JP7250629B2 - Hydrogen production method and hydrogen production device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a hydrogen production method and a hydrogen production apparatus for generating hydrogen from reformed water and metals with a strong ionization tendency such as iron, nickel, zinc, magnesium, aluminum and tin.

The use of hydrogen as fuel gas is known in the prior art.
Many inventions have been provided as production methods for producing hydrogen for that purpose.
For example, a. a method of thermally decomposing 100% water to obtain hydrogen; b. The IS (Iodine-Sulfe) method and the like are known, in which sulfuric acid is thermally decomposed and hydrogen is extracted using iodine water.
b. In the IS method, hydrogen and oxygen are decomposed and extracted from water through three processes of a Bunsen reaction process, a hydrogen iodide concentration decomposition process, and a sulfuric acid concentration decomposition process (Japanese Patent Application Laid-Open No. 2005-41764). , see Patent Document 1).
In addition, c. A water decomposition method is known in which metallic zinc, magnetite and water are reacted to generate hydrogen as a reaction product (Japanese Patent Application Laid-Open No. 2001-270701, Patent Document 2).

Furthermore, d. A method for producing hydrogen is also known in which hydrogen is generated by contacting aluminum or magnesium with water (Japanese Patent Application Laid-Open No. 2007-290888, Patent Document 3).

JP-A-2005-41764 Japanese Patent Application Laid-Open No. 2001-270701 JP 2007-290888 A

a. In the method of thermally decomposing 100% water to obtain hydrogen, since water has a strong bond with hydrogen and oxygen, it will not decompose into hydrogen and oxygen unless it is given a temperature of 3,000°C to 5,000°C theoretically. It is said. The method of obtaining hydrogen by thermally decomposing water at a temperature of 3,000°C or higher does not provide a substantial method of obtaining a high temperature of 3,000°C or higher. There are many problems, such as the inability to make inexpensive equipment to maintain the temperature and the inability to think of a means of continuously supplying water to a high-temperature space. has not been realized.

Moreover, b. Since the IS method disclosed in Patent Document 1 requires high heat of about 900° C., a high-temperature gas furnace or the like must be used as a heat source. This high-temperature gas-cooled reactor is expensive to manufacture, and hydrogen is produced through three processes, making the cost of producing hydrogen extremely high.

Furthermore, c. In the water decomposition method disclosed in Patent Document 2, hydrogen is produced by reacting metallic zinc and magnetite with steam at 600°C, and heating means for producing steam at 600°C must be provided.

d. In the method for producing hydrogen disclosed in Patent Document 3, non-freezing water having a pH of 4 to 10 is used as water, and hydrogen is generated even at 0° C. or below. In this patent document 3, hydrogen is generated by the reaction of aluminum and water, but since the reaction is performed at a low temperature of 0 ° C. or less, a large amount of hydrogen cannot be generated at low temperatures, and hydrogen can be generated with high economic efficiency. cannot be generated.

The present invention provides a hydrogen production method capable of producing hydrogen by bringing reformed water into contact with iron, nickel, zinc, magnesium, aluminum, and tin, and reformed water and iron, nickel, zinc, By contacting magnesium, aluminum, and tin (hereinafter referred to as metals with a strong ionization tendency), hydrogen is efficiently produced at low temperatures using the heat of its own reaction, using as little external energy as possible. It is an object of the present invention to provide a hydrogen production apparatus for

In the method for producing hydrogen of the present invention, water is tap water standard as drinking water in Japan, and other water is water filtered by a water purifier, sea water, water with severe dirt, hard water, soft water, RO membrane etc. Use pure water. In addition, water with minerals added to such water is used as a condition. After that, by passing through natural ore or artificial ore, or natural ore and artificial ore, the product is used as modified water, and the modified water and the metal having a strong ionization tendency are put into the reaction vessel and placed in the reaction vessel. By setting the temperature in the reaction vessel to 1 ° C or higher and lower than the boiling point of the reformed water in a state of contact with the water, the reformed water and the metal with a strong ionization tendency are reacted to generate hydrogen. and

In the present invention, a metal with a strong ionization tendency is powdered, ingot-shaped, granular, or powdered in any form, and the temperature in the reaction vessel is set to 1° C. or higher and lower than the boiling point of reformed water to generate hydrogen. The modified water may be acidic (acidic modified water) or alkaline (alkaline modified water). Then, by supplying the special acidic or alkaline water in the reaction vessel with a new powder made of a metal with a strong ionization tendency, or ingot-shaped, granular, or powder of any shape, the reaction can be carried out without heating by a heating means. It is characterized in that the temperature in the vessel is maintained between 1° C. or higher and lower than the boiling point of reformed water to generate hydrogen.

The present invention is also characterized in that when the temperature in the reaction vessel is 1° C. or more and less than 80° C., the temperature in the reaction vessel is continuously increased by heating means and electrolysis.

The present invention uses pyrite, marcasite, cinnabar, galena, bornite, halide minerals, fluorite, cryolite, tourmaline, obsidian, magnesium, calcite, as natural ores for producing modified water. Ulexite (TV stone), Coleman stone, borax, howlite, gypsum, barite, celestite, uranium apatite, carnotite, brocade stone, black sand gold stone, maifan stone, bad gastein ore, quartz, etc. The particle size may be 1 to 5 mm, 5 to 10 mm, 10 to 20 mm, 20 to 40 mm, or 30 to 50 mm depending on the type. Artificial ores for generating reformed water include terahertz ores. When artificial ore is used, at least one kind of metal consisting of silica, aluminum, iron, calcium, zinc, chromium, manganese, zirconium, strontium, stainless steel, silver, etc. is mixed as a substance other than artificial ore. It is characterized. In addition to natural ores, it is also effective to add minerals that can be extracted from natural ores. For example, minerals extracted from caustic granite are used. Examples of added mineral components and added solid substances include the following calcium, phosphorus, silicon, magnesium, sodium, selenium, zinc, vanadium, germanium, nickel, manganese, molybdenum, copper, tungsten, cobalt, lithium, barium, and iron. , potassium, aluminum, rubidium, titanium and the like. The present invention is characterized in that 3 parts by weight or more, preferably 15 parts by weight or more of a metal having a strong ionization tendency is added to 100 parts by weight of the reformed water. Further, the present invention is characterized in that the weight part of the metal having a strong ionization tendency is 10 to 40 weight parts or more.

The present invention adds an acidic substance or an alkaline substance to the reformed water. For example, typical acidic substances include sulfuric acid. Alkaline substances include sodium hydroxide. The procedure for preparing an acidic aqueous solution is the same as for preparing an alkaline aqueous solution. The next step is to prepare an alkaline aqueous solution. It is characterized by preparing an aqueous sodium hydroxide solution containing sodium hydroxide and bringing it into contact with a metal having a strong ionization tendency in a reaction vessel.
The present invention is characterized in that the temperature in the reaction vessel is raised to 25° C. or higher only by the heat of reaction between an aqueous sodium hydroxide solution and a metal having a strong ionization tendency without using a heating means for applying heat from the outside of the reaction vessel. and
The present invention is characterized in that the temperature in the reaction vessel is raised to 25° C. or higher by the heat of reaction between the acidic dilute sulfuric acid aqueous solution or the sodium hydroxide aqueous solution and the metal having a strong ionization tendency.
In the present invention, for example, when sulfuric acid is used, it is diluted to a concentration of 0.1% or more in the case of acidity, and the concentration of sodium hydroxide in the sodium hydroxide aqueous solution is 0.1% or more in the case of alkalinity. It is characterized by
The present invention is characterized in that the concentration range of the sulfuric acid aqueous solution is 0.1% to 15%, and in the case of alkalinity, the concentration of sodium hydroxide in the sodium hydroxide aqueous solution is 0.1% to 3%. It is characterized by

In the present invention, in order to bring reformed water into contact with a metal having a strong ionization tendency in the reaction vessel, a reaction vessel for containing a metal having a strong ionization tendency and a metal having a strong ionization tendency are introduced into the reaction vessel. The metal with a strong ionization tendency introduced into the reaction vessel from the metal introduction means with a strong ionization tendency becomes an oxide powder after hydrogen is generated, and the metal with a strong ionization tendency undergoes a change. . The metal having a strong ionization tendency to be charged should be in the form of a cartridge so that it can be easily replaced in the reaction vessel, and the changed metal oxide powder can be separated and recovered in the cartridge. It is characterized by being a device that can be taken out in a state.

Further, the present invention is characterized in that the metal having a strong ionization tendency is put into the bottom of the reaction vessel, and the liquid level of the acidic or alkaline aqueous solution is set above the top of the metals. Moreover, the water that comes into contact with the metal having a strong ionization tendency can be brought into contact with the metal in a flowing state as well as in a stationary state. A method of continuously bringing water into contact with a fixed metal having a strong ionization tendency is also available. Conversely, the reaction can be carried out continuously in any desired state by continuously bringing a metal having a strong ionization tendency into contact with water. By doing so, the reaction can be stopped and started, and the reaction can be repeated at any desired time. Another feature is that when the pressure in the reaction vessel reaches 6 atmospheres, the reaction is suppressed and becomes difficult to react. Hydrogen is generated from within the reaction vessel, and when the hydrogen cannot move out of the reaction vessel, pressure builds up within the reaction vessel. At this time, when a pressure of 6 atmospheres or more is applied to the inside of the reaction vessel, the reaction speed tends to be suppressed. Since this reformed water and a metal with a strong ionization tendency promote the reaction, it is possible to simultaneously generate hydrogen by electrolysis by providing an electrode in a tank in the reformed water. In addition to the electrodes, metals with a strong ionization tendency also react, generating a large amount of hydrogen from the charged metals and reformed water. An electrode rod or an electrode plate can be used as the electrode, and examples of materials thereof include stainless steel, copper, and titanium. At this time, reformed water, which is water in which hydrogen, oxygen, and water move in a manner similar to the state of a subcritical point, is mixed, and the hydrogen concentration can be arbitrarily increased, and oxyhydrogen gas can be generated. This is a gaseous substance in the form of oxyhydrogen gas (HHO), which is also called Brown's gas.

The materials used in claim 1 of the hydrogen production method of the present invention are only two types of materials, many of which can be said to be commercially available and can be easily prepared, and reformed water. Hydrogen is generated by raising the temperature in the container to 1°C or higher. In the present invention, hydrogen can be produced at a very low cost by using only metals with a strong ionization tendency and reformed water without using chemical agents or metals other than aluminum as main materials. It is also characterized by the fact that it is safe to use only substances that are safe and harmless to the body by using natural minerals as main ingredients.

The reformed water used in the present invention contains a large amount of hydrogen atoms such as hydroxyl ions (H ₃ O ₂₋ ), hydroxide ions (OH+) and hydrogen ions (H+). Since the metal with a strong ionization tendency to be used is an electrode amphoteric element, many positive electrodes and negative electrodes appear in the metal when the temperature of the reformed water reaches 25 ° C or higher, and the positive electrodes and negative electrodes generates a weak electric current to promote the electrolysis (ion reaction) of the reformed water in the reaction vessel, generating a large amount of hydrogen from the reformed water. Furthermore, since it takes a long time to generate hydrogen from the reformed water, a large amount of hydrogen can be generated. It is believed that the present invention has the effect of delaying the formation of a film on the surface of a metal with a strong ionization tendency due to hydroxyl ions (H ₃ O ₂₋ ), which are typical states contained in the modified water. guessed.

1 is a schematic structural plan view of a hydrogen production apparatus applied to the hydrogen production method of the present invention; FIG. 1 is a schematic structural elevation view of a hydrogen production apparatus applied to the hydrogen production method of the present invention; FIG.

A method for producing hydrogen according to the present invention will be described with reference to the drawings.
1 and 2 show a hydrogen production apparatus used in the hydrogen production method of the present invention.
In the structural diagrams of the hydrogen production apparatus shown in FIGS. 1 and 2, a main reaction tank 11 holds an aluminum cartridge 12, into which raw water (reformed water) 11a is injected. immersed in. A catalyst feeder 13 is installed on the lid 11b of the upper portion of the reaction tank 11, and a catalyst composed of an aqueous sodium hydroxide solution is injected into the reaction tank 11 at an appropriate timing or amount.
Also, the level of the raw water 11a is constantly measured and constantly refilled to keep the aluminum cartridge 12 in the raw water 11a. Further, a relief valve 14 is provided at an appropriate position so as to release gas pressure when the pressure inside the reaction vessel 11 becomes too high.
In addition, a second reaction tank 18 is installed adjacent to the main reaction tank 11, and the hydrogen gas generated in each reaction tank 11, 12 is sent to a separation tank 15, where only hydrogen gas is taken out, It can be stored in the storage tank 17 under vacuum at the same pressure as that generated by the reaction.
Hydrogen gas can be pressurized by a compressor 16 or the like and sent to the storage tank 17 as necessary.
20 is a control panel for controlling the whole.

In the present invention, when hydrogen is generated by contacting reformed water with a metal having a strong ionization tendency in a reaction vessel, the heating temperature of the reaction vessel is 1 ° C. or higher and less than the boiling point of the reformed water. Heating the reaction vessel under atmospheric pressure can suffice. Since it is heated under atmospheric pressure, it is inexpensive and simple without the need for a special device that has to raise the temperature to 3,000°C to 5,000°C, unlike the conventional thermal decomposition of water. Hydrogen can be generated with a simple device. In the case of using a heating means to heat the highly ionized metal and the reformed water in the reaction vessel, stop the contact between the water and the highly ionized metal to be used, and stop the heating. , the generation of hydrogen can be stopped. Therefore, it is possible to quickly generate and stop hydrogen, and it can be applied to various devices using hydrogen as fuel.

A reaction vessel containing reformed water and a metal with a strong ionization tendency is once heated to 25° C. or higher to generate hydrogen, and then the reformed water is brought into contact with a new metal with a strong ionization tendency. For example, the temperature in the reaction vessel can be maintained at 25° C. or higher without heating by a heating means due to contact between the reformed water after hydrogen generation and the same new metal (if placed in the reaction vessel). and hydrogen continues to be generated. Since hydrogen is continuously generated without using a heating means in this way, the fuel cost required for heating can be saved. This is because neutral or alkaline reformed water reacts with a metal with a strong ionization tendency to partially generate hydrogen, and then the reformed water becomes alkaline, and this reaction can be performed without heating with a heating means. The alkaline reformed water in the vessel reacts with the same newly added metal, the temperature in the reaction vessel is maintained above 25° C., and hydrogen is continuously generated. When a metal with a strong ionization tendency is made into powder, the amount of hydrogen generated is greatly increased and the reaction occurs in a short time. Therefore, the reaction completion time is also early. This is because the metal surface area is large and there are many contacts with the reformed water.

A metal with a strong ionization tendency is placed in a reaction vessel, and the top of the metal with a strong ionization tendency is covered with modified water, an aqueous sulfuric acid solution, or an aqueous sodium hydroxide solution. That is, if a metal having a strong ionization tendency is immersed in modified water, an aqueous sulfuric acid solution, or an aqueous sodium hydroxide solution, the hydroxyl ion (H ₃ O ₂₋ ) contained in the modified water reduces the ionization tendency. It is possible to delay the generation of an oxide film on the surface of a strong metal, and to prolong the hydrogen generation time.

An aqueous sodium hydroxide solution in which sodium hydroxide is mixed with modified water may be used instead of only the modified water. Alternatively, a sulfuric acid aqueous solution obtained by diluting sulfuric acid in reformed water may be used. For example, when using an aqueous sodium hydroxide solution obtained by mixing modified water with sodium hydroxide, heat of reaction is generated by bringing the aqueous sodium hydroxide solution and a metal with a strong ionization tendency into contact in the reaction vessel. The reaction heat can raise the temperature in the reaction vessel to 1 to 25° C. by self-heating, and hydrogen can be generated in the reaction vessel without using a heating means for applying heat from the outside of the reaction vessel. can. Due to the heat of reaction between the metal with a strong ionization tendency and the sodium hydroxide aqueous solution, the temperature inside the reaction vessel rises from 25°C to 80°C, at which a large amount of hydrogen is generated. can also be adapted.
Conventional heating means for applying heat from the outside of the reaction vessel has a temperature of 600° C. to 5,000° C., requiring expensive equipment, but in the present invention, the heating means for applying heat from the outside of the reaction vessel is omitted. It uses an aqueous sodium hydroxide solution obtained by adding sodium hydroxide to reformed water or an aqueous sulfuric acid solution obtained by diluting sulfuric acid and a metal with a strong ionization tendency, and can produce hydrogen at low cost.

The present invention generates hydrogen by self-heating due to reaction heat, and does not use a heating means for applying heat from the outside of the reaction vessel by fire or electricity. It becomes possible to mount it on an automobile or the like.
The purity of the generated hydrogen is very high. The hydrogen concentration of a normal hydrogen cylinder is about 88% to 95%. The hydrogen generated in the present invention has a purity ranging from 98% to 100%. Moreover, the apparatus of the present invention is characterized in that the wettability of hydrogen can be freely adjusted. The wettability is considered to be about 0.5% to 5%. In addition, it is characterized by being able to burn at a higher temperature than ordinary hydrogen burning due to the influence of the humidity.
In addition, by increasing the humidity, when the hydrogen is supplied to the fuel cell, it is combined with the oxygen in the fuel cell and has the effect of increasing the power generation capacity. The hydrogen of the present invention has a high efficiency rate even for fuel cells because the reaction with the electrolytic solution film in the fuel cell is better and it is easier to generate power at a lower temperature when the humidity is higher than when it is dry hydrogen. It can be said.

In the method for producing hydrogen of the present invention, by using an aqueous sodium hydroxide solution in which sodium hydroxide is mixed with reformed water or an aqueous sulfuric acid solution in which sulfuric acid is mixed and diluted, hydrogen can be increased, and the amount of oxygen generated can be greatly reduced. If the oxygen generation ratio is made as low as possible, the method of separating oxygen from the gas containing hydrogen and oxygen can be simplified, and the cost of producing hydrogen can be reduced.

The hydrogen generator of the present invention uses reformed alkaline or acidic water that generates hydrogen only by contact with a metal having a strong ionization tendency without using a heating means. As water that generates hydrogen only by contact with a metal with a strong ionization tendency, reformed water is brought into contact with a metal with a strong ionization tendency, and is heated from 25° C. to 80° C. to generate hydrogen. A typical example is to use either water (alkaline or acidic) or an aqueous solution of sulfuric acid mixed with special water and sulfuric acid and an aqueous solution of sodium hydroxide mixed with sodium hydroxide, but other acidity And it can also react with an alkaline aqueous solution. A mounting member (cartridge) for mounting a metal is contained in a reaction container for containing acid- or alkaline-modified water and a metal with a strong ionization tendency, and the mounting member is placed on the bottom surface of the reaction container. Arrange in the reaction vessel so as to be higher. The metal on the mounting member melts and changes to an oxide by reacting with the alkaline modified water. Converts to dissolved hydroxides by reaction with acidic reformed water.

11 Main Reactor 11a Raw Water 11b Lid 12 Cartridge 13 Catalyst Feeder 14 Relief Valve 15 Separation Tank 16 Compressor 17 Storage Tank 18 Secondary Reactor 20 Control Panel

Claims (1)

As raw water, use water that has been filtered by a water purifier, water that has been filtered through a water purifier, sea water, water that is extremely polluted, hard water, or soft water that has been purified using an RO membrane. or modified water obtained by using water to which minerals have been added, and passing the raw water through natural ore or artificial ore, or natural ore and artificial ore;
a metal consisting of iron, nickel, zinc, magnesium, aluminum, or tin;
a reaction vessel for containing the metal consisting of iron, nickel, zinc, magnesium, aluminum, or tin;
a cartridge-type metal charging means for charging the metal consisting of iron, nickel, zinc, magnesium, aluminum, or tin into the reaction vessel;
In a hydrogen production device consisting of
The metal made of any one of iron, nickel, zinc, magnesium, aluminum, and tin charged into the reaction vessel from the metal charging means is brought into contact with the reformed water and converted into oxide powder after hydrogen generation. The hydrogen production apparatus is such that the metal consisting of any one of iron, nickel, zinc, magnesium, aluminum, and tin undergoes a change, and the changed metal oxide powder is separated and recovered in the cartridge. A hydrogen production apparatus that makes it possible to extract hydrogen in a possible state ,
The apparatus for producing hydrogen is characterized in that the reaction vessel is adapted to suppress the reaction speed when the pressure inside the reaction vessel rises and a pressure of 6 atmospheres or more is applied to the inside of the reaction vessel.

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