WO2015093547A1 - Method for generating hydrogen and hydrogen generator - Google Patents

Method for generating hydrogen and hydrogen generator Download PDF

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WO2015093547A1
WO2015093547A1 PCT/JP2014/083464 JP2014083464W WO2015093547A1 WO 2015093547 A1 WO2015093547 A1 WO 2015093547A1 JP 2014083464 W JP2014083464 W JP 2014083464W WO 2015093547 A1 WO2015093547 A1 WO 2015093547A1
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alkali metal
hydrogen
generation step
hydrogen generation
generated
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French (fr)
Japanese (ja)
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小島　由継
裕樹 宮岡
市川　貴之
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国立大学法人広島大学
昭和電工株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0203—Preparation of oxygen from inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
    • C01D1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
    • C01D1/04—Hydroxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a hydrogen production method and a hydrogen production apparatus.
  • Patent Document 1 and Non-Patent Document 1 disclose a method for generating hydrogen using an alkali metal.
  • an alkali metal hydroxide and an alkali metal are reacted to generate an alkali metal oxide and hydrogen (first step), the generated alkali metal oxide is decomposed, and an alkali metal peroxide and an alkali metal are decomposed.
  • the second step is a step of reacting an alkali metal peroxide with water to generate an alkali metal hydroxide and oxygen (third step).
  • Patent Document 1 and Non-Patent Document 1 1 mol of hydrogen is produced using 2 mol of alkali metal hydroxide and 2 mol of alkali metal in one cycle of the first step, the second step, and the third step. It is a thing and cannot be said to be efficient.
  • the present invention has been made in view of the above matters, and an object of the present invention is to provide a hydrogen production method and a hydrogen production apparatus capable of efficiently producing hydrogen.
  • the hydrogen production method includes: A first hydrogen generation step in which an alkali metal and an alkali metal hydroxide are reacted to generate an alkali metal oxide and a hydrogen molecule; A reduction step of decomposing the alkali metal oxide produced in the first hydrogen generation step to produce an alkali metal and oxygen molecules; A second hydrogen generation step of reacting the alkali metal produced in the reduction step with water to produce an alkali metal hydroxide and hydrogen molecules,
  • the first hydrogen generation step, the reduction step, and the second hydrogen generation step are performed in this order. It is characterized by that.
  • the second hydrogen generation step a part of the alkali metal generated in the reduction step is reacted with water
  • the first hydrogen generation step the remaining alkali metal generated in the reduction step and the alkali metal hydroxide generated in the second hydrogen generation step are used.
  • the first hydrogen generation step, the reduction step, and the second hydrogen generation step are performed in this order.
  • the alkali metal is preferably lithium, sodium or potassium.
  • the hydrogen production apparatus comprises: A first hydrogen generation step of reacting an alkali metal with an alkali metal hydroxide to generate an alkali metal oxide and hydrogen molecules; an alkali metal oxide generated in the first hydrogen generation step is decomposed; And a reduction step for generating oxygen molecules, and a second hydrogen generation step for generating alkali metal hydroxide and hydrogen molecules by reacting the alkali metal generated in the reduction step with water.
  • a reaction vessel An alkali metal storage container connected to the reaction container and storing alkali metal; An inlet for introducing water into the reaction vessel; A discharge port for discharging hydrogen molecules and oxygen molecules generated inside the reaction vessel; A heating device for heating the reaction vessel; A heating and cooling device for heating and cooling the alkali metal storage container, It is characterized by that.
  • the hydrogen production method has a first hydrogen generation step, a reduction step, and a second hydrogen generation step as shown in FIG. And it is the method of manufacturing hydrogen by repeating in order of a 1st hydrogen generating process, a reduction process, and a 2nd hydrogen generating process.
  • Second hydrogen generation process In the first hydrogen generation step, as shown in Formula 1, an alkali metal hydroxide and an alkali metal are reacted to generate an alkali metal oxide and hydrogen.
  • M represents an alkali metal
  • g, l, and s represent a gas, liquid, and solid state, respectively.
  • 2MOH (s) + 2M (l) ⁇ 2M 2 O (s) + H 2 (g) (Formula 1)
  • each state of gas, liquid, and solid described in Formula 1 is one of the examples of various aspects.
  • the preferred reaction temperature in the first hydrogen generation step is 200 to 800 ° C., more preferably 300 to 600 ° C.
  • the preferred pressure is 0.001 to 0.1 MPa, more preferably 0.01 to 0.1 MPa.
  • inert gas atmosphere such as argon gas.
  • the water concentration and the oxygen concentration are each preferably 1 ppm by volume or less.
  • the alkali metal oxide is used in the reduction step.
  • the method for separating the alkali metal oxide and hydrogen is not particularly limited, and can be separated by, for example, discharging hydrogen molecules out of the reaction vessel or applying a method such as using a hydrogen storage material. .
  • the alkali metal oxide is reduced by heating to decompose into alkali metal and oxygen.
  • the alkali metal oxide here can use what was produced
  • the reaction temperature in the reduction step is preferably 400 to 1000 ° C, more preferably 600 to 900 ° C.
  • the pressure is preferably 0.1 MPa or less.
  • the enthalpy change of Formula 2 is 1266 kJ and a big endothermic reaction.
  • the oxygen pressure is preferably 1 Pa or less, more preferably 0.01 Pa or less, which is the solid vapor pressure.
  • the water concentration and the oxygen concentration are each 1 ppm or less.
  • the produced alkali metal is evaporated and then produced as an alkali metal solid by a technique such as adsorption. In addition, it is desirable to discharge the produced oxygen out of the reaction vessel.
  • the reaction temperature in the second hydrogen generation step is preferably room temperature (25 ° C.) to 300 ° C., more preferably room temperature (25 ° C.) to 100 ° C.
  • the reaction pressure is preferably about 0.1 MPa.
  • inert gas atmosphere such as argon gas.
  • the second hydrogen generation step a part of the alkali metal generated in the reduction step may be used instead of all.
  • the remaining alkali metal generated in the reduction step and the alkali metal hydride generated in the second hydrogen generation step may be used in the first hydrogen generation step.
  • the first hydrogen generation step 2 moles of alkali metal hydroxide and 2 moles of alkali metal are used to generate 2 moles of alkali metal oxide and 1 mole of hydrogen.
  • the reduction step 2 mol of alkali metal oxide is reduced to generate 4 mol of alkali metal and 1 mol of oxygen.
  • 1/2 (2 moles) of alkali metal is used in the second hydrogen generation step.
  • 2 moles of alkali metal hydroxide and 1 mole of hydrogen are produced by the reaction of 2 moles of alkali metal with 2 moles of water.
  • generated at the 2nd hydrogen generation process are utilized for a 1st hydrogen generation process.
  • the first hydrogen generation process, the reduction process, and the second hydrogen generation process described above can be performed by supplying only water. It can be repeated in this order. That is, by performing the above-mentioned process for one cycle, for example, using 2 mol of alkali metal and 2 mol of alkali metal hydroxide, 2 mol of water is decomposed to produce 2 mol of hydrogen as shown in Formula 4. can do. 2H 2 O (l) ⁇ 2H 2 (g) + O 2 (g) (Formula 4)
  • Patent Document 1 and Non-Patent Document 1 only 1 mole of hydrogen can be produced in 1 cycle using 2 moles of alkali metal hydroxide and 2 moles of alkali metal. Since it can produce twice as much hydrogen, it is excellent in efficiency.
  • lithium (Li), sodium (Na), or potassium (K) is mentioned as an alkali metal. Therefore, lithium hydroxide, sodium hydroxide, or potassium hydroxide is used as the alkali metal hydroxide, and lithium oxide (Li 2 O), sodium oxide (Na 2 O), or potassium oxide (K) is used as the alkali metal oxide. 2 O). From the viewpoint of the thermodynamic properties of each reaction, high vapor pressure, and relatively low corrosivity, sodium is most preferable as the alkali metal.
  • the above-described hydrogen production can be performed using, for example, the hydrogen production apparatus 1 shown in FIG.
  • the hydrogen production apparatus 1 has produced a reaction vessel 10 in which the respective reactions in the first hydrogen generation step, the reduction step, and the second hydrogen generation step are performed, an introduction port 20 into which an inert gas such as water or argon gas is introduced.
  • a discharge port 30 through which hydrogen and oxygen are discharged, an alkali metal storage container 40 in which alkali metal generated in the reduction process is stored, a heating device 50 for heating the reaction container 10, and heating and cooling for heating and cooling the alkali metal storage container 40
  • a device 60 is provided.
  • an alkali metal hydroxide is placed in the reaction vessel 10, and an alkali metal is placed in the alkali metal storage vessel 40. Further, the pressure in the reaction vessel 10 is adjusted to the above-described pressure condition with a suction device (not shown) or the like. Then, the alkali metal is dropped into the reaction vessel 10 from the alkali metal storage vessel 40, and the heating device 50 heats the reaction vessel 10 so that the inside of the reaction vessel 10 is in the above-described temperature condition. Thereby, an alkali metal hydroxide and an alkali metal react, and an alkali metal oxide and hydrogen are generated. The generated hydrogen is discharged from the discharge port 30.
  • the inside of the reaction vessel 10 is adjusted by the heating device 50 so as to satisfy the above-described temperature condition, and the alkali metal oxide generated in the first hydrogen generation step is reduced.
  • the alkali metal oxide is decomposed to produce gaseous alkali metal and oxygen.
  • the gaseous alkali metal enters the alkali metal storage container 40.
  • the alkali metal storage container 40 is cooled by the heating / cooling device 60, the alkali metal contained in the alkali metal storage container 40 is solidified and stored. Alternatively, the alkali metal may be used in the next cycle while maintaining the fluid state. Further, oxygen is discharged from the discharge port 30. In order to prevent vaporized alkali metal from being discharged from the discharge port 30, it is preferable to install a separation membrane or the like that allows oxygen to pass through the discharge port 30 without passing through the alkali metal.
  • water is introduced into the reaction vessel 10 from the introduction port 20. Furthermore, when the alkali metal in the alkali metal storage container 40 is solid by the heating / cooling device 60, it is liquefied and dropped into the reaction container 10. And it adjusts so that the inside of reaction container 10 may become the temperature conditions mentioned above with the heating apparatus 50, an alkali metal and water react, and an alkali metal hydroxide and hydrogen produce
  • a valve is installed in a passage connecting the reaction vessel 10 and the alkali metal storage container 40, and in the second hydrogen generation step, part of the alkali metal is dropped from the alkali metal storage vessel 40.
  • the alkali metal remaining in the alkali metal storage container 40 can be used in the first hydrogen generation step, and the alkali metal, alkali metal hydroxide, and alkali metal oxide remain in the reaction system while remaining in the reaction system.
  • Hydrogen can be produced by repeating the first hydrogen generation step, the reduction step, and the second hydrogen generation step in order. Therefore, it is possible to produce hydrogen by decomposing water using only water as a raw material.
  • a cooling unit was provided above the Na 2 O heating unit to produce an experimental system for aggregating (solidifying) and recovering the metal vapor to reduce Na 2 O.
  • Na 2 O was placed in a reaction vessel of the experimental system, and heat treatment was performed for 20 hours in a closed system at 650 ° C. under vacuum (0.01 Pa). And it was investigated whether reaction could advance by identifying a reaction product. As a result, it was confirmed that metal Na was generated. Moreover, the gas analysis in a container was performed after reaction and it confirmed that oxygen was producing
  • the hydrolysis reaction is an exothermic reaction and is a reaction that proceeds spontaneously thermodynamically.
  • water was added to sodium metal produced in the reduction step and heated to 100 ° C. to identify the reaction product.
  • the reaction rate was 95% or more, and it was confirmed that NaOH and H 2 were produced.
  • Li 2 O is placed in the reaction vessel of the experimental system of Example 1, and heat treatment is performed in a closed system at a temperature of 800 ° C. under vacuum (0.01 Pa) for 20 hours, and the reaction proceeds by identifying reaction products. We examined whether it could be done. The reaction rate was estimated to be 50% from the intensity of the X-ray diffraction peak, and it was confirmed that Li 2 O was decomposed into Li and O 2 .
  • the hydrogen production method can efficiently produce hydrogen and can be used as an alternative energy to conventional fossil fuels.

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Abstract

This method for generating hydrogen comprises: a first hydrogen generation step for generating an alkali metal oxide and hydrogen molecules by reacting an alkali metal with an alkali metal hydroxide; a reduction step for generating an alkali metal and oxygen molecules by decomposing the alkali metal oxide generated in the first hydrogen generation step; and a second hydrogen generation step for generating an alkali metal hydroxide and hydrogen molecules by reacting water with the alkali metal generated in the reduction step. The first hydrogen generation step, the reduction step and the second hydrogen generation step are carried out in this order.

Description

水素製造方法及び水素製造装置Hydrogen production method and hydrogen production apparatus
　本発明は、水素製造方法及び水素製造装置に関する。 The present invention relates to a hydrogen production method and a hydrogen production apparatus.
　エネルギーとして、これまで石炭や石油等の化石燃料が広く使用されてきたが、近年では資源の枯渇、地球温暖化等の問題があり、これらに代わる代替エネルギーとして水素エネルギーが注目されている。 Until now, fossil fuels such as coal and oil have been widely used as energy, but in recent years, there are problems such as depletion of resources and global warming, and hydrogen energy has attracted attention as an alternative energy alternative.
　水素を発生させる方法として、特許文献１、非特許文献１には、アルカリ金属を利用した水素の発生方法が開示されている。この方法は、アルカリ金属水酸化物とアルカリ金属を反応させてアルカリ金属酸化物、水素を生成させる工程（第１工程）、生成したアルカリ金属酸化物を分解し、アルカリ金属過酸化物とアルカリ金属を生成する工程（第２工程）、アルカリ金属過酸化物と水とを反応させ、アルカリ金属水酸化物と酸素を生成する工程（第３工程）から構成されている。そして、第２工程で生成したアルカリ金属、及び、第３工程で生成したアルカリ金属水酸化物を第１工程に用いることで、第１工程、第２工程、第３工程の順に繰り返し、水から水素を発生させる方法である。 As a method for generating hydrogen, Patent Document 1 and Non-Patent Document 1 disclose a method for generating hydrogen using an alkali metal. In this method, an alkali metal hydroxide and an alkali metal are reacted to generate an alkali metal oxide and hydrogen (first step), the generated alkali metal oxide is decomposed, and an alkali metal peroxide and an alkali metal are decomposed. The second step is a step of reacting an alkali metal peroxide with water to generate an alkali metal hydroxide and oxygen (third step). And by using the alkali metal produced | generated at the 2nd process and the alkali metal hydroxide produced | generated at the 3rd process for the 1st process, it repeats in order of a 1st process, a 2nd process, and a 3rd process, from water. This is a method for generating hydrogen.
特開昭４９－６４５８９号公報JP 49-64589 A
　特許文献１、非特許文献１では、第１工程、第２工程、第３工程の１サイクルで、２モルのアルカリ金属水酸化物と２モルのアルカリ金属を用いて１モルの水素を製造するものであり、効率がよいものとは言えない。 In Patent Document 1 and Non-Patent Document 1, 1 mol of hydrogen is produced using 2 mol of alkali metal hydroxide and 2 mol of alkali metal in one cycle of the first step, the second step, and the third step. It is a thing and cannot be said to be efficient.
　本発明は上記事項に鑑みてなされたものであり、その目的とするところは、効率的に水素を製造することが可能な水素製造方法及び水素製造装置を提供することにある。 The present invention has been made in view of the above matters, and an object of the present invention is to provide a hydrogen production method and a hydrogen production apparatus capable of efficiently producing hydrogen.
　本発明の第１の態様に係る水素製造方法は、
　アルカリ金属とアルカリ金属水酸化物とを反応させて、アルカリ金属酸化物と水素分子を生成させる第１水素発生工程と、
　前記第１水素発生工程で生成したアルカリ金属酸化物を分解させて、アルカリ金属と酸素分子を生成させる還元工程と、
　前記還元工程で生成したアルカリ金属と水とを反応させて、アルカリ金属水酸化物と水素分子を生成させる第２水素発生工程と、を有し、
　前記第１水素発生工程、前記還元工程、前記第２水素発生工程の順に行う、
　ことを特徴とする。 The hydrogen production method according to the first aspect of the present invention includes:
A first hydrogen generation step in which an alkali metal and an alkali metal hydroxide are reacted to generate an alkali metal oxide and a hydrogen molecule;
A reduction step of decomposing the alkali metal oxide produced in the first hydrogen generation step to produce an alkali metal and oxygen molecules;
A second hydrogen generation step of reacting the alkali metal produced in the reduction step with water to produce an alkali metal hydroxide and hydrogen molecules,
The first hydrogen generation step, the reduction step, and the second hydrogen generation step are performed in this order.
It is characterized by that.
　また、前記第２水素発生工程では、前記還元工程で生成したアルカリ金属の一部と水とを反応させ、
　前記第１水素発生工程では、前記還元工程で生成したアルカリ金属の残りと前記第２水素発生工程で生成したアルカリ金属水酸化物を用い、
　前記第１水素発生工程、前記還元工程、前記第２水素発生工程の順に行うことが好ましい。 In the second hydrogen generation step, a part of the alkali metal generated in the reduction step is reacted with water,
In the first hydrogen generation step, the remaining alkali metal generated in the reduction step and the alkali metal hydroxide generated in the second hydrogen generation step are used.
Preferably, the first hydrogen generation step, the reduction step, and the second hydrogen generation step are performed in this order.
　また、前記アルカリ金属がリチウム、ナトリウム又はカリウムであることが好ましい。 The alkali metal is preferably lithium, sodium or potassium.
　本発明の第２の態様に係る水素製造装置は、
　アルカリ金属とアルカリ金属水酸化物とを反応させて、アルカリ金属酸化物と水素分子を生成させる第１水素発生工程、前記第１水素発生工程で生成したアルカリ金属酸化物を分解させて、アルカリ金属と酸素分子を生成させる還元工程、及び、前記還元工程で生成したアルカリ金属と水とを反応させて、アルカリ金属水酸化物と水素分子を生成させる第２水素発生工程のそれぞれの反応が行われる反応容器と、
　前記反応容器に接続しアルカリ金属を貯留するアルカリ金属貯留容器と、
　前記反応容器に水を導入する導入口と、
　前記反応容器の内部で生成した水素分子及び酸素分子を排出する排出口と、
　前記反応容器を加熱する加熱装置と、
　前記アルカリ金属貯留容器を加熱、冷却する加熱冷却装置と、を備える、
　ことを特徴とする。 The hydrogen production apparatus according to the second aspect of the present invention comprises:
A first hydrogen generation step of reacting an alkali metal with an alkali metal hydroxide to generate an alkali metal oxide and hydrogen molecules; an alkali metal oxide generated in the first hydrogen generation step is decomposed; And a reduction step for generating oxygen molecules, and a second hydrogen generation step for generating alkali metal hydroxide and hydrogen molecules by reacting the alkali metal generated in the reduction step with water. A reaction vessel;
An alkali metal storage container connected to the reaction container and storing alkali metal;
An inlet for introducing water into the reaction vessel;
A discharge port for discharging hydrogen molecules and oxygen molecules generated inside the reaction vessel;
A heating device for heating the reaction vessel;
A heating and cooling device for heating and cooling the alkali metal storage container,
It is characterized by that.
　本発明に係る水素製造方法では、第１水素発生工程、還元工程、第２水素発生工程の１サイクルで、２モルのアルカリ金属水酸化物と２モルのアルカリ金属を用いた場合、２モルの水素を製造することができる。 In the hydrogen production method according to the present invention, when 2 mol of alkali metal hydroxide and 2 mol of alkali metal are used in one cycle of the first hydrogen generation step, the reduction step, and the second hydrogen generation step, Hydrogen can be produced.
水素製造方法を示すブロック図である。It is a block diagram which shows the hydrogen production method. 水素製造装置の概略図である。It is the schematic of a hydrogen production apparatus.
　水素製造方法は、図１に示すように、第１水素発生工程、還元工程、第２水素発生工程を有している。そして、第１水素発生工程、還元工程、第２水素発生工程の順に繰り返し行うことで水素を製造する方法である。 The hydrogen production method has a first hydrogen generation step, a reduction step, and a second hydrogen generation step as shown in FIG. And it is the method of manufacturing hydrogen by repeating in order of a 1st hydrogen generating process, a reduction process, and a 2nd hydrogen generating process.
（第１水素発生工程）
　第１水素発生工程では、式１に示すように、アルカリ金属水酸化物とアルカリ金属とを反応させ、アルカリ金属酸化物と水素とを発生させる。なお、式１及び後述する式２，３中、Ｍはアルカリ金属を示し、また、式１－４中、ｇ、ｌ、ｓはそれぞれ気体、液体、固体状態であることを表す。
　　　２ＭＯＨ（ｓ）＋２Ｍ（ｌ）→２Ｍ２Ｏ（ｓ）＋Ｈ２（ｇ）・・・（式１）
　なお、式１に記載の気体、液体、固体の各状態は、各種態様のうちの例示のひとつである。 (First hydrogen generation process)
In the first hydrogen generation step, as shown in Formula 1, an alkali metal hydroxide and an alkali metal are reacted to generate an alkali metal oxide and hydrogen. In Formula 1 and Formulas 2 and 3 described later, M represents an alkali metal, and in Formula 1-4, g, l, and s represent a gas, liquid, and solid state, respectively.
2MOH (s) + 2M (l) → 2M 2 O (s) + H 2 (g) (Formula 1)
In addition, each state of gas, liquid, and solid described in Formula 1 is one of the examples of various aspects.
　第１水素発生工程における好ましい反応温度は２００～８００℃、より好ましくは３００～６００℃である。また、好ましい圧力は０．００１～０．１ＭＰａ、より好ましくは０．０１～０．１ＭＰａである。また、アルゴンガス等の不活性ガス雰囲気下で行うことが好ましい。 The preferred reaction temperature in the first hydrogen generation step is 200 to 800 ° C., more preferably 300 to 600 ° C. The preferred pressure is 0.001 to 0.1 MPa, more preferably 0.01 to 0.1 MPa. Moreover, it is preferable to carry out in inert gas atmosphere, such as argon gas.
　また、アルカリ金属は、水や酸素と反応しやすいため、水分濃度及び酸素濃度はそれぞれ１体積ｐｐｍ以下であることが好ましい。 In addition, since alkali metal easily reacts with water and oxygen, the water concentration and the oxygen concentration are each preferably 1 ppm by volume or less.
　生成したアルカリ金属酸化物と水素とを分離した後、アルカリ金属酸化物を還元工程に用いる。アルカリ金属酸化物と水素との分離方法は、特に限定されず、例えば、反応容器の外へ水素分子を排出するか、または、水素貯蔵材料の利用などの方法を適用して分離することができる。 After separating the produced alkali metal oxide and hydrogen, the alkali metal oxide is used in the reduction step. The method for separating the alkali metal oxide and hydrogen is not particularly limited, and can be separated by, for example, discharging hydrogen molecules out of the reaction vessel or applying a method such as using a hydrogen storage material. .
（還元工程）
　還元工程では、式２に示すように、アルカリ金属酸化物を加熱することで還元し、アルカリ金属と酸素に分解する。ここでのアルカリ金属酸化物は第１水素発生工程にて生成したものを用いることができる。
　　　２Ｍ２Ｏ（ｓ）→４Ｍ（ｓ）＋Ｏ２（ｇ）・・・（式２） (Reduction process)
In the reduction step, as shown in Formula 2, the alkali metal oxide is reduced by heating to decompose into alkali metal and oxygen. The alkali metal oxide here can use what was produced | generated at the 1st hydrogen generating process.
2M 2 O (s) → 4M (s) + O 2 (g) (Formula 2)
　還元工程における反応温度は、好ましくは４００～１０００℃、より好ましくは６００～９００℃である。また、圧力は０．１ＭＰａ以下であることが好ましい。なお、式２のエンタルピー変化は１２６６ｋＪと大きな吸熱反応である。反応を進行させるためには酸素圧力を固体の蒸気圧である１Ｐａ以下で行うことがより好ましく、０．０１Ｐａ以下で行うことが更に好ましい。また、アルゴンガス等、不活性ガス雰囲気下で行うことが好ましい。 The reaction temperature in the reduction step is preferably 400 to 1000 ° C, more preferably 600 to 900 ° C. The pressure is preferably 0.1 MPa or less. In addition, the enthalpy change of Formula 2 is 1266 kJ and a big endothermic reaction. In order to advance the reaction, the oxygen pressure is preferably 1 Pa or less, more preferably 0.01 Pa or less, which is the solid vapor pressure. Moreover, it is preferable to carry out in inert gas atmosphere, such as argon gas.
　生成するアルカリ金属は水や酸素と反応しやすいため、水分濃度、酸素濃度はそれぞれ１ｐｐｍ以下で行うことが好ましい。 Since the generated alkali metal easily reacts with water and oxygen, it is preferable that the water concentration and the oxygen concentration are each 1 ppm or less.
　生成したアルカリ金属は蒸発させた後、吸着などの手法により、アルカリ金属固体として生成する。また、生成した酸素は反応容器外に排出することが望ましい。 The produced alkali metal is evaporated and then produced as an alkali metal solid by a technique such as adsorption. In addition, it is desirable to discharge the produced oxygen out of the reaction vessel.
（第２水素発生工程）
　第２水素発生工程では、式（３）に示すように、アルカリ金属と水を反応させ、加水分解によってアルカリ金属水酸化物と水素を生成する。
　　　２Ｍ（ｓ）＋２Ｈ２Ｏ（ｌ）→２ＭＯＨ（ｓ）＋Ｈ２（ｇ）・・・（式３）
　なお、式１に記載の気体、液体、固体の各状態は、各種態様のうちの例示のひとつである。 (Second hydrogen generation process)
In the second hydrogen generation step, as shown in the formula (3), an alkali metal and water are reacted to generate an alkali metal hydroxide and hydrogen by hydrolysis.
2M (s) + 2H 2 O (l) → 2MOH (s) + H 2 (g) (Formula 3)
In addition, each state of gas, liquid, and solid described in Formula 1 is one of the examples of various aspects.
　第２水素発生工程における反応温度は、好ましくは室温（２５℃）～３００℃、より好ましくは室温（２５℃）～１００℃である。また、反応圧力は、好ましくは０．１ＭＰａ程度である。また、アルゴンガス等の不活性ガス雰囲気下で行うことが好ましい。 The reaction temperature in the second hydrogen generation step is preferably room temperature (25 ° C.) to 300 ° C., more preferably room temperature (25 ° C.) to 100 ° C. The reaction pressure is preferably about 0.1 MPa. Moreover, it is preferable to carry out in inert gas atmosphere, such as argon gas.
　第２水素発生工程においては、還元工程で生成したアルカリ金属の全てではなく一部を使用してもよい。そして、還元工程で生成したアルカリ金属の残りと第２水素発生工程で生じたアルカリ金属水素化物とを第１水素発生工程に用いてもよい。 In the second hydrogen generation step, a part of the alkali metal generated in the reduction step may be used instead of all. The remaining alkali metal generated in the reduction step and the alkali metal hydride generated in the second hydrogen generation step may be used in the first hydrogen generation step.
　例えば、第１水素発生工程において、２モルのアルカリ金属水酸化物と２モルのアルカリ金属を用い、２モルのアルカリ金属酸化物と１モルの水素を発生させる。そして、還元工程において、２モルのアルカリ金属酸化物を還元し、４モルのアルカリ金属及び１モルの酸素を生成させる。ここで生成した４モルのアルカリ金属うち、１／２（２モル）のアルカリ金属を第２水素発生工程で利用する。第２水素発生工程で２モルのアルカリ金属と２モルの水との反応により、２モルのアルカリ金属水酸化物及び１モルの水素が生成する。そして、還元工程で生成したアルカリ金属の残り（２モル）と第２水素発生工程で生成した２モルのアルカリ金属水酸化物を第１水素発生工程に利用する。 For example, in the first hydrogen generation step, 2 moles of alkali metal hydroxide and 2 moles of alkali metal are used to generate 2 moles of alkali metal oxide and 1 mole of hydrogen. In the reduction step, 2 mol of alkali metal oxide is reduced to generate 4 mol of alkali metal and 1 mol of oxygen. Of the 4 moles of alkali metal produced here, 1/2 (2 moles) of alkali metal is used in the second hydrogen generation step. In the second hydrogen generation step, 2 moles of alkali metal hydroxide and 1 mole of hydrogen are produced by the reaction of 2 moles of alkali metal with 2 moles of water. And the remainder (2 mol) of the alkali metal produced | generated at the reduction process and 2 mol alkali metal hydroxide produced | generated at the 2nd hydrogen generation process are utilized for a 1st hydrogen generation process.
　このように、還元工程で生成したアルカリ金属の一部を第２水素発生工程に利用して行うことにより、水のみの供給で、上述した第１水素発生工程、還元工程、第２水素発生工程の順に繰り返し行うことができる。即ち、上記の工程を１サイクル行うことにより、例えば、２モルのアルカリ金属と２モルのアルカリ金属水酸化物を用いて、式４に示すように、水を２モル分解し水素を２モル製造することができる。
　　　２Ｈ２Ｏ（ｌ）→２Ｈ２（ｇ）＋Ｏ２（ｇ）・・・（式４） As described above, by performing a part of the alkali metal generated in the reduction process in the second hydrogen generation process, the first hydrogen generation process, the reduction process, and the second hydrogen generation process described above can be performed by supplying only water. It can be repeated in this order. That is, by performing the above-mentioned process for one cycle, for example, using 2 mol of alkali metal and 2 mol of alkali metal hydroxide, 2 mol of water is decomposed to produce 2 mol of hydrogen as shown in Formula 4. can do.
2H 2 O (l) → 2H 2 (g) + O 2 (g) (Formula 4)
　特許文献１、非特許文献１では、２モルのアルカリ金属水酸化物と２モルのアルカリ金属を用いて、１サイクルで１モルの水素しか製造できないが、本願では、１サイクルで２モルの水素を製造でき、２倍量の水素を製造できるので効率に優れる。 In Patent Document 1 and Non-Patent Document 1, only 1 mole of hydrogen can be produced in 1 cycle using 2 moles of alkali metal hydroxide and 2 moles of alkali metal. Since it can produce twice as much hydrogen, it is excellent in efficiency.
　なお、アルカリ金属として、リチウム（Ｌｉ）、ナトリウム（Ｎａ）又はカリウム（Ｋ）が挙げられる。したがって、アルカリ金属水酸化物として、水酸化リチウム、水酸化ナトリウム又は水酸化カリウムが挙げられ、アルカリ金属酸化物として、酸化リチウム（Ｌｉ２Ｏ）、酸化ナトリウム（Ｎａ２Ｏ）又は酸化カリウム（Ｋ２Ｏ）が挙げられる。各反応の熱力学特性、高い蒸気圧、比較的低い腐食性といった観点から、アルカリ金属としてナトリウムが最も好ましい。 In addition, lithium (Li), sodium (Na), or potassium (K) is mentioned as an alkali metal. Therefore, lithium hydroxide, sodium hydroxide, or potassium hydroxide is used as the alkali metal hydroxide, and lithium oxide (Li 2 O), sodium oxide (Na 2 O), or potassium oxide (K) is used as the alkali metal oxide. 2 O). From the viewpoint of the thermodynamic properties of each reaction, high vapor pressure, and relatively low corrosivity, sodium is most preferable as the alkali metal.
　上述した水素の製造は、例えば、図２に示す水素製造装置１を用いて行い得る。水素製造装置１は、第１水素発生工程、還元工程、第２水素発生工程におけるそれぞれの反応が行われる反応容器１０、水やアルゴンガス等の不活性ガスが導入される導入口２０、生成した水素、酸素が排出される排出口３０、還元工程で生成したアルカリ金属が貯留されるアルカリ金属貯留容器４０、反応容器１０を加熱する加熱装置５０、アルカリ金属貯留容器４０を加熱、冷却する加熱冷却装置６０を備えている。 The above-described hydrogen production can be performed using, for example, the hydrogen production apparatus 1 shown in FIG. The hydrogen production apparatus 1 has produced a reaction vessel 10 in which the respective reactions in the first hydrogen generation step, the reduction step, and the second hydrogen generation step are performed, an introduction port 20 into which an inert gas such as water or argon gas is introduced. A discharge port 30 through which hydrogen and oxygen are discharged, an alkali metal storage container 40 in which alkali metal generated in the reduction process is stored, a heating device 50 for heating the reaction container 10, and heating and cooling for heating and cooling the alkali metal storage container 40 A device 60 is provided.
　第１水素発生工程では、反応容器１０にはアルカリ金属水酸化物が入れられており、アルカリ金属貯留容器４０にはアルカリ金属が入れられている。また、不図示の吸引装置等で、反応容器１０内の圧力を上述した圧力条件に調節する。そして、アルカリ金属貯留容器４０からアルカリ金属が反応容器１０内に滴下され、反応容器１０内が上述した温度条件になるよう加熱装置５０が反応容器１０を加熱する。これにより、アルカリ金属水酸化物とアルカリ金属が反応し、アルカリ金属酸化物と水素が生成する。生成した水素は排出口３０から排出される。 In the first hydrogen generation step, an alkali metal hydroxide is placed in the reaction vessel 10, and an alkali metal is placed in the alkali metal storage vessel 40. Further, the pressure in the reaction vessel 10 is adjusted to the above-described pressure condition with a suction device (not shown) or the like. Then, the alkali metal is dropped into the reaction vessel 10 from the alkali metal storage vessel 40, and the heating device 50 heats the reaction vessel 10 so that the inside of the reaction vessel 10 is in the above-described temperature condition. Thereby, an alkali metal hydroxide and an alkali metal react, and an alkali metal oxide and hydrogen are generated. The generated hydrogen is discharged from the discharge port 30.
　還元工程では、加熱装置５０にて反応容器１０内を上述した温度条件になるように調節し、第１水素発生工程で生成したアルカリ金属酸化物を還元する。アルカリ金属酸化物が分解され、気体状のアルカリ金属及び酸素が生成する。気体状のアルカリ金属はアルカリ金属貯留容器４０に入る。加熱冷却装置６０によりアルカリ金属貯留容器４０が冷却されることにより、アルカリ金属貯留容器４０に入ったアルカリ金属は固化され貯留される。あるいは、アルカリ金属は流体状態を保持したままで次のサイクルに使用してもよい。また、酸素は排出口３０から排出される。なお、気化したアルカリ金属が排出口３０から排出されないように、排出口３０にはアルカリ金属を通過させず酸素を通過させる分離膜等が設置されることが好ましい。 In the reduction step, the inside of the reaction vessel 10 is adjusted by the heating device 50 so as to satisfy the above-described temperature condition, and the alkali metal oxide generated in the first hydrogen generation step is reduced. The alkali metal oxide is decomposed to produce gaseous alkali metal and oxygen. The gaseous alkali metal enters the alkali metal storage container 40. When the alkali metal storage container 40 is cooled by the heating / cooling device 60, the alkali metal contained in the alkali metal storage container 40 is solidified and stored. Alternatively, the alkali metal may be used in the next cycle while maintaining the fluid state. Further, oxygen is discharged from the discharge port 30. In order to prevent vaporized alkali metal from being discharged from the discharge port 30, it is preferable to install a separation membrane or the like that allows oxygen to pass through the discharge port 30 without passing through the alkali metal.
　第２水素発生工程では、導入口２０から水が反応容器１０内に導入される。更に、加熱冷却装置６０によってアルカリ金属貯留容器４０内のアルカリ金属が固体であった場合は液化され、反応容器１０内に滴下される。そして、加熱装置５０により反応容器１０内が上述した温度条件になるように調節され、アルカリ金属と水が反応してアルカリ金属水酸化物及び水素が生成する。生成した水素は排出口３０から排出される。 In the second hydrogen generation step, water is introduced into the reaction vessel 10 from the introduction port 20. Furthermore, when the alkali metal in the alkali metal storage container 40 is solid by the heating / cooling device 60, it is liquefied and dropped into the reaction container 10. And it adjusts so that the inside of reaction container 10 may become the temperature conditions mentioned above with the heating apparatus 50, an alkali metal and water react, and an alkali metal hydroxide and hydrogen produce | generate. The generated hydrogen is discharged from the discharge port 30.
　なお、反応容器１０とアルカリ金属貯留容器４０とをつなぐ通路にはバルブが設置され、第２水素発生工程においては、アルカリ金属貯留容器４０から一部のアルカリ金属が滴下されるよう行う。これにより、アルカリ金属貯留容器４０に残ったアルカリ金属を第１水素発生工程に利用することができ、アルカリ金属、アルカリ金属水酸化物、アルカリ金属酸化物を反応系内に残存させたまま、第１水素発生工程、還元工程、第２水素発生工程を順に繰り返し行い、水素を製造できる。したがって、水のみを原料とし、水を分解して水素を製造することが可能である。 In addition, a valve is installed in a passage connecting the reaction vessel 10 and the alkali metal storage container 40, and in the second hydrogen generation step, part of the alkali metal is dropped from the alkali metal storage vessel 40. Thereby, the alkali metal remaining in the alkali metal storage container 40 can be used in the first hydrogen generation step, and the alkali metal, alkali metal hydroxide, and alkali metal oxide remain in the reaction system while remaining in the reaction system. Hydrogen can be produced by repeating the first hydrogen generation step, the reduction step, and the second hydrogen generation step in order. Therefore, it is possible to produce hydrogen by decomposing water using only water as a raw material.
（第一水素発生工程）
　ＮａＯＨとＮａ（１モル／１モル）を３５０℃で２０時間加熱して、水素とＮａ２Ｏを生成した。生成物の同定及び発生した水素の定量評価を行った。定量評価には、室温で速やかに水素を吸蔵可能なＮｂ２Ｏ５を添加したＭｇを用いた。つまり、このＮｂ２Ｏ５添加Ｍｇを用い、生成した水素をＭｇＨ２として吸蔵分離した。得られた水素量から反応率を求め、Ｘ線回折により生成物の分析を行った。その結果、反応率は約８０％であり、Ｎａ２ＯとＨ２が生成したことを確認した。 (First hydrogen generation process)
NaOH and Na (1 mol / 1 mol) were heated at 350 ° C. for 20 hours to produce hydrogen and Na 2 O. The product was identified and the generated hydrogen was quantitatively evaluated. For quantitative evaluation, Mg added with Nb 2 O 5 capable of quickly absorbing hydrogen at room temperature was used. That is, using this Nb 2 O 5 -added Mg, the produced hydrogen was occluded and separated as MgH 2 . The reaction rate was determined from the amount of hydrogen obtained, and the product was analyzed by X-ray diffraction. As a result, the reaction rate was about 80%, and it was confirmed that Na 2 O and H 2 were produced.
（還元工程）
　Ｎａ２Ｏ加熱部上方に冷却部を設け金属蒸気を凝集（固化）させて回収する実験システムを作製して、Ｎａ２Ｏの還元を行った。Ｎａ２Ｏを実験システムの反応容器に入れ、真空下（０．０１Ｐａ）、６５０℃の閉鎖系において熱処理を２０時間行った。そして、反応生成物の同定を行うことで反応が進行し得るかどうか検討した。その結果、金属Ｎａが生成することが確認された。また、反応後に容器内のガス分析を行い、酸素が生成していることを確認した。Ｎａ２ＯのＸ線回折ピーク強度の変化から反応率は約８０％であると見積もられた。以上の結果から、Ｎａ２ＯがＮａとＯ２に分解されたことを確認した。Ｎａ２Ｏの還元工程におけるエンタルピー変化は１２６６ｋＪと大きな吸熱反応である。酸素圧力を０．０１Ｐａにすることで反応が進行した。 (Reduction process)
A cooling unit was provided above the Na 2 O heating unit to produce an experimental system for aggregating (solidifying) and recovering the metal vapor to reduce Na 2 O. Na 2 O was placed in a reaction vessel of the experimental system, and heat treatment was performed for 20 hours in a closed system at 650 ° C. under vacuum (0.01 Pa). And it was investigated whether reaction could advance by identifying a reaction product. As a result, it was confirmed that metal Na was generated. Moreover, the gas analysis in a container was performed after reaction and it confirmed that oxygen was producing | generating. From the change in the intensity of the X-ray diffraction peak of Na 2 O, the reaction rate was estimated to be about 80%. From the above results, it was confirmed that Na 2 O was decomposed into Na and O 2 . The enthalpy change in the reduction process of Na 2 O is an endothermic reaction as large as 1266 kJ. The reaction proceeded by setting the oxygen pressure to 0.01 Pa.
（第二水素発生工程）
　加水分解反応は発熱反応であり、熱力学的には自発的に進行する反応である。本実験においては、還元工程で生成した金属ナトリウムに水を加えて１００℃まで加熱し、反応生成物の同定を行った。その結果、反応率は９５％以上であり、ＮａＯＨとＨ２が生成したことを確認した。 (Second hydrogen generation process)
The hydrolysis reaction is an exothermic reaction and is a reaction that proceeds spontaneously thermodynamically. In this experiment, water was added to sodium metal produced in the reduction step and heated to 100 ° C. to identify the reaction product. As a result, the reaction rate was 95% or more, and it was confirmed that NaOH and H 2 were produced.
（第一水素発生工程）
　ＬｉＯＨとＬｉ（１モル／１モル）を５００℃の温度で２０時間加熱した。そして、生成物の同定及び発生したガスの評価を行った。ガス分析により、反応後には水素が生成していることが確認された。またＸ線回折ピーク強度から反応率はほぼ１００％と見積もられ、Ｌｉ２ＯとＨ２が生成したことを確認した。 (First hydrogen generation process)
LiOH and Li (1 mol / 1 mol) were heated at a temperature of 500 ° C. for 20 hours. Then, the product was identified and the generated gas was evaluated. Gas analysis confirmed that hydrogen was produced after the reaction. The reaction rate was estimated to be almost 100% from the X-ray diffraction peak intensity, and it was confirmed that Li 2 O and H 2 were formed.
（還元工程）
　Ｌｉ２Ｏを実施例１の実験システムの反応容器に入れ、真空下（０．０１Ｐａ）、８００℃の温度で閉鎖系において２０時間熱処理を行い、反応生成物の同定を行うことで反応が進行し得るかどうか検討した。Ｘ線回折ピークの強度から反応率は５０％と見積もられ、Ｌｉ２ＯがＬｉとＯ２に分解したことを確認した。 (Reduction process)
Li 2 O is placed in the reaction vessel of the experimental system of Example 1, and heat treatment is performed in a closed system at a temperature of 800 ° C. under vacuum (0.01 Pa) for 20 hours, and the reaction proceeds by identifying reaction products. We examined whether it could be done. The reaction rate was estimated to be 50% from the intensity of the X-ray diffraction peak, and it was confirmed that Li 2 O was decomposed into Li and O 2 .
（第二水素発生工程）
　Ｌｉに水を加え、３００℃まで加熱した後反応生成物の同定を行った。反応率はほぼ１００％であり、ＬｉＯＨとＨ２が生成したことを確認した。 (Second hydrogen generation process)
After adding water to Li and heating to 300 ° C., the reaction product was identified. The reaction rate was almost 100%, and it was confirmed that LiOH and H 2 were formed.
　以上のように、第１水素発生工程、還元工程、第２水素発生工程における反応はそれぞれ可能であることから、第１水素発生工程、還元工程、第２水素発生工程の順に繰り返し水素を製造することが実現可能であることがわかる。 As described above, since the reactions in the first hydrogen generation step, the reduction step, and the second hydrogen generation step are possible, hydrogen is repeatedly produced in the order of the first hydrogen generation step, the reduction step, and the second hydrogen generation step. It can be seen that this is feasible.
　なお、本発明は、本発明の範囲を逸脱することなく、様々な実施形態及び変形が可能とされるものである。また、上述した実施形態は、本発明を説明するためのものであり、本発明の範囲を限定するものではない。 It should be noted that the present invention can be variously modified and modified without departing from the scope of the present invention. Further, the above-described embodiment is for explaining the present invention, and does not limit the scope of the present invention.
　本出願は、２０１３年１２月２０日に出願された日本国特許出願２０１３－２６４０３０号に基づく。本明細書中に、日本国特許出願２０１３－２６４０３０号の明細書、特許請求の範囲、図面全体を参照として取り込むものとする。 This application is based on Japanese Patent Application No. 2013-264030 filed on Dec. 20, 2013. In this specification, the specification, claims, and entire drawings of Japanese Patent Application No. 2013-264030 are incorporated by reference.
　上述したように、水素製造方法では、効率よく水素を製造することができ、これまでの化石燃料の代替エネルギーとして利用可能である。 As described above, the hydrogen production method can efficiently produce hydrogen and can be used as an alternative energy to conventional fossil fuels.
　　１　水素製造装置
　１０　反応容器
　２０　導入口
　３０　排出口
　４０　アルカリ金属貯留容器
　５０　加熱装置
　６０　加熱冷却装置 DESCRIPTION OF SYMBOLS 1 Hydrogen production apparatus 10 Reaction container 20 Inlet 30 Discharge 40 Alkali metal storage container 50 Heating device 60 Heating and cooling device

Claims (4)

  1. 　アルカリ金属とアルカリ金属水酸化物とを反応させて、アルカリ金属酸化物と水素分子を生成させる第１水素発生工程と、
    　前記第１水素発生工程で生成したアルカリ金属酸化物を分解させて、アルカリ金属と酸素分子を生成させる還元工程と、
    　前記還元工程で生成したアルカリ金属と水とを反応させて、アルカリ金属水酸化物と水素分子を生成させる第２水素発生工程と、を有し、
    　前記第１水素発生工程、前記還元工程、前記第２水素発生工程の順に行う、
    　ことを特徴とする水素製造方法。     A first hydrogen generation step in which an alkali metal and an alkali metal hydroxide are reacted to generate an alkali metal oxide and a hydrogen molecule;
    A reduction step of decomposing the alkali metal oxide produced in the first hydrogen generation step to produce an alkali metal and oxygen molecules;
    A second hydrogen generation step of reacting the alkali metal produced in the reduction step with water to produce an alkali metal hydroxide and hydrogen molecules,
    The first hydrogen generation step, the reduction step, and the second hydrogen generation step are performed in this order.
    A method for producing hydrogen.
  2. 　前記第２水素発生工程では、前記還元工程で生成したアルカリ金属の一部と水とを反応させ、
    　前記第１水素発生工程では、前記還元工程で生成したアルカリ金属の残りと前記第２水素発生工程で生成したアルカリ金属水酸化物を用い、
    　前記第１水素発生工程、前記還元工程、前記第２水素発生工程の順に行う、
    　ことを特徴とする請求項１に記載の水素製造方法。     In the second hydrogen generation step, a part of the alkali metal generated in the reduction step is reacted with water,
    In the first hydrogen generation step, the remaining alkali metal generated in the reduction step and the alkali metal hydroxide generated in the second hydrogen generation step are used.
    The first hydrogen generation step, the reduction step, and the second hydrogen generation step are performed in this order.
    The hydrogen production method according to claim 1, wherein:
  3. 　前記アルカリ金属がリチウム、ナトリウム又はカリウムである、
    　ことを特徴とする請求項１又は２に記載の水素製造方法。     The alkali metal is lithium, sodium or potassium;
    The method for producing hydrogen according to claim 1 or 2, wherein:
  4. 　アルカリ金属とアルカリ金属水酸化物とを反応させて、アルカリ金属酸化物と水素分子を生成させる第１水素発生工程、前記第１水素発生工程で生成したアルカリ金属酸化物を分解させて、アルカリ金属と酸素分子を生成させる還元工程、及び、前記還元工程で生成したアルカリ金属と水とを反応させて、アルカリ金属水酸化物と水素分子を生成させる第２水素発生工程のそれぞれの反応が行われる反応容器と、
    　前記反応容器に接続しアルカリ金属を貯留するアルカリ金属貯留容器と、
    　前記反応容器に水を導入する導入口と、
    　前記反応容器の内部で生成した水素分子及び酸素分子を排出する排出口と、
    　前記反応容器を加熱する加熱装置と、
    　前記アルカリ金属貯留容器を加熱、冷却する加熱冷却装置と、を備える、
    　ことを特徴とする水素製造装置。     A first hydrogen generation step of reacting an alkali metal with an alkali metal hydroxide to generate an alkali metal oxide and hydrogen molecules; an alkali metal oxide generated in the first hydrogen generation step is decomposed; And a reduction step for generating oxygen molecules, and a second hydrogen generation step for generating alkali metal hydroxide and hydrogen molecules by reacting the alkali metal generated in the reduction step with water. A reaction vessel;
    An alkali metal storage container connected to the reaction container and storing alkali metal;
    An inlet for introducing water into the reaction vessel;
    A discharge port for discharging hydrogen molecules and oxygen molecules generated inside the reaction vessel;
    A heating device for heating the reaction vessel;
    A heating and cooling device for heating and cooling the alkali metal storage container,
    The hydrogen production apparatus characterized by the above-mentioned.
PCT/JP2014/083464 2013-12-20 2014-12-17 Method for generating hydrogen and hydrogen generator WO2015093547A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2580864A (en) * 2018-10-22 2020-08-05 Ouadi Miloud Apparatus to generate hydrogen from water splitting

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4964589A (en) * 1972-06-22 1974-06-22
JP2004182496A (en) * 2002-11-29 2004-07-02 Toshiba Corp Hydrogen-generating apparatus
JP2007145686A (en) * 2005-03-18 2007-06-14 Tokyo Institute Of Technology Hydrogen generating apparatus, laser reduction apparatus, energy conversion apparatus, method for generating hydrogen and power generation system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4964589A (en) * 1972-06-22 1974-06-22
JP2004182496A (en) * 2002-11-29 2004-07-02 Toshiba Corp Hydrogen-generating apparatus
JP2007145686A (en) * 2005-03-18 2007-06-14 Tokyo Institute Of Technology Hydrogen generating apparatus, laser reduction apparatus, energy conversion apparatus, method for generating hydrogen and power generation system

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2580864A (en) * 2018-10-22 2020-08-05 Ouadi Miloud Apparatus to generate hydrogen from water splitting

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