JP2013237599A - Hydrogen generation method to collect hydrogen from water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen generation method for generating a large amount of hydrogen from water.SOLUTION: The inside of a reaction cell 1 formed of stainless steel, iron, or the like is made to be in an oxygen-free state with no oxygen in the air; NaOH or KOH is supplied into the reaction cell 1 as a reaction agent 5; the reaction cell 1 is heated from a peripheral wall thereof to 300°C or higher so as to make fine particles be scattered from a reaction agent surface and to form a reaction space S; water vapor is supplied thereto so as to form special oxide films l, l, lon the inner wall of the reaction cell 1; oxygen in water, oxygen in the reaction agent, and sodium or potassium in the reaction agent are absorbed in the special oxide films; and the special oxide films are made to further decompose water; and as a result, a large amount of hydrogen is made to be taken out from water.

Description

  The present invention relates to a hydrogen generation method for generating hydrogen using water.

  Means for bringing nickel, chromium and iron elements into contact with an alkali metal molten salt, scattering fine particles from the surface of the molten salt into a reaction space, and bringing hydrogen from water by bringing water into contact with the fine particles. The present inventor has filed several applications.

Japanese Patent Application No. 2009-009733 Japanese Patent Application No. 2009-039485 Japanese Patent Application No. 2009-120757 Japanese Patent Application No. 2009-178741

  However, in these applications, the reaction principle is insufficient and the reason why hydrogen is generated in large quantities is insufficient.

  In the hydrogen generation method for collecting hydrogen from water of the present invention, a metal element supplier is present in an oxygen-free sealed atmosphere free from oxygen in the air, and an alkali metal hydroxide is contained in the sealed atmosphere. And heating the sealed atmosphere to convert the alkali metal hydroxide into a molten salt, spattering metal hydroxide fine particles from the surface to form a reaction space, and supplying water vapor into the reaction space Then, an oxide film having a certain thickness is formed on the surface of the metal element supplier, and when the oxide film becomes a certain thickness, the oxide film is peeled off from the surface of the metal element supplier, and a new metal element supplier surface is newly formed. Oxide films were formed, and these oxide films reacted with water vapor supplied to generate hydrogen.

The alkali metal hydroxide is preferably sodium hydroxide (NaOH) or potassium hydroxide (KOH). Furthermore, in order to melt and liquefy these alkali metal hydroxides, it is preferable to heat the atmospheric temperature to 300 ° C. or higher. Furthermore, the oxide film is preferably made of sodium ferrate (Na ₃ Fe ₅ O ₉ ), sodium chromate (Na ₃ Cr ₅ O ₉ ), or a mixture thereof. Furthermore, it is preferable that the metal element supply body is made of a cylindrical stainless steel material, and an oxide film is formed in a ring shape on the inner wall of the stainless steel material.

The metal element supply body such as stainless steel or iron is supplied into the sealed container (reaction cell) as fins, or the sealed container itself is used as the metal element supply body, and air (oxygen) is removed from the sealed container. When an alkali metal hydroxide such as NaOH or KOH is housed inside and heated to 300 ° C or higher in order to melt and liquefy the metal element supplier and the alkali metal hydroxide, fine particles are scattered from the alkali metal hydroxide. Thus, a reaction space is formed, and water vapor is supplied into the reaction space. This produces special oxide film on the metal element supply surface, oxygen in the water, the oxygen gas is absorbed as the special oxide film is not present in any closed container, the special oxide film Na ₃ Fe ₅ O ₉ or K ₃ Fe ₅ O ₉ is the main component, and fine particles come out of this, react with water vapor, and make a new special oxide film on the surface of the metal element supplier. At the same time, the generated special oxide film is peeled off from the surface when the thickness is constant, and a new metal element supplier surface is exposed. A special oxide film is formed on the exposed surface, and the special oxide film gradually develops. Can generate a large amount of hydrogen.

  That is, oxygen in the water is completely absorbed as a special oxide film, and this special oxide film further decomposes the water to form a new special oxide film. If it becomes a state that obstructs the flow of water, it is necessary to remove a part of it and create a flow of water vapor. It has been confirmed that if the removed special oxide film is transferred to another sealed container and water vapor is supplied, further hydrogen can be generated.

The schematic block diagram of the 1st hydrogen generator which concerns on this invention, 1 is a cutaway view of the apparatus of FIG. FIG. 1 shows a growth state diagram of a special oxide film in the apparatus of FIG. Growth process diagram of special oxide film generated in fin shape, The schematic block diagram of the 2nd hydrogen generator which concerns on this invention, A perspective view of a reactant container accommodated in the second hydrogen generator; Atomic ratio spectrum diagram of mass spectrometer showing components of generated hydrogen gas, An open view of a third hydrogen generator according to the present invention, A cutaway view showing a state in which the special oxide film is stored in the cylindrical cell, The figure which shows the ionic component contained in the microparticles | fine-particles of a reactive agent.

  Embodiments of the present invention will be described below with reference to the drawings.

In FIG. 1, a first hydrogen generator M ₁ for carrying out the hydrogen generation method of the present invention has a cylindrical stainless steel (SUS304) or iron (SS) reaction cell 1 at one end thereof. Is provided with a water pipe 2 for supplying water and a hydrogen pipe 3 for discharging hydrogen at the other end, and the reaction cell 1 is heated by a burner 4 at its outer peripheral wall. Contains an alkali metal hydroxide such as sodium hydroxide (NaOH) or potassium hydroxide (KOH) as the reactant 5. The heating method of the reaction cell 1 may be gas heating or a planar electric heater, but it is necessary that the reaction cell 1 is sufficiently heated so that the fine particles of the reactant are sufficiently scattered. Providing a heating means is not preferable because the structure becomes complicated, and it is preferable in terms of structure to heat the outer wall surface of the reaction cell. In this system, the diameter of the reaction cell is limited, and in order to uniformly heat the inside of the cell, a diameter of 10 cm or less is preferable. Air needs to be completely discharged from the reaction cell 1 by a vacuum pump or the like, and the reaction cell is heated to a temperature (about 300 ° C.) or higher at which the reactant is liquefied and melted.

  When the reaction cell 1 and the reactant 5 therein are heated to 300 ° C. or higher (particularly preferably about 500 ° C.), innumerable nano-order fine particles 6 scatter from the liquid surface of the liquefied reactant 5 and are liquid. A reaction space S is formed on the surface.

  When a predetermined amount of water is supplied from the water pipe 2 into the water chamber 1a, the water immediately becomes water vapor of about 120 to 130 ° C., and this water vapor is supplied to the reaction space 6, and the particles of the water vapor and the reactants. Microparticles collide with each other and react. Note that the fine particles of the reactant are abnormally large in hydrophilicity and completely capture the water vapor particles.

  The bottom of the reaction cell 1 is provided with stainless steel or iron fins 7 at predetermined intervals as required, and the fins 7 are provided with a number of holes 8 so that the reactant can move. (Fig. 2). In order to decompose water, it is necessary for the reactant to react with water vapor in the presence of the metal element, and the metal element is supplied from the inner wall of the reaction cell 1 and the fin 7 provided as necessary, When the inner wall of the reaction cell 1 or the fin 7 functions as a metal element supplier, and the reaction cell 1 is formed of a non-metallic material such as ceramic, a metal element supplier such as the fin 7 is indispensable.

The fine particles of the reactant (in the case of NaOH) are Na ⁺ , OH ⁻ , Fe ²⁺ , Cr ²⁺ , since the reactant is in contact with a high-temperature metal wall (the surface of the fin 7 and the inner wall of the reaction cell) It contains ^ions such as Ni ²⁺ (if iron material is used for reaction cell 1 and fin 7, there is no Cr ²⁺ , Ni ²⁺ ) (FIG. 10), and when the fine particles collide with water vapor particles,

(Equation 1)
10M (Fe, Cr) + 6NaOH + 12H 2 O → 2Na 3 M (Fe 5, C r5) O 9 + 15H 2 ↑ ... formula (1)
According to the reaction formula, sodium ferrate (Na ₃ Fe ₅ O ₉ ) and sodium chromate (Na ₃ Cr ₅ O ₉ ) are generated. Ni ²⁺ ions do not form oxides, and Ni oxides have never been detected in experiments. When KOH is used as the reactant, K is substituted for Na, and K ₃ Fe ₅ O ₉ and K ₃ Cr ₅ O ₉ are generated as oxides.

  When oxygen in the air is present in the reaction cell 1,

(Equation 2)
_{2M (Fe, C r) +} 2NaOH + 2H 2 O → 2NaM (Fe, C r) O 2 + 3H 2 ↑ ... formula (2)
It has been confirmed that sodium ferrate (NaFeO ₂ ) and sodium chromate (NaC _r O ₂ ) with a small number of oxygen are produced.

Although the above-mentioned oxygen number (O ₉ ), Na ₃ Fe ₅ O ₉ and Na ₃ Cr ₅ O ₉ are semiconductors, they are conductive, hard, and hydrophilic, and even when heated to about 1000 ° C., they do not melt. If left in the air at room temperature, it absorbs moisture and deliquesces due to its hydrophilicity. The same applies to K ₃ Fe ₅ O ₉ and K ₃ Cr ₅ O ₉ . On the other hand, NaFeO ₂ and NaC _r O _{2 with} a low oxygen number are hydrophilic, but they are insulating, brittle and low in hardness. When this oxide is formed, its function as a reactant is reduced in a short period of time. Only a small amount of hydrogen can be collected.

The Na ₃ Fe ₅ (Cr ₅ ) O ₉ is formed on the inner wall of the reaction cell 1 as a film over a plurality of layers (l ₁ , l _2, l ₃ ), as shown in FIG. The center is a water vapor passage. The formation of the fin 7 will be described below. First, as shown in FIG. 4, a film (Na ₃ Fe ₅ (Cr ₅ ) O ₉ ) l ₁ having a thickness of 0.1 mm to 0.5 mm is formed on the surface of the fin 7. When the film is formed (FIG. 4a) and this film has a predetermined thickness, it is peeled off from the surface of the fin 7 (FIG. 4b), and a new surface (7a) of the fin 7 is exposed, and a new film l ₂ is exposed on the exposed surface 7a. When this film l ₂ is also peeled off from the surface of the fin 7, a new film l ₃ is formed, and this film l ₃ is also peeled off, so that the special film is sequentially formed in layers. Similarly, special films l ₁ , l _{2, and} l ₃ are formed on the inner wall of the reaction cell 1 while being sequentially peeled off. That is, as shown in FIG. 3A, fine particles scattered from the surface of the reactant 5 form a special oxide film l ₁ on the inner wall of the reaction cell 1 while capturing water vapor, and this film l ₁ has a predetermined thickness. Then, a new exposed surface comes out from the inner wall and a new oxide film l ₂ is formed on this exposed surface, and this oxide film l ₂ is peeled off to form a further oxide film l _3. As shown in FIG. 3B, a ring-shaped oxide film aggregate (FIG. 3B) is formed. Similar to the case of molten salt (NaOH, KOH) from the surface of these special films l ₁ , l _2, l ₃ , Na ⁺ (K ⁺ ), Fe ₂ , Cr ²⁺ , Ni ²⁺ , O ²⁻ Particles containing ions collide with water vapor particles,

(Equation 3)
3Na (K) + 5Fe (Cr ) + 3O 2 + 3 H 2 O → Na 3 (K 3) Fe 5 (Cr 5) O 9 + 3H 2 ··· (3)
In the same manner, the special oxide Na ₃ (K ₃ ) Fe ₅ (Cr ₅ ) O ₉ is generated, and a special film is sequentially formed on the surface of the fin 7 and the inner wall of the reaction cell 1. This reaction is likely to occur on the surface of the metal element supplier that is rich in metal elements, and when the film of a predetermined thickness is peeled off, a new film is formed on the new metal surface. This reaction is performed by oxygen in the air. As long as it does not flow into the cell 1, it continues for a long time, and according to experiments, it has been confirmed that it is heated for about 7 hours a day and continued for 190 days or more.

[Experiment 1]
In order to confirm the formation state of the special oxide film, as shown in FIGS. 5 and 6, a second hydrogen generator M < _b > ₂ was made. That is, one end of a cylindrical reaction cell 10 made of SUS304 (Cr18% -Ni8% -Fe residue) can be opened and closed by the lid cylinder 11, and the sealing portion 12 is separated from the heating portion by the burner 13.

  The lid cylinder 11 is provided with a spacer cylinder 14 for eliminating an extra space, and a long box-like reactant container 15 is accommodated in a part corresponding to the heating part in the reaction cell 10. , 5 moles (200 g) of NaOH is added. A water pipe 17a is formed at the other end of the reaction cell 10, and a hydrogen discharge pipe 17b is formed at the lid cylinder 11 side.

  At one time, 0.3 cc of water was supplied from the water pipe 17a, the amount of hydrogen generated was measured with a flow meter, and the change in the weight of the entire reaction cell 10 was measured.

前記反応剤入れ１５の周壁１５ａの内壁、外壁にもNa₃Fe₅O₉の膜が形成されており、反応セル１０の上部内壁にも同様の膜が検出された。前記反応剤入れ（反応剤を含む）１５の重量変化は２８ｇであり、これはNaOHが２８ｇ減少していることを示す。

Na ₃ Fe ₅ O ₉ films were also formed on the inner and outer walls of the peripheral wall 15 a of the reactant container 15, and similar films were detected on the upper inner wall of the reaction cell 10. The change in the weight of the reactants containing (including the reactants) 15 was 28 g, indicating that the NaOH was reduced by 28 g.

  Further, the reaction cell 10 as a whole increased by 60 g. The amount of water injected was 38.4 cc, and the amount of oxygen in this was 34.1 g. Here, all the NaO in NaOH remained in the cell, and oxygen and oxygen in the injected water were produced. Then

６１．４ｇの重量が増加することとなるが、実測では６０ｇであることから、１．４ｇのNaOHが水素と共に外部に流出したものと思われる。すなわち、注入した水の中の酸素と消費したNaOH中の酸素とナトリウムは、ほぼ完全に反応セル内でNa₃Fe₅(Cr₅)O₉の特殊酸化膜を形成しているものと判断できる。

Although the weight of 61.4 g is increased, it is 60 g in actual measurement, so that it seems that 1.4 g of NaOH flows out together with hydrogen. That is, it can be determined that oxygen in injected water and oxygen and sodium in consumed NaOH almost completely form a special oxide film of Na ₃ Fe ₅ (Cr ₅ ) O ₉ in the reaction cell. .

  Incidentally, when the gas discharged from the hydrogen discharge pipe 17b was analyzed with a mass analyzer and the atomic ratio was measured, as shown in FIG. 7, 99.5% or more was hydrogen and oxygen with a mass of 32 was not detected at all. It turned out that oxygen does not exist as a gas at all.

[Experiment 2]
The special oxide films Na ₃ Fe ₅ O ₉ and Na ₃ Cr ₅ O ₉ were confirmed to be conductive, hygroscopic, hard and heat-resistant, and the oxide itself decomposes water. First, as shown in FIG. 8, it was prepared third hydrogen generator M ₃ of a shallow box shape. The hydrogen generator M ₃ has a main body 30 (30 cm × 30 cm × 5 cm) made of SUS304, fins 31, 31... 31 installed at predetermined intervals in the main body 30, closed with a lid 32, and dispersed in 4 mol of NaOH (160 g). Stored. After heating the gas for 6 days, the fins 31, 31... 31 to which the special oxide film is attached and the special oxide films l, l... L attached to the surface of the main body 30 are peeled off to form a cylindrical shape (SUS304) as shown in FIG. In the reaction cell 40 (fourth hydrogen generator M ₄ ) and heated by the burner 41 to generate hydrogen.

第３水素発生装置Ｍ_３は、その本体３０は比較的大きいため注水量７２．２ｃｃに対して水素１４１．６ｌが発生しており、注水量に対する水素発生量が著しく多いことが注目される。

Since the main body 30 of the third hydrogen generator M ₃ is relatively large, hydrogen 141.6 l is generated with respect to the water injection amount 72.2 cc, and it is noted that the hydrogen generation amount with respect to the water injection amount is remarkably large.

１〜４日間は、注水量に対する水素収量がある程度確保されていたが、５日目以降はその比率が低下している。しかしながら、１８日間のみデータとして掲載したが、５０日目以降も水素を出し続けている。これにより、特殊酸化膜はそれ自体反応剤の機能を有していることが判明した。

The hydrogen yield relative to the amount of water injected was secured to some extent for 1 to 4 days, but the ratio decreased after the 5th day. However, although it was published as data only for 18 days, it continues to produce hydrogen after the 50th day. This revealed that the special oxide film itself has the function of a reactant.

  In addition, as a reactant, NaOH and KOH are used alone, respectively, but even if they are mixed in an appropriate ratio, the reactivity is not significantly inferior, but NaOH alone is better than KOH or a mixture thereof. It has been found that

  Furthermore, it has been confirmed that the reaction of the reactant becomes more active when molybdenum (Mo) is added to the reactant as 1/4 to 1/2 of the weight of the reactant.

DESCRIPTION OF SYMBOLS 1 ... Reaction cell 2 ... Water pipe 3 ... Hydrogen pipe 4 ... Burner 5 ... Reactant 7 ... Fin 10 ... Reaction cell 11 ... Lid cylinder 14 ... Spacer cylinder 15 ... Reactant container 30 ... Main body 40 ... Reaction cell.

Claims (6)

Let the metal element supplier exist in an oxygen-free sealed atmosphere where there is no oxygen in the air,
An alkali metal hydroxide as a reactant is disposed in the sealed atmosphere, and the sealed atmosphere is heated to form the molten salt of the reactant, and the reactant fine particles are scattered from the surface into the sealed atmosphere to react. A space is formed, water vapor is supplied into the reaction space, an oxide film is formed on the surface of the metal element supplier, and when the oxide film reaches a predetermined thickness, the oxide film is peeled off from the surface of the metal element supplier At least, a new metal element supplier surface was exposed, an oxide film was further formed on the new surface, and hydrogen was generated from water by reacting these oxide film and water vapor. Hydrogen generation method for collecting water.   The method for generating hydrogen according to claim 1, wherein the reactant is at least one of potassium hydroxide and sodium hydroxide.   The method for generating hydrogen according to claim 1, wherein the inside of the sealed atmosphere is heated to a temperature equal to or higher than the melting point of the reactant so that the reactant is melted.   The method for generating hydrogen according to claim 1, wherein molybdenum (Mo) is added to the reactant. The oxide film includes sodium ferrate (Na ₃ Fe ₅ O ₉ ), sodium chromate (Na ₃ Cr ₅ O ₉ ), potassium ferrate (K ₃ Fe ₅ O ₉ ), and potassium chromate (K ₃ Cr ₅ O). The hydrogen generation method according to claim 1, which is at least one of ₉ ).   The metal element supply body is formed of a cylindrical stainless steel material to form a reaction cell. The reactant is supplied into the reaction cell, and the outer peripheral wall of the reaction cell is heated to a temperature equal to or higher than the melting point of the reactant to form the oxide film. The hydrogen generation method according to claim 1, wherein the hydrogen generation method is formed in a ring shape along the inner wall of the reaction cell.

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