 6 Partition, 7 Liquid surface, 8 Oxygen gas extraction pipe, 9 Hydrogen oxygen mixed gas extraction pipe, 10, 11 Coating material, 12 Electrolyte Replenishment pipe, 13 Electrolyte discharge pipe, 14 Fixing member, 15 Heat exchanger vessel, 16a, 16b Conductor wire, 17 Control device, 18 Power supply, 19 Flow meter, 20, 49 Pipe line, 21, 39 Valve, 22 Mass spectrometry 23, heat exchange medium, 31 fuel cell, 32 electroluminescence device, 33 humidity controller / gas-liquid separator, 34 external power source, 35 watt-hour meter, 36 power distribution device, 37 power conversion device, 38 water supply source, 40 Hot water storage tank, 41, 45, 46, 48 pump, 42 heat exchanger for heat dissipation, 43 low temperature water absorption refrigerator, 44 cooling tower, 47 heat exchanger for hot water supply, 60 power supply, 61 doin recovery, 6 2,63 Waste heat recovery.

Claims (14)

An electrolytic cell;
An electrolytic solution held inside the electrolytic layer and having an electrolyte concentration of 0.05 mol / liter or more;
A cathode disposed in contact with the electrolyte and comprising a refractory metal;
An anode disposed in contact with the electrolyte, comprising a refractory metal and having a surface area greater than or equal to 10 times the surface area of the cathode;
An electroluminescent device comprising: an electroluminescent reaction means that causes an electroluminescent reaction by applying a voltage of 100 V or more to the cathode and the anode.   The electroluminescent device according to claim 1, further comprising a concentration adjusting unit that adjusts an electrolyte concentration in the electrolytic solution. The electroluminescent device according to claim 1 or 2,
A hydrogen gas generator, comprising: a gas extraction member connected to the electrolytic cell and configured to extract hydrogen gas generated as a result of decomposition of the electrolytic solution by the electroluminescence reaction to the outside of the electrolytic cell. A hydrogen gas generator according to claim 3;
A power generation device comprising: a fuel cell that generates power using hydrogen gas extracted from the hydrogen gas generation device as fuel.   The power generation device according to claim 4, further comprising an adjustment device that removes a liquid from the hydrogen gas taken out of the hydrogen gas generation device and adjusts a humidity of the hydrogen gas. The hydrogen gas generator includes an oxygen gas extraction member that extracts oxygen gas generated as a result of decomposition of the electrolytic solution by the electroluminescence reaction to the outside of the electrolytic cell,
A supply line for supplying the fuel cell with the hydrogen gas and the oxygen gas extracted from the gas extraction member and the oxygen gas extraction member of the hydrogen gas generator;
A reflux line for returning water generated from the hydrogen gas and the oxygen gas as a result of power generation in the fuel cell to the electrolytic cell of the hydrogen gas generator;
The power generator according to claim 4 or 5, wherein the hydrogen gas generator and the fuel cell constitute a closed circuit. The power generation device according to any one of claims 4 to 6,
A cogeneration system comprising: a thermal energy extraction member that extracts thermal energy from the power generation device. Placing an electrolytic solution having an electrolyte concentration of 0.05 mol / liter or more in an electrolytic cell;
A step of immersing a cathode containing a refractory metal and an anode containing a refractory metal and having a surface area of 10 times or more the surface area of the cathode in the electrolytic solution;
A step of causing electroluminescence reaction by applying a voltage of 350 V or more to the cathode and the anode;
And a step of taking out hydrogen gas generated as a result of decomposition of the electrolytic solution by the electroluminescence reaction to the outside of the electrolytic cell.   The method for generating hydrogen gas according to claim 8, wherein the step of causing the electroluminescence reaction includes adjusting the temperature of the electrolytic solution to be 70 ° C. or higher and 100 ° C. or lower.   The method for generating hydrogen gas according to claim 8 or 9, wherein, in the step of causing the electroluminescence reaction, a voltage applied to the cathode and the anode is a pulse voltage. A step of obtaining hydrogen gas by carrying out the method for generating hydrogen gas according to any one of claims 8 to 10,
Using the hydrogen gas as a fuel gas and generating electricity with a fuel cell.   The power generation method according to claim 11, further comprising a step of removing a liquid from the hydrogen gas supplied to the fuel cell and adjusting a humidity of the hydrogen gas. An electric energy supply step of supplying electric energy from the fuel cell to the outside by carrying out the power generation method according to claim 11 or 12,
An energy supply method comprising: a heat energy supply step of supplying heat energy generated by performing the power generation method from at least one of the electrolytic cell and the fuel cell to the outside. An electrode for an electroluminescent device that is disposed in contact with an electrolytic solution and is used to generate an electroluminescent reaction,
A cathode containing a refractory metal;
An electrode for an electroluminescence device, comprising an anode containing a refractory metal and having a surface area of 10 times or more the surface area of the cathode.

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