Apparatus and method for the simultaneous production of O3 and H2 gases.

Abstract

This invention provides a simultaneous production apparatus and manufacturing method for O3 gas and H2 gas, which uses a Ti plate for the (+) electrode without using any platinum-based metals, removes all of the Ti oxide film from its surface, and firmly deposits an inexpensive metal oxide onto the surface to eliminate peeling, while using an inexpensive SUS plate for the (-) electrode. [Solution] Placed inside a glass aquarium, In an apparatus for simultaneously producing O3 gas and H2 gas, in which O3 gas is generated from a (+) electrode and H2 gas from a (-) electrode, the (+) electrode is an O3 generating electrode made of a Ti matrix material without any Ti oxide films of TiO, TiO2, or Ti2O3 on its surface, and a vapor-deposited film is formed on its surface in which at least one metal oxide of SnO2, ZnO2, CuO2, or NiO2 is present within the TiB2, and the (-) electrode is an H2 generating electrode made of martensitic SUS material of SUS403 or SUS410, and these O3 generating electrode and H2 generating electrode are The aforementioned An apparatus for simultaneously producing O3 gas and H2 gas, characterized in that multiple electrodes are arranged vertically at predetermined intervals in a water tank, a hood is placed over the O3 generating electrode to guide the O3 generated around its sides upward, the tops of each hood are connected to provide an O3 collection manifold for extracting the O3 to the outside, and an H2 collection hood is provided above the water tank to collect the H2 generated around the H2 generating electrode and raised, and extract it to the outside.

Description

Technical Field

[0001] The present invention relates to a device and method for simultaneously producing inexpensive and simple O3 and H2 gases.

Background Art

[0002] According to Non-Patent Document 3, research on hydrogen gas has been rapidly progressing since the discovery that it has the effect of selectively removing reactive oxygen species when taken into the body. In particular, it has been reported to be effective against post-cardiac arrest syndrome, acute myocardial infarction, lifestyle-related diseases such as hypertension, diabetes, and hyperlipidemia, and coronavirus disease. That is, reactive oxygen species play an important role in the body such as immune function, but when they increase excessively, they are said to harm the human body by damaging cells or causing inflammation. It has been found that various diseases are induced by an excess of this reactive oxygen species, and hydrogen can remove the reactive oxygen species, which is the main culprit, to obtain benefits such as cancer prevention and the cure of lifestyle-related diseases.

[0003] A method for producing hydrogen gas is an electrolytic cell for electrolyzing water, in which two electrodes (anode and cathode) separated by an ion exchange membrane are arranged. And a high-cost platinum-based metal catalyst such as Pt, Pd, Ro, or Ir has been used for the (+) pole of the electrode.

[0004] On the other hand, according to the Japanese Society for Occupational Health, the allowable concentration of ozone for humans is set at 0.1 ppm or less. Ozone gas generated while keeping the concentration can be safely used for deodorization measures by oxidizing and decomposing malodors in the living area, sterilization, bleaching, etc.

[0005] This ozone gas generator mainly employs a device that generates ozone by the "corona discharge method". The corona discharge method is a device that generates ozone from oxygen-containing air passing through a glass discharge tube by arranging a dielectric body (a glass discharge tube) between electrodes and applying a high voltage to the electrodes. Here too, expensive platinum-based metal catalysts such as Pt, Pd, Ro, and Ir have been used for the (+) electrode of the aforementioned electrode.

[0006] In recent years, a device for simultaneously producing the hydrogen gas and ozone gas described above, "Ozone and Hydrogen Generation Method and Generating Apparatus" as shown in Patent Document 1, has been introduced. The distinguishing feature of this ozone and hydrogen generator is that it is an improved electrolytic gas generator that uses a cation exchange membrane (perfluorocarbon sulfonic acid-based cation exchange membrane) with porous anode material and cathode material tightly packed on both sides as a solid electrolyte, and produces ozone gas and oxygen gas from the anode side and hydrogen gas from the cathode side by supplying pure water to the anode-side chamber where platinum is placed and performing electrolysis. The device also features means for controlling the pressure on the anode side and / or cathode side so that the pressure on the anode side is always greater than the pressure on the cathode side and the difference between them is within 2.0 kg / cm2. In this example, the complex device configuration, including the use of a solid electrolyte, and the placement of expensive platinum are particularly noticeable.

[0007] Therefore, based on their long and valuable experience, the inventors focused on the fact that in the production of O3 gas, a Ti plate is used as the base material for the (+) electrode to remove the strong oxide film of TiO2, Ti2O3, Ti2O4, etc. on the surface (as introduced in Patent Document 2), and that comparable effects can be obtained by using inexpensive flux and metal oxides such as SnO2, ZnO2, CuO2, and NiO2, compared to expensive platinum-based metals, and continued their research. However, since the etching method described above uses a strong acid, the Kirkendall effect caused by the strong acid creates irregularities on the surface of the Ti plate in the order of 10 μm, leading to surface delamination. This surface delamination is also prone to occurring with platinum-based etching. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 3432136, "Method and apparatus for generating ozone and hydrogen" [Patent Document 2] Japanese Patent Publication No. 7108984, "Method for Removing Oxide Film from Titanium Alloy Surface," Inventor: Tetsuo Harada [Non-patent literature]

[0009] [Non-Patent Document 1] Hydrogen: The Ultimate Key to Healthy Longevity (by Toshifumi Wakayama) Chapter 1: Hydrogen's Potential is Expanding in Treatment of Intractable Diseases Chapter 2: Hydrogen as a Path to "Japan's Revival" Chapter 3: Why Does Hydrogen Have These Effects? Chapter 4: Hydrogen's Effectiveness in Cancer Treatment Chapter 5: Experiences with Hydrogen's Effects and How They Work [Non-Patent Document 2] Triglyceride Nursing Terminology Dictionary "Kangoroo" [Non-Patent Document 3] Enjoying Quantum Theory (PHP Bunko edition, by Katsuhiko Sato): Bohr's Quantum Conditions, pp. 95-96 [Overview of the Initiative] [Problems that the invention aims to solve]

[0010] The present inventors provide a method and apparatus for the simultaneous production of O3 gas and H2 gas, which enables simultaneous electrolysis production of O3 gas and H2 gas by using a Ti plate for the (+) electrode, strongly etching the Ti oxide film on its surface with a strong acid, and firmly depositing an inexpensive metal oxide on the surface to eliminate the aforementioned peeling, and by using an inexpensive SUS plate for the (-) electrode.

[0011] The technical features of this invention that solve the aforementioned problems are as follows (1) and (2). (1) A simultaneous production apparatus for O3 gas and H2 gas, wherein the (+) electrode and (-) electrode are characterized in that the (+) electrode is made of a Ti base material from which the oxide films of TiO, TiO2, and T2O3 on the surface have been removed by etching, and a vapor-deposited film is formed on its surface in which any one of the oxide metals SnO2, ZnO2, CuO2, or NiO2 exists within the TiB2, and the (-) electrode is made of a martensitic SUS system of SUS403 or SUS410, and a plurality of electrodes are arranged vertically alternately at predetermined intervals in a water tank, the O3 generating electrode is covered with a hood that guides the O3 generated around its side upward, the tops of each hood are connected to provide an O3 collection manifold for taking the O3 out to the outside, and an H2 collection hood is provided at the top of the water tank to collect the H2 generated around the H2 generating electrode and take it out to the outside. (2) In the (+) electrode and (-) electrode of the simultaneous production apparatus for O3 gas and H2 gas, the (+) electrode is made of a Ti base material from which the oxide films of TiO, TiO2, and T2O3 on the surface have been removed by etching, and H3BO3 is used as a flux on its surface, to which at least one metal powder of Sn, Zn, Cu, or Ni is mixed and arranged, and then heated at 400 to 700°C to form a vapor-deposited film in which the metal oxide of the metal powder exists within the TiB2, and the (-) electrode is made of SUS403 or A method for simultaneously producing O3 gas and H2 gas, characterized in that the H2 generating electrode is made of SUS410 martensitic SUS material, multiple electrodes are arranged vertically at predetermined intervals alternately in a water tank, the O3 generating electrode is covered with a hood to guide the O3 generated around its sides upward, the tops of each hood are connected to provide an O3 collection manifold for extracting the O3 to the outside, and an H2 collection hood is provided at the top of the water tank to collect the H2 generated around the H2 generating electrode and extracted to the outside.

[0012] <Definition of the constituent conditions of the above-mentioned features in the present invention> The etching method for removing the oxide films of TiO, TiO2, and T2O3 from the surface of the O3 generating electrode (+) electrode in this invention refers to the "method for removing oxide films from titanium alloy surfaces" etching method proposed in Patent Document 2. Specifically, this method for removing the oxide film on the surface of a titanium alloy involves chemically treating the surface with a first etching solution containing a fluoride-containing compound and methyl alcohol at pH 1, or chemically treating it with a second etching solution containing a fluoride-containing compound, hydrochloric acid, nitric acid, methyl alcohol, potassium cyanide (KCN) as an accelerator, and lead nitrate (Pb(NO3)2) as a modifier at pH 1, and then anodic treating it with a third etching solution containing ammonium fluoride, potassium hydroxide solution, hydrazine as a reducing agent, potassium iodide (KI) as a stabilizer, ethylene glycol (C2H6O2), glycerin (CH3H8O3), methanol (CH3OH), and water (H2O) at pH 7.

[0013] Furthermore, in this invention, when H3BO3 is used as a flux on the surface of an etched Ti base material, and one or two metal powders of Sn, Zn, Cu, and Ni are added to it and heated at 400 to 700°C, the oxygen in H3BO3 separates, and TiB2 and the metals oxidized from the metal powders are mixed into the surface of the Ti base material, forming a strong, peel-free vapor-deposited plating film. In other words, upon heating, Ti + 2H3BO3 is converted to → 2HBO2 (metaboric acid) + H2O → TiB2 + 3O2↑ 3O2↑ + Sn → SnO2 + 2O2↑ → ZnO2 + O2↑ → CuO2 Through oxidation, the Ti electrode developed a mixed plating structure of TiB2 + SnO2 + ZnO2 + CuO2, which allowed for the generation of ozone (O3). Of these, the Ti electrode with the TiB2 + SnO2 vapor deposition plated was the most efficient at generating O3, although the reason for this is unclear. Therefore, the heating temperature in the heating furnace is 400 to 700 °C. If it is less than 400 °C, the formation state of the metal oxide in the vapor deposition film is dilute, the strength decreases, and it peels off in a short period, making it inapplicable. If it exceeds 700 °C, the metal oxide and TiB2 melt, O separates, and a strong vapor deposition film cannot be obtained sufficiently. (Essential)

[0014] Regarding the heating and vapor deposition of the flux (H3BO3) + Sn + Zn + Cu in the heating furnace at 400 to 700 °C, the explanation based on Bohr's quantum condition is as follows. First, the formula: 2πrxmV = nh Here, r: the radius of the electron orbit m: the mass of the electron V: the velocity of the electron n: an integer h: Planck's constant H3BO3 begins to decompose as follows during heating at 400 to 700 °C. 2HBO3 → 2HBO2 + H2O → B2O3 + 3H2↑ (outside the external air) B2O3 + Ti → TiB2 + O3↑ That is, simple gases are generated by mixing in the vapor. The hydrogen gas does not decompose further, and Planck's constant h only pertains to quantum theory. H2 (-) → has electrons in the minimum orbit and cannot move outside or inside the orbit even due to thermal motion during heating at 400 to 700 °C. This is hydrogen. This hydrogen atom is also the smallest in terms of molecules and can shine through vibration, which is called the Bohr seismic intensity. Although the H3BO3 is simple, the novel discovery that TiB2 is generated as per the chemical reaction formula is the proof of O3 generation in the (+) electrode according to the present invention. Although H3BO3 is also contained in the conventional welding flux, it was impossible to prove O3 generation due to the reaction with 3 to 6 types of inorganic substances.

[0015] In the present invention, the water in the water tank is pure water, tap water, spring water, purified water, etc., and is not particularly limited and is extremely simple. For example, in the case of tap water, the contained chlorine (Cl), calcium hypochlorite, calcium, magnesium, etc. will adhere to both the positive (+) and negative (-) electrodes, but this can be cleaned periodically using an appropriate method. For example, cleaning can be done by alternately passing current through the positive (+) and negative (-) electrodes for 10 minutes every 1 to 2 hours.

[0016] Furthermore, the Ti plate (+) electrode in this invention will have a reduced lifespan due to the ionization of the TiB2+SnO2, CuO2, and ZnO2 metal oxides on its surface. Replacement will be necessary after a maximum of one year. Although the negative electrode of SUS has a long lifespan, any deposits can be dissolved and removed by washing with a weak acid such as citric acid (C6H8O7, pH 4). [Effects of the Invention]

[0017] <Effect 1> The present invention provides a simultaneous generation apparatus and method for O3 gas and H2 gas, which allows for the production of sufficient O3 gas using inexpensive H3BO3 and materials such as Sn, Zn, Cu, and Ni, without employing expensive CVD or AIP methods for metal deposition on the (+) electrode or using any platinum-based metals in the (+) electrode.

[0018] <Effects and Effects 2> Therefore, the (+) electrode is made using a Ti plate as the base plate, completely removing the Ti oxide film on its surface by strong acid etching, and then mixing one or two inexpensive metal powders such as Sn, Zn, Cu, and Ni in addition to the flux onto the surface as a flux and dowband (conductive), heating and oxidizing them to firmly deposit the O3 gas, thereby eliminating the problem of peeling and ensuring excellent performance. The O3 gas generated from the (+) electrode is collected in its entirety without leakage by the O3 gas rising guide hood and O3 gas collection manifold of the present invention. The recovered O3 gas is safely used for deodorization measures in living areas through oxidation and decomposition of malodorous odors, as well as for sterilization and bleaching.

[0019] <Effects and Effects 3> The concentration of O3 gas is diluted to 0.1 ppm to 0.3 ppm by adjusting the voltage to the electrodes or the amount of diluting air mixed in, and then supplied to rooms such as hospitals, clinics, and offices to deodorize and kill viruses, thereby maintaining a healthy and pleasant indoor environment free from unpleasant odors. For example, when changing the diapers of a patient with a care level of 4-5 in a hospital room, the release or emission of the substance can provide deodorizing and sterilizing effects. The voltage adjustment to the aforementioned electrodes is such that, for example, the amount of O3 and H2 generated is proportional to the current and voltage. For this reason, a simple dial adjustment device that adjusts from 24VDC to 48VDC is attached to the outlet of a commercially available product. Specifically, the H2 gas concentration is set to 10,000 ppm (max 1%) and the O3 gas concentration to 0.1-0.3 ppm. Since it is impossible to adjust the O3 gas generation electrode side using only 24VDC-48VDC, a bifurcated joint hose is used, with 4mm and 6mm diameter hoses separated to vent to the outside (across two chambers). For unattended indoor disinfection, open both of these nozzles fully to a maximum of 5 ppm, resulting in a room concentration of m³ x 2.14...X ppm. If you keep pets such as birds, dogs, or cats indoors, you can remove the odor of pet waste by first taking the pets outside and then releasing O3 gas at a maximum concentration of 5 ppm. Room: In the case of an 8-tatami mat room (8 x 8 x 8 x 2.14 ≈ 10000 = 0.109 ppm)

[0020] <Effects and Effects 4> Since H2 gas can become explosive at a maximum concentration of 4%, the maximum concentration is set at 10,000 ppm. Conventional water electrolysis attempts to prevent O2 and H2 from mixing at all, but to produce O3 and H2 simultaneously, complete separation and collection are necessary. In this invention, an inexpensive SUS plate is used for the (-) electrode to easily generate H2 gas. The H2 gas generated on the (-) electrode side is collected in its entirety without leakage by an H2 collection hood located above the water tank of the apparatus of this invention.

[0021] <Effects and Effects 4> Furthermore, the hydrogen gas generated by this invention can be effectively utilized, as described in detail in Non-Patent Document 3 above, to improve brain damage, prevent and treat cancer, and even cure lifestyle-related diseases, by removing reactive oxygen species in the body through the hydrogen gas inhalation method, which is a known advanced medical technology. For example, triglycerides are used as a barometer of a person's health. This neutral fat is oxidized by hydrogen to produce carbon dioxide, water, and energy. C55H104O6 (triglyceride molecule) + 78O2 → 55CO2 + 52H2O + energy As is clear from this reaction equation, for example, reducing triglycerides by 10 kg would require 29 kg of oxygen and 58 kg of hydrogen. This shows how much hydrogen must be inhaled to reduce triglycerides. [Brief explanation of the drawing]

[0022] [Figure 1] This is an overall explanatory diagram of a schematic longitudinal cross-section of the apparatus of the present invention. [Figure 2] This is an explanatory diagram showing a modified and enlarged portion of Figure 1. [Figure 3] Figure 2: Side view from the left. [Figure 4] This figure shows the amount of ozone and hydrogen produced. [Modes for carrying out the invention]

[0023] Figure 1 shows an example of the simultaneous generation device for O3 gas and H2 gas according to the present invention. A Ti plate (+) electrode 31 (O3 gas generation electrode) and a SUS plate (-) electrode 32 (H2 gas generation electrode) are vertically arranged alternately at equal intervals in a glass water tank 60 via a support connecting shaft 50 and a support ring 51 (insulating ring and conductive ring), and power is supplied to the Ti plate (+) electrode 31 and the SUS plate (-) electrode 32 via a simple dial adjustment device 34 that adjusts the voltage from 24VDC to 48VDC from a power supply 33. The glass aquarium 60 has an automatic water supply pipe 61 connected to the top and a drain pipe 62 connected to the bottom. Figures 2 and 3 show modified versions of Figure 1, in which the support connecting shaft 50 in Figure 1 is replaced with a positive conduction rod 50-1, a negative conduction rod 50-2, and an insulating support rod 50-3, and the support rings 30 between them and each electrode plate are replaced with an insulating ring 30-1 and a conduction ring 30-2. The Ti plate (+) electrode 31 is an O3 generating electrode formed by etching the surface of a Ti plate base material, then using H3BO3 as a flux on its surface, mixing in one or two metal powders of Sn, Zn, Cu, and Ni, and heating it in an electric heating furnace within the range of 400 to 700°C to form a vapor-deposited film in which metal oxides of SnO2, ZnO2, CuO2, and NiO2 exist within the TiB2. The O3 generating electrode 31 is covered with a transparent insulating hood 41 that guides the O3 generated around its sides upward, and the tops of each hood 41 are connected to form a transparent insulating O3 collection manifold 42 (hose joint) that collects the O3 gas and extracts the entire amount of O3 gas to the outside. An exhaust duct 43 is connected to the O3 collection manifold 42 and the O3 gas is sent to an external O3 gas supply destination.

[0024] The SUS plate (-) electrode 32 is an H2 generating electrode made of martensitic SUS material, either SUS403 or SUS410. The H2 gas generated around the side of this H2 generating electrode 32 rises within the water tank and is collected in a collection hood 51 formed above the water tank, and then sent out to an external hydrogen supply destination via a discharge duct 52. The collection hood 51 has an inverted funnel shape on its lower surface and is equipped with a discharge duct 52 in the center from which the entire amount of H2 gas collected is taken outside.

[0025] The detailed conditions for O3 gas generation and H2 gas generation methods in the above apparatus, as well as the O3 gas generation and H2 gas generation status, are shown in Figure 4 below. As is clear from Figure 4, the method examples of the present invention are Examples No. 1 to 6, and it has been found that they generate O3 gas and H2 gas better than comparative examples No. 7 to 12. [Industrial applicability]

[0026] As described above, the present invention exhibits excellent effects and capabilities, and therefore will make a significant contribution to the development of the ozone generation and H2 gas generation equipment industry, as well as the ozone utilization medicine society. [Explanation of Symbols]

[0027] 30: Insulator 30-1: Insulating ring 30-2: Dentsu Ring 31: Ti plate (+) electrode (O3 gas generating electrode) 32: (-) electrode (H2 gas generating electrode) 33: Power supply 34: Dial adjustment device 41: Food 42: O3 Collection Manifold 43: Exhaust duct 50: Support connecting shaft 50-1:+Electrical rod 50-2:-Electrical rod 50-3: Insulating support rod 51: Collectible Food 52: Exhaust duct 60: Glass aquarium 61: Automatic water supply pipe 62: Drain pipe

Claims

【Request Item 1】 In a simultaneous production apparatus for O3 gas and H2 gas, the (+) electrode and (-) electrode are made of TiO, TiO 2 , T 2 O 3 An apparatus for the simultaneous production of O3 gas and H2 gas, characterized in that a Ti matrix material from which the oxide film of TiB2 has been removed by etching is used as the O3 generating electrode, on which a vapor-deposited film is formed on the surface thereof containing at least one metal oxide, such as SnO2, ZnO2, CuO2, or NiO2, is present in TiB2, the (-) electrode is an H2 generating electrode made of martensite SUS material of SUS403 or SUS410, multiple electrodes of the O3 generating electrode and the H2 generating electrode are arranged vertically alternately at predetermined intervals in a water tank, the O3 generating electrode is covered with a hood that guides the O3 generated around its sides upward, the tops of each hood are connected to provide an O3 collection manifold for extracting the O3 to the outside, and an H2 collection hood is provided at the top of the water tank to collect the H2 generated around the H2 generating electrode and extracted to the outside. 【Request Item 2】 In a simultaneous production apparatus for O3 gas and H2 gas, the (+) electrode and (-) electrode are made of TiO, TiO 2 , T 2 O 3 A method for simultaneously producing O3 gas and H2 gas is characterized by the following: a Ti base material from which the oxide film of Ti has been removed by etching is used as the O3 generating electrode, on its surface H3BO3 is used as a flux and mixed with at least one metal powder of Sn, Zn, Cu, or Ni and then heated at 400 to 700°C to form a vapor-deposited film in which the metal oxide of the metal powder exists within TiB2; the (-) electrode is an H2 generating electrode made of martensite SUS system SUS403 or SUS410; multiple electrodes of the O3 generating electrode and the H2 generating electrode are arranged vertically alternately at predetermined intervals in a water tank; the O3 generating electrode is covered with a hood to guide the O3 generated around its sides upward, and the tops of each hood are connected to provide an O3 collection manifold for extracting the O3 to the outside; and an H2 collection hood is provided at the top of the water tank to collect the H2 generated around the H2 generating electrode and extracted to the outside.

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