Apparatus and method for simultaneous production of O3 and H2 gas.

Abstract

To provide an apparatus for simultaneously producing O3 gas and H2 gas, and a method for producing the same, which uses a Ti plate for the (+) electrode without using any platinum-based metal, removes all of the Ti oxide film on its surface, and firmly deposits an inexpensive metal oxide on the surface to eliminate peeling, and uses an inexpensive SUS plate for the (-) electrode. [Solution] Placed in a glass aquarium, In an apparatus for simultaneously producing O3 gas and H2 gas, which generates O3 gas from a (+) electrode and H2 gas from a (-) electrode, respectively, the (+) electrode is an O3 generating electrode having a Ti base material on the surface free of any Ti oxide film such as TiO, TiO2, or Ti2O3, on which a vapor deposition film is formed in which at least one metal oxide of SnO2, ZnO2, CuO2, or NiO2 is present in TiB2, and the (-) electrode is an H2 generating electrode made of martensite SUS such as SUS403 or SUS410, and these O3 generating electrodes and H2 generating electrodes 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, the O3 generating electrodes are covered with hoods that guide the O3 generated around the sides upward, and an O3 collection manifold is provided by connecting the tops of each hood to remove the O3 to the outside, and an H2 collection hood is provided above the water tank to collect the H2 that is generated around the H2 generating electrode and rises, and removes it to the outside.

Description

[Technical Field]

[0001] The present invention relates to an inexpensive and simple apparatus and method for simultaneously producing O3 and H2 gases. [Background technology]

[0002] According to Non-Patent Document 3, hydrogen gas has been rapidly researched following the discovery that its incorporation into the body has the effect of selectively removing active oxygen. It has been reported to be particularly effective against post-cardiac arrest syndrome, acute myocardial infarction, lifestyle-related diseases such as hypertension, diabetes, and excess triglycerides, as well as COVID-19. In other words, while active oxygen plays an important role in the body, such as in immune function, if it increases too much it can damage cells, cause inflammation, and harm the human body. It is known that an excess of this reactive oxygen species can cause various diseases, and by removing the active oxygen species that are the root cause of these diseases, hydrogen can provide benefits such as preventing cancer and curing lifestyle-related diseases.

[0003] The method for producing hydrogen gas is to place two electrodes (anode and cathode) separated by an ion exchange membrane in an electrolytic cell, which is a water electrolysis device, where the electrolysis reaction occurs. Expensive platinum-based metal catalysts such as Pt, Pd, Ro, and Ir have been used for the (+) electrode.

[0004] On the other hand, the Japan Society for Occupational Health has set the permissible concentration of ozone gas for humans at 0.1 ppm or less. Ozone gas generated within this concentration can be safely used for deodorizing by oxidizing and decomposing odors in living areas, as well as for sterilization and bleaching.

[0005] The most widely used ozone gas generators are those that generate ozone using the "corona discharge method." Corona discharge is a method in which a dielectric (a glass discharge tube) is placed between electrodes, a high voltage is applied to the electrodes, and ozone is generated from oxygen-containing air that passes through the glass discharge tube. Here too, expensive platinum-based metal catalysts such as Pt, Pd, Ro, and Ir have been used for the (+) electrode.

[0006] Recently, an apparatus for simultaneously producing the hydrogen gas and ozone gas described above, "Ozone and Hydrogen Generating Method and Generating Apparatus" shown in Patent Document 1, has been introduced. This ozone and hydrogen generation device is characterized by an improved electrolytic gas generator that uses a cation exchange membrane (perfluorocarbon sulfonic acid cation exchange membrane) with porous anode and cathode materials tightly attached to 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 chamber containing platinum and electrolyzing it.It is equipped with a means for controlling the pressure on the anode side and / or the pressure on the cathode side so that the pressure on the anode side is always higher than the pressure on the cathode side, and the difference 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 also noticeable.

[0007] Based on their long and valuable past experience, the inventors of the present invention have continued their research, focusing on the fact that, in order to produce O3 gas, a Ti plate is used as the base material for the (+) electrode, and the strong oxide films such as TiO2, Ti2O3, and Ti2O4 on the surface are removed (as described in Patent Document 2), and that, compared to expensive platinum-based metals, an effect comparable to that of the expensive platinum-based metals can be obtained by using inexpensive flux and metal oxides such as SnO2, ZnO2, CuO2, and NiO2. However, because the etching method uses strong acid, the Kirkendall effect of the strong acid creates irregularities on the surface of the Ti plate, resulting in surface peeling. This surface peeling is also likely to continue in platinum-based materials. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Patent No. 3432136 "Ozone and hydrogen generation method and generation device" [Patent Document 2] Patent No. 7108984 "Method for removing oxide film from titanium alloy surface" Inventor: Tetsuo Harada [Non-patent literature]

[0009] [Non-Patent Document 1] Hydrogen is the ultimate key to a long and healthy life. Written by Toshifumi Wakayama Chapter 1: Hydrogen's potential for treating intractable diseases is expanding. Chapter 2: Hydrogen and the road to "revitalizing Japan." Chapter 3: Why hydrogen has such an effect. Chapter 4: Hydrogen that increases the effectiveness of cancer treatment. Chapter 5: Experience the effects of hydrogen and how it works. [Non-patent document 2] Neutral Fat Nurse's Dictionary "Kangoroo" [Non-patent document 3] "Enjoying Quantum Theory" PHP Bunko (by Katsuhiko Sato) Bohr's Quantum Conditions, pp. 95-96 Summary of the Invention [Problem to be solved by the invention]

[0010] The inventors have provided a method and apparatus for simultaneously producing O3 gas and H2 gas by using a Ti plate for the (+) electrode without using any platinum-based metal, etching the Ti oxide film on the surface of the plate with strong acid, and then firmly depositing an inexpensive metal oxide on the surface to completely eliminate the peeling, while using an inexpensive SUS plate for the (-) electrode, enabling simultaneous electrolytic production of O3 gas and H2 gas.

[0011] The technical features of the present invention that solve the above-mentioned problems are as follows (1) and (2). (1) Placed in a glass aquarium, In an apparatus for simultaneously producing O3 gas and H2 gas, O3 gas is generated from a (+) electrode and H2 gas is generated from a (-) electrode, respectively. The (+) electrode is an O3 generating electrode having a Ti base material on the surface of which is free of any Ti oxide film such as TiO, TiO2, or Ti2O3, and on whose surface is formed a vapor-deposited film in which at least one metal oxide of SnO2, ZnO2, CuO2, or NiO2 is present in TiB2; The negative electrode is an H2 generating electrode made of martensite SUS such as SUS403 or SUS410, and the O3 generating electrode and the H2 generating electrode are The aforementioned Multiple poles are arranged vertically at predetermined intervals in the tank, The O3 generating electrode is covered with a hood that guides the O3 generated around the side upward, and an O3 collecting manifold is provided by connecting the tops of the hoods to extract the O3 to the outside. An H2 collecting hood is provided above the water column to collect the H2 generated around the H2 generating electrode and extract it to the outside. (2) Placed in a glass aquarium, A method for simultaneously producing O3 gas and H2 gas, which generates O3 gas from a (+) electrode and H2 gas from a (-) electrode, The (+) electrode is a Ti base material from which all of the oxide films of TiO, TiO2, and Ti2O3 on the surface have been removed by etching, and on its surface, at least one metal powder of Sn, Zn, Cu, or Ni is mixed and placed in a flux of H3BO3, and then heated at 400 to 700°C to form a vapor-deposited film in which the metal oxide of the metal powder exists in TiB2, making it an O3 generating electrode. The (-) electrode is a H2 generating electrode made of martensitic SUS-based SUS403 or SUS410, and these O3 generating electrodes and the H2 generating electrode are The aforementioned A method for simultaneously producing O3 gas and H2 gas, characterized in that multiple electrodes are arranged vertically at predetermined intervals in a water tank, the O3 generating electrodes are covered with hoods that guide the O3 generated around the sides upward, the top of each hood is connected to an O3 collection manifold to remove the O3 to the outside, and an H2 collection hood is provided above the water tank to collect and remove the H2 generated around the H2 generating electrodes and rising to the outside.

[0012] <Definition of the constitutive conditions of the above-described features of the present invention> The O3 generating electrode in the present invention: TiO, TiO2, on the surface of the (+) electrode Ti 2 O The etching method for removing all of the oxide film in 3 refers to the etching method proposed in Patent Document 2 as "Method for removing oxide film from the surface of titanium alloy." Specifically, this method involves chemically treating the oxide film on the surface of a titanium alloy with a first etching solution containing a fluoride-containing compound and methyl alcohol at an acidic pH of 1, or 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 an acidic pH of 1, followed by anodizing 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 a neutral pH of 7.

[0013] In addition, in the present 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 this and placed and heated at 400 to 700°C, the O in H3BO3 separates and TiB2 and the metal powder oxidized therein are mixed on the surface of the Ti base material, forming a strong vapor deposition plating film that does not peel off. That is, when heated, Ti + 2H3BO3 → 2HBO2 (metaboric acid) + H2O → TiB2 + 3O2↑ 3O2↑+Sn→SnO2+2O2↑→ZnO2+O2↑→CuO2 By the oxidation reaction with TiB2, the Ti electrode side became a mixed plating structure of TiB2 + SnO2 + ZnO2 + CuO2, and was able to generate ozone O3. Of these, the Ti electrode with vapor deposition plating of TiB2 + SnO2 was the most efficient in generating O3, although the reason for this is unclear. Therefore, the heating temperature in the heating furnace is 400 to 700°C. If the temperature is below 400°C, the metal oxide in the vapor-deposited film is weak, the strength is reduced, and the film peels off in a short period of time, making it unsuitable for use. If the temperature exceeds 700°C, the metal oxide and TiB2 melt, O separates, and a sufficiently strong vapor-deposited film cannot be obtained. (Required)

[0014] The deposition of the flux (H3BO3)+Sn+Zn+Cu by heating in a heating furnace at 400 to 700°C can be explained as follows using Bohr's quantum conditions. First, the formula: 2πrxmV=nh where r is the radius of the electron orbit m: electron mass V: electron velocity n: integer h: Planck's constant H3BO3 begins to decompose during heating at 400-700°C as follows: 2HBO3 → 2HBO2 + H2O → B2O3 + 3H2↑ (outside air) B2O3+Ti→TiB2+O3↑ In other words, it mixes with the steam to produce a single gas. Hydrogen gas cannot be decomposed further, and the Planck constant of h is only a matter of quantum mechanics. H2 (-) → has an electron in the smallest orbit, and even if it is heated to 400-700℃ and moves thermally, it cannot move in or out of the orbit. This is hydrogen. This hydrogen atom is the smallest molecule and can emit light through vibration, which is called the Bohr vibration. The H3BO3 reaction is simple, but the novel discovery that TiB2 is produced according to the chemical reaction formula is proof of the generation of O3 at the (+) electrode according to the present invention. Conventional welding fluxes also contain H3BO3, but it has been impossible to prove that O3 is generated because it reacts with 3 to 6 types of inorganic substances.

[0015] In the present invention, the water in the tank may be 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, Cl (chlorine), calcium hypochlorite (calcium hypochlorite), Ca, Mg, etc., will adhere to both the (+) and (-) electrodes, but this can be washed periodically using an appropriate method. For example, this can be done by passing a current alternately between the (+) and (-) electrodes for 10 minutes every 1 to 2 hours.

[0016] In addition, the Ti plate (+) electrode of the present invention has a lifespan that is reduced due to the ionization of the TiB2+SnO2, CuO2, and ZnO2 metal oxides on the surface, and must be replaced after a maximum of one year. The negative electrode of SUS has a long life, but the deposits can be safely dissolved and removed by washing with a weak acid such as citric acid C6H8O7 (PH4). [Effects of the Invention]

[0017] <Effect 1> The simultaneous generation device and method of O3 gas and H2 gas of the present invention does not require the use of expensive CVD or AIP methods for metal deposition on the (+) electrode, and can generate sufficient O3 gas using inexpensive H3BO3 and Sn, Zn, Cu, Ni, etc., without using any platinum-based metals for the (+) electrode.

[0018] <Effect 2> Therefore, the (+) electrode is made from a Ti plate, and the Ti oxide film on its surface is completely removed by etching with strong acid. Then, in addition to the flux, one or two inexpensive metal powders of Sn, Zn, Cu, Ni, etc. are mixed on the surface as a flux and dopant (conductive), and the mixture is heated and oxidized to form a strong vapor deposition, which completely eliminates the peeling problem and generates O3 gas that reliably provides excellent effects. The O3 gas generated from the (+) electrode is collected without leakage by the device's hood that guides the O3 gas upward and the O3 gas collection manifold. The collected O3 gas can be safely used for deodorizing by oxidizing and decomposing odors in living areas, as well as for sterilization and bleaching.

[0019] <Effect 3> The O3 gas concentration is diluted to 0.1 ppm to 0.3 PPm by adjusting the voltage to the electrodes or by adjusting the amount of diluted air mixed in. The gas is then supplied to rooms in hospitals, clinics, offices, etc. to deodorize and kill viruses, maintaining a healthy, odor-free indoor environment. For example, when changing the diaper of a patient with a care level of 4 to 5 in a hospital room, the deodorizing and sterilizing effects can be achieved by diffusing or discharging the air. The voltage regulation to the electrodes, for example, the amount of O3 and H2 generated, is proportional to the current and voltage, so a simple dial adjustment device that adjusts from 24VDC to 48VDC is attached to the outlet of a commercially available product. In particular, to keep the H2 gas concentration at 10,000 ppm (max 1%) and the O3 gas at 0.1 to 0.3 ppm, it is not possible to adjust the O3 gas generating electrode side with only 24 VDC to 48 VDC, so a two-pronged joint hose is used, with hoses of 4 mm and 6 mm diameter separated to allow the gas to escape to the outside (across two chambers). For unattended indoor disinfection, open these two bottles fully to achieve a maximum of 5 ppm, which is 2.14 x 7 ppm per m3 of room. If you keep pets such as birds, dogs, or cats indoors, you can remove the smell of pet waste by first letting the pet outside and then emitting O3 gas at a maximum concentration of 5 ppm. Room: 8 tatami mats (8 x 8 x 8 x 2.14 ≒ 10000 = 0.109 ppm)

[0020] <Effect 4> The maximum concentration of H2 gas is 10,000 ppm because there is a risk of explosion if the maximum concentration is 4%. In conventional water electrolysis, O2 and H2 are prevented from mixing at all, but to generate O3 and H2 simultaneously, complete separation and collection are required. In this invention, an inexpensive stainless steel plate is used as the negative electrode to easily generate H2 gas. The H2 gas generated at the negative electrode side is collected in its entirety by the H2 collection hood above the water tank of the device of this invention without leaking anywhere else.

[0021] <Effect 4> The hydrogen gas generated by the present invention can be effectively used to alleviate brain damage, prevent and treat cancer, and even cure lifestyle-related diseases by removing active oxygen from the body using hydrogen gas inhalation, a well-known advanced medical technology, as described in detail in the aforementioned Non-Patent Document 3. For example, triglycerides are a barometer of a person's health. This neutral fat is oxidized by hydrogen to carbon dioxide, water, and energy. C55H104O6 (triglyceride molecule) + 78O2 → 55CO2 + 52H2O + energy As is clear from this reaction equation, for example, to reduce 10 kg of neutral fat, 29 kg of oxygen and 58 kg of hydrogen are required. This shows how much hydrogen must be inhaled to reduce neutral fat. [Brief explanation of the drawings]

[0022] [Figure 1] 1 is a schematic longitudinal sectional view illustrating an overall configuration of an apparatus according to the present invention. [Figure 2] FIG. 2 is an explanatory diagram showing a modified and enlarged view of a part of FIG. [Figure 3] Left side view of Figure 2 [Figure 4] FIG. 10 is a graph showing the amounts of ozone and hydrogen generated. DETAILED DESCRIPTION OF THE INVENTION

[0023] An example of an apparatus for simultaneously generating O3 gas and H2 gas according to the present invention is shown in Figure 1. A Ti plate (+) electrode 31 (O3 gas generating electrode) and a SUS plate (-) electrode 32 (H2 gas generating electrode) are vertically arranged in a glass water tank 60, alternately and at equal intervals without contact, via support rings 51 (insulating rings and current-carrying rings) on a support connecting shaft 50. Power is supplied to the Ti plate (+) electrode 31 and the SUS plate (-) electrode 32 from a power source 33 via a simple dial adjustment device 34 that adjusts the voltage from 24 VDC to 48 VDC. An automatic water supply pipe 61 is connected to the top of a glass water tank 60, and a drain pipe 62 is connected to the bottom. Figures 2 and 3 show a modified example of Figure 1, in which the support connecting shaft 50 in Figure 1 is replaced by a + conductive rod 50-1, a - conductive rod 50-2, and an insulating support rod 50-3, and the support rings 30 between these and each electrode plate are replaced by insulating rings 30-1 and conductive rings 30-2. The Ti plate (+) electrode 31 is an O3 generating electrode formed by etching the surface of a Ti plate base material, then applying H3BO3 as a flux to the surface, mixing in one or two metal powders of Sn, Zn, Cu, and Ni, and heating the mixture in an electric heating furnace at a temperature in the range of 400 to 700°C to form a vapor-deposited film in which metal oxides SnO2, ZnO2, CuO2, and NiO2 exist within TiB2. The O3 generating electrode 31 is covered with a hood 41 made of a transparent insulating material that guides the O3 generated around the sides upward, and the tops of the hoods 41 are connected together to collect the O3 gas and provide an O3 collection manifold 42 (hose joint) made of a transparent insulating material that extracts the entire 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 martensite SUS such as SUS403 or SUS410. H2 gas generated around the side of this H2 generating electrode 32 rises in the water tank, is collected in a collection hood 51 formed above the water tank, and is sent out from an exhaust duct 52 to an external hydrogen supply destination. The collection hood 51 has an inverted funnel-shaped bottom surface and an exhaust duct 52 in the center, from which all of the collected H2 gas is taken out to the outside.

[0025] The detailed conditions for generating O3 gas and H2 gas in the above-mentioned device and the status of O3 gas generation and H2 gas generation are shown in Figure 4 below. As is clear from FIG. 4, Examples Nos. 1 to 6 are examples of the method of the present invention, and it has been found that they are superior in terms of generation of O3 gas and H2 gas compared to Comparative Examples Nos. 7 to 12. [Industrial Applicability]

[0026] As described above, the present invention exhibits excellent effects as explained in the effects of the invention, and therefore will make a great contribution to the ozone generation and H2 gas generator industry, the ozone utilization medical society, etc. [Explanation of symbols]

[0027] 30: Insulator 30-1: Insulation 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 type 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: Collected Food 52: Exhaust duct 60: Glass aquarium 61: Automatic water supply pipe 62: Drain pipe

Claims

1. A device for detecting the voltage between the (+) electrode and O ３ gas and H from the (-) electrode ２ O which generates gas ３ Gas and H ２ In a gas simultaneous production device, The (+) electrode has a surface made of TiO, TiO ２ , Ti ２ O ３ All of the above Ti base materials are free of Ti oxide films, and TiB is deposited on the surface. ２ Inside SnO ２ or ZnO ２ or CuO ２ or NiO ２ A vapor-deposited film containing at least one metal oxide of ３ The generating electrode is The negative electrode is an H2 generating electrode made of martensite SUS403 or SUS410. ３ The generating electrode and the H ２ A plurality of generating electrodes are arranged vertically at predetermined intervals in the water tank, The above O ３ The generating electrode is ３ The top of each hood is connected to the hood that guides the lift. ３ Take it out to the outside ３ A collection manifold is provided, and above the aqueous solution, a H ２ The H generated around the generating electrode rises ２ Collect and take out H ２ A collection hood is provided. ３ Gas and H ２ Gas simultaneous production equipment.

2. A device for detecting the voltage between the (+) electrode and O ３ gas and H from the (-) electrode ２ O which generates gas ３ Gas and H ２ In a method for simultaneously producing gas, The (+) electrode is made of TiO, TiO ２ , Ti ２ O ３ The entire oxide film was removed by etching to form a Ti base material, and H was applied to the surface. ３ BO ３ The flux is mixed with at least one metal powder of Sn, Zn, Cu, or Ni, and then heated at 400 to 700°C to form TiB. ２ A vapor-deposited film containing the metal oxide of the metal powder is formed. ３ The generating electrode is The (-) electrode is made of martensite SUS403 or SUS410. ２ These O ３ The generating electrode and the H ２ A plurality of generating electrodes are arranged vertically at predetermined intervals in the water tank, and the O ３ The generating electrode is ３ The top of each hood is covered with a hood that guides the rise of the ３ Connect to the collection manifold ３ The water is taken out and H is placed on top of the water. ２ Collection hood set up H ２ The H generated around the generating electrode rises ２ and extracting it to the outside. ３ Gas and H ２ Method for simultaneous production of gas.

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