A sustained-release hydrogen microbubble type capsule, a preparation method and application thereof

Abstract

The application provides a slow-release hydrogen microbubble type capsule, a preparation method and application thereof, and the slow-release hydrogen microbubble type capsule comprises hydrogen generating particles and a microporous capsule shell coated on the surface of the hydrogen generating particles, and raw materials of the hydrogen generating particles comprise a hydrogen generating agent, a skeleton forming agent, an organic acid and curved graphene.In the application, the hydrogen generating agent, the skeleton forming agent, the organic acid and the curved graphene are used to cooperatively prepare the hydrogen generating particles, and the hydrogen generating particles are encapsulated into the microporous capsule shell, water molecules penetrate into the inside through micropores on the capsule, react with the hydrogen generating particles, generate hydrogen molecules, and then overflow and penetrate into the water liquid through the micropores on the capsule, so that the hydrogen concentration of the water solution is greatly improved, and the purposes of slow-releasing hydrogen molecules for a long time and preparing super-saturated hydrogen-rich water are achieved.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen-rich water technology, and relates to a slow-release hydrogen microbubble capsule, its preparation method and application. Background Technology

[0002] Hydrogen has wide-ranging applications across various fields. Scientific practice has proven that hydrogen possesses excellent biological affinity and exhibits no side effects, producing ideal antioxidant, anti-inflammatory, and anti-apoptotic effects. Various hydrogen therapies, such as inhaling hydrogen, drinking hydrogen water, injecting hydrogen water, and bathing in hydrogen water, have shown good therapeutic effects, offering broad prospects for the future development of hydrogen medicine. The biological effects of hydrogen molecules have good adjuvant therapeutic effects on many common chronic diseases, such as cardiovascular disease, diabetes, Alzheimer's disease, and even tumors. It can scavenge free radicals in the body, achieving antioxidant effects, slowing aging, improving immunity, enhancing physical fitness, promoting longevity, and aiding in weight loss, among other benefits.

[0003] The existing technologies for preparing slow-release hydrogen agents and hydrogen-rich water mainly include: (1) directly filling water with hydrogen gas, but hydrogen gas has poor water solubility and is very easy to escape, so it cannot be slow-released or stored for a long time; (2) using magnesium to react with water to generate hydrogen gas, but at room temperature, magnesium reacts with water slowly and there is a problem of hydrogen loss due to dissolution; (3) preparing hydrogen-rich water by electrolysis of hydrogen. Hydrogen gas can be prepared by purifying water or directly passing pure water through electrolysis, but the cost of water electrolysis equipment is high and it is inconvenient to use and not easy to carry.

[0004] Therefore, how to efficiently and sustainably release hydrogen and achieve supersaturated hydrogen-rich water has become one of the important research topics in this field. Summary of the Invention

[0005] To address the problems in existing technologies, the present invention aims to provide a slow-release hydrogen microbubble capsule, its preparation method, and its applications. In this invention, hydrogen-generating particles are synergistically prepared using raw materials such as a hydrogen-generating agent, a framework-forming agent, organic acid, and curved graphene. These hydrogen-generating particles are then encapsulated in a microporous capsule shell. Water molecules permeate into the capsule through the micropores, react with the hydrogen-generating particles, and generate hydrogen molecules. These hydrogen molecules then overflow through the micropores and permeate into the aqueous solution, significantly increasing the dissolved hydrogen concentration in the aqueous solution. This achieves the goal of ultra-long-term slow release of hydrogen molecules and the preparation of supersaturated hydrogen-rich water.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a slow-release hydrogen microbubble capsule, particularly a slow-release hydrogen microbubble capsule that releases hydrogen gas efficiently and for an ultra-long time and achieves supersaturated hydrogen-rich water. The slow-release hydrogen microbubble capsule includes hydrogen-generating particles and a microporous capsule shell covering the surface of the hydrogen-generating particles. The raw materials of the hydrogen-generating particles include a hydrogen-generating agent, a framework forming agent, an organic acid, and curved graphene.

[0008] In this invention, "high efficiency" refers to the high hydrogen production efficiency of the slow-release hydrogen microbubble capsules and the supersaturated hydrogen dissolution phenomenon after hydrogen is nano-sized, which means that the utilization rate of the substance is very high; "ultra-long-term slow-release hydrogen" refers to the slow-release time of hydrogen as long as 2 to 6 months.

[0009] Hydrogen is a relatively safe and effective antioxidant. It reacts with harmful reactive oxygen species to scavenge free radicals, thus achieving an antioxidant effect. Hydrogen not only has reducing properties but also oxidizing properties. After reducing other substances, hydrogen atoms lose electrons and become hydrogen ions. A single electron outside the nucleus of a hydrogen atom can also accept electrons from other strongly reducing substances, at which point the hydrogen atom can oxidize those substances.

[0010] This invention utilizes a hydrogen-generating agent, a framework-forming agent, an organic acid, and curved graphene in a synergistic process to prepare hydrogen-generating particles, which are then encapsulated in a microporous capsule shell. The micropores of the shell allow water and hydrogen to pass through freely. The hydrogen-generating particles, prepared from specific raw materials, are then placed inside the shell. The hydrogen generation and release process is slow and continuous, allowing the slow-release hydrogen microbubble capsule to continuously produce hydrogen. Specifically, the hydrogen-generating agent reacts with water to release hydrogen; the framework-forming agent has a skeletal structure, serving to form the framework and control the slow-release of the hydrogen generation reaction; the organic acid effectively catalyzes hydrogen generation; and curved graphene, a novel functional material, is small in size, exhibits quantum effects, possesses a strong electric field, and has excellent adsorption capabilities. Furthermore, it possesses strong antibacterial, bactericidal, and antioxidant properties, which are significantly enhanced when combined with hydrogen molecules. The resulting slow-release hydrogen microbubble capsule can be applied in beauty and skincare, health care, and other fields, comprehensively improving human health and immune function.

[0011] Meanwhile, the sustained-release hydrogen microbubble capsules prepared by this invention exhibit microbubble characteristics, producing extremely small hydrogen bubbles that exist in water as small molecules. During the formation of nanobubbles, this invention discovered that when microbubbles reach a certain particle size, due to various reasons such as ionization, ion adsorption, ion substitution, and frictional contact, a large number of negative charges accumulate on the surface of the microbubble particles. Because charged particles attract oppositely charged particles in the dispersion system, ions near the particle surface are strongly bound, while more distant ions form a loose electron cloud. Due to the capacitance principle, a symmetrical ionization layer is formed at the interface, creating a spherical super-electric field around each particle. This field attracts oppositely charged ions in the solution to adhere to the interface and move with it. The generation and accumulation of this super-electric field potential plays a crucial role in the stability of the dispersion system. This stable dispersion system significantly increases the hydrogen molecule content and stability in water, enabling hydrogen-rich water to reach a supersaturated state and efficiently utilize hydrogen molecules.

[0012] In summary, this invention uses a variety of specific raw materials to prepare hydrogen-generating particles and encapsulates them in a microporous capsule shell. The synergistic effect effectively controls the generation and slow release of hydrogen, with an effective duration of 2 to 6 months. Furthermore, the released hydrogen bubbles have microbubble characteristics, achieving supersaturated hydrogen solubility, which is beneficial for cell penetration and absorption, thus achieving the goal of efficient hydrogen production and effective utilization.

[0013] Preferably, the hydrogen-generating agent comprises any one or a combination of at least two of magnesium dihydrogenide (MgH2), calcium hydroxylamine, and tourmaline. For example, it may be a combination of magnesium dihydrogenide and calcium hydroxylamine, a combination of calcium hydroxylamine and tourmaline, a combination of magnesium dihydrogenide and tourmaline, or a combination of magnesium dihydrogenide, calcium hydroxylamine, and tourmaline, preferably a combination of magnesium dihydrogenide, calcium hydroxylamine, and tourmaline.

[0014] In this invention, tourmaline, also known as elbaite, possesses a spontaneous polarization effect. Due to the electrostatic field surrounding tourmaline particles, it exhibits excellent functional properties such as emitting far-infrared rays and releasing negative oxygen ions and hydrogen ions. Simultaneously, it slowly releases hydrogen molecules upon reaction with water. Hydrogenated coral calcium, an edible solid form of hydrogen-ion coral calcium, reacts with water to produce H₂ and H₂. + and H - Simultaneous release will occur. In this invention, three specific hydrogen-producing substances—magnesium dihydrogen hydride, calcium hydride coral, and tourmaline—are preferably used synergistically. The combination of these three substances promotes catalysis and achieves the best hydrogen production efficiency, significantly improving the efficiency of the sustained-release hydrogen microbubble capsules.

[0015] It should be noted that among magnesium dihydrogenide, calcium coral hydride, and tourmaline, calcium coral hydride and tourmaline are irreplaceable. Calcium hydride can produce a similar effect to magnesium dihydrogenide, but magnesium dihydrogenide is a non-toxic, harmless, and edible product, while calcium hydride does not have the same superior performance. Therefore, the synergistic use of magnesium dihydrogenide, calcium coral hydride, and tourmaline is necessary to significantly improve the efficiency of sustained-release hydrogen microbubble capsules.

[0016] Preferably, the skeleton forming agent comprises any one or a combination of at least two of porous materials, KDF powder, and hydroxypropyl methylcellulose. For example, it may be a combination of porous materials and KDF powder, a combination of KDF powder and hydroxypropyl methylcellulose, a combination of porous materials and hydroxypropyl methylcellulose, or a combination of porous materials, KDF powder, and hydroxypropyl methylcellulose; more preferably, it is a combination of porous materials, KDF powder, and hydroxypropyl methylcellulose.

[0017] In this invention, the porous materials possess a framework structure. Within their crystals, molecules are interconnected like a framework, forming numerous hollow microporous structures, exhibiting excellent delayed reaction and slow-release effects. KDF powder is a high-purity copper-zinc alloy capable of removing heavy metals and acid radicals from water via electrochemical methods. It removes oxidants, residual chlorine, and heavy metals from water, while also inhibiting bacteria and preventing scaling, thus maintaining the cleanliness and safety of the water. The framework-forming agent of this invention serves to form the framework and control the slow-release effect of the hydrogen production reaction. Synergistically, it works with the specific hydrogen-producing agent, organic acid, and curved graphene in this invention to improve hydrogen production efficiency and effectively control the slow release of hydrogen.

[0018] Preferably, the porous material includes any one or a combination of at least two of zeolite, montmorillonite and diatomite, such as a combination of zeolite and montmorillonite, a combination of montmorillonite and diatomite, a combination of zeolite and diatomite, or a combination of zeolite, montmorillonite and diatomite.

[0019] It should be noted that hydroxypropyl methylcellulose in this invention can also be replaced with hydroxymethylcellulose and / or hydroxyethyl methylcellulose, but the effect is worse than that of hydroxypropyl methylcellulose. Therefore, hydroxypropyl methylcellulose is used to achieve the best effect in synergy with other raw materials in this invention.

[0020] Preferably, the organic acid includes citric acid and / or malic acid, which can effectively catalyze hydrogen production. Citric acid is a relatively strong organic acid with three hydrogen atoms. + It can ionize. Citric acid reacts with magnesium: 3Mg + 2H3Cit = Mg3(Cit)2 + 3H2↑, producing hydrogen molecules.

[0021] As a preferred technical solution for the sustained-release hydrogen microbubble capsules of the present invention, the raw materials of the hydrogen-generating particles include a combination of magnesium dihydrogenide, calcium coral dihydrogenide, tourmaline, organic acid, porous materials, KDF powder, hydroxypropyl methylcellulose and curved graphene. By using the above eight specific raw materials in combination, they can synergistically enhance each other, achieve high efficiency and ultra-long-term sustained release of hydrogen, and prepare supersaturated hydrogen-rich water.

[0022] Preferably, the raw materials for the hydrogen-generating particles, by weight, include:

[0023]

[0024] The components include: magnesium dihydrogenide in parts by weight of 40-50 parts, for example, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 parts; calcium coral dihydrogenide in parts by weight of 15-25 parts, for example, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 parts; tourmaline in parts by weight of 5-10 parts, for example, 5, 6, 7, 8, 9, or 10 parts; and organic acids in parts by weight of 5-25 parts, for example, 5, 8, 9, or 10 parts. The mass fractions of porous materials are 10 to 20 parts, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 parts. The mass fractions of KDF powder are 1 to 5 parts, for example, 1, 2, 3, 4, or 5 parts. The mass fractions of hydroxypropyl methylcellulose are 5 to 15 parts, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 parts.

[0025] In this invention, the mass fraction of specific raw materials is further optimized to control the hydrogen production rate of the sustained-release hydrogen microbubble capsules, thereby greatly extending the sustained-release time and achieving the effect of supersaturated hydrogen-rich water.

[0026] As a preferred technical solution for the sustained-release hydrogen microbubble capsule of the present invention, the raw materials of the microporous capsule shell include high molecular polymers, porous materials, and curved graphene. The microporous capsule shell is prepared from high molecular raw materials, and the micropores allow water and hydrogen to pass through freely. Curved graphene has excellent adsorption function and antibacterial, bactericidal, and antioxidant effects. After interacting with hydrogen molecules, the antibacterial, bactericidal, and antioxidant effects are significantly enhanced. After the hydrogen-generating particles are filled into the capsule prepared by the above-mentioned high molecular foaming agent, water molecules permeate into the interior through the micropores on the capsule, react with the particles, generate hydrogen molecules, and then overflow through the micropores on the capsule, thereby increasing the dissolved hydrogen concentration of the aqueous solution and the sustained-release hydrogen molecule effect.

[0027] Preferably, the polymer comprises any one or at least two composite materials selected from polyethylene (PE), polyamide (PA), polypropylene (PP), and polytetrafluoroethylene (PTFE). For example, it may be a composite material composed of PE and PA, a composite material composed of PP and PTFE, a composite material composed of PE, PA, and PTFE, or a composite material composed of PE, PA, PP, and PTFE, etc. The polymer is further preferably an ultra-high molecular weight polymer, with the polymer type remaining unchanged, and the molecular weight being 3 million to 6 million, for example, 3 million, 3.5 million, 4 million, 4.5 million, 5 million, 5.5 million, or 6 million, etc.

[0028] Preferably, the raw material for the microporous capsule shell, by weight, comprises:

[0029] 55-85 parts of polymer;

[0030] 20-40 parts of porous material;

[0031] 5-15 parts of curved graphene.

[0032] The polymer is in the range of 55 to 85 parts by mass, for example, 55, 60, 65, 70, 75, 80 or 85 parts by mass; the porous material is in the range of 20 to 40 parts by mass, for example, 20, 22, 25, 28, 30, 32, 35, 38 or 40 parts by mass; and the curved graphene is in the range of 5 to 15 parts by mass, for example, 5, 6, 8, 10, 12, 14 or 15 parts by mass.

[0033] Preferably, the microporous capsule shell is a hollow cylindrical capsule or a hollow spherical capsule. The hydrogen rod-shaped and spherical designs not only obtain hydrogen with high purity but also facilitate storage and carrying.

[0034] In a second aspect, the present invention provides a method for preparing a sustained-release hydrogen microbubble capsule according to the first aspect, the method comprising:

[0035] (1) The hydrogen-generating agent, the skeleton forming agent, the organic acid and the curved graphene are mixed and granulated, and the resulting particles are calcined to obtain hydrogen-generating particles.

[0036] (2) The hydrogen-generating particles described in step (1) are loaded into a microporous capsule shell and encapsulated to obtain a sustained-release hydrogen microbubble capsule.

[0037] This invention involves mixing specific raw materials, granulating them, refining, and then calcining the extruded granules to solidify them. The calcined hydrogen-generating granules are then encapsulated in microporous capsules. Water molecules can permeate through the micropores of the capsule, react with the granules to produce hydrogen molecules, and then escape through the micropores. The hydrogen molecules, through the micropore walls, create hydrogen microbubbles (small molecular clusters and high specific surface area) that permeate into the aqueous solution, significantly increasing the dissolved hydrogen concentration and achieving ultra-long-term sustained release of hydrogen molecules and supersaturated hydrogen-rich water. The sustained-release hydrogen microbubble capsules of this invention have low production costs, use mature specialized processing equipment, and are easy to operate. The prepared sustained-release hydrogen microbubble capsules can efficiently and for an ultra-long time release hydrogen, exhibiting microbubble characteristics, and simultaneously providing comprehensive benefits such as improving human health and immune function.

[0038] As a preferred technical solution of the preparation method described in this invention, the curved graphene in step (1) is prepared in the following manner:

[0039] Carbon rods are obtained by mixing white coal and coal tar, and then carbonized and graphitized to obtain conductive carbon rods. Two of the conductive carbon rods are placed in ultrapure water as anode and cathode, respectively, and subjected to voltage-stabilized electrolysis to obtain a mixed solution. The mixed solution is filtered and centrifuged to obtain a curved graphene solution, which includes curved graphene.

[0040] Preferably, the pressure at which the white coal and coal tar are mixed is 1 to 5 MPa, for example, 1 MPa, 2 MPa, 3 MPa, 4 MPa or 5 MPa.

[0041] Preferably, the two conductive carbon rods are identical conductive carbon rods.

[0042] Preferably, the white coal is pre-crushed and screened before mixing, and the particle size of the screened white coal is less than 100μm, for example, it can be 10μm, 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm or 99μm, etc.

[0043] Preferably, the carbonization and graphitization temperature is 700℃ to 1200℃, for example, 700℃, 800℃, 900℃, 1000℃, 1100℃, 1200℃, etc. The carbonization and graphitization time is 1.5h to 4h, for example, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, etc.

[0044] Preferably, the static potential of the voltage-stabilized electrolyzer is 10 to 60V, for example, it can be 10V, 20V, 30V, 40V, 50V or 60V.

[0045] Preferably, the solid content of the curved graphene solution is 2-6‰, for example, it can be 2‰, 2.5‰, 3‰, 3.5‰, 4‰, 4.5‰, 5‰, 5.5‰ or 6‰, etc.

[0046] Preferably, the D50 particle size of the curved graphene in the curved graphene solution is 5-20 nm, for example, it can be 5 nm, 8 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm or 20 nm.

[0047] The curved graphene prepared in this invention is water-soluble, with particle size at the nanometer level. It will not be removed along with impurities during filtration and centrifugation. After centrifugation, a curved graphene solution is obtained. When using curved graphene to prepare hydrogen-generating particles, the curved graphene solution can be directly mixed with other raw materials and subsequent operations can be performed. The mass fraction of curved graphene during mixing is calculated according to the actual mass of curved graphene contained in the solution.

[0048] Preferably, the calcination temperature in step (1) is 120 to 150°C, for example, it can be 120°C, 125°C, 130°C, 135°C, 140°C, 145°C or 150°C.

[0049] Preferably, the diameter of the hydrogen-generating particles is 1 to 10 mm, for example, it can be 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm or 10 mm.

[0050] As a preferred technical solution of the preparation method of the present invention, the microporous capsule shell in step (2) is prepared in the following manner:

[0051] A microporous capsule shell is obtained by mixing a polymer, a porous material, and curved graphene, molding the mixture, and then sintering it.

[0052] Preferably, the porous material has a mesh size of 150 to 250 mesh, such as 150 mesh, 180 mesh, 200 mesh, 220 mesh, or 250 mesh.

[0053] Those skilled in the art should understand that the mold is designed according to the external shape and internal structural dimensions required by the present invention, preferably a mold for hollow cylindrical capsules or hollow spherical capsules, the hollow structure being a space for storing hydrogen-generating particles.

[0054] Preferably, the sintering temperature is 160-240℃, for example, it can be 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃ or 240℃, etc.; the sintering time is 1-4h, for example, it can be 1h, 2h, 3h or 4h, etc.

[0055] Preferably, a gradient temperature increase is performed after molding and before sintering.

[0056] Preferably, the gradient heating is performed in the following manner:

[0057] Heat to 130–155℃ and hold for 1–2 hours, then heat to 160–240℃ and hold.

[0058] The temperature is raised to 130–155℃, for example, 130℃, 135℃, 140℃, 145℃, 150℃, or 155℃, and held for 1–2 hours, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, or 2 hours; after raising the temperature to 160–240℃, the holding time can be, for example, 1 hour.

[0059] As a preferred embodiment of the preparation method of the present invention, the preparation method includes:

[0060] (1) After crushing and screening the white coal to a particle size of less than 100 μm, coal tar is added at 1-5 MPa to obtain carbon rods. Carbonization and graphitization treatment are carried out to obtain conductive carbon rods. Two identical conductive carbon rods are placed in ultrapure water as anode and cathode respectively. A static potential of 10-60 V is applied between the anode and cathode and stirred. After voltage stabilization and electrolysis, a mixed solution is obtained. The mixed solution is filtered and centrifuged to obtain a curved graphene solution with a solid content of 2-6‰. The D50 particle size of the curved graphene in the curved graphene solution is 5-20 nm.

[0061] (2) The hydrogen-generating agent, the skeleton forming agent, the organic acid and the curved graphene described in step (1) are mixed and granulated, and the resulting particles are calcined at 120-150°C to obtain hydrogen-generating particles with a diameter of 1-10 mm.

[0062] (3) Mix the polymer, porous material and curved graphene, heat to 130-155℃, keep warm for 1-2 hours, then heat to 160-240℃ and keep warm, and sinter at 160-240℃ for 1-4 hours to obtain microporous capsule shell.

[0063] (4) The hydrogen-generating particles described in step (2) are loaded into the microporous capsule shell described in step (3) and sealed to obtain a sustained-release hydrogen microbubble capsule.

[0064] Thirdly, the present invention provides an application of the sustained-release hydrogen microbubble capsule as described in the first aspect, wherein the sustained-release hydrogen microbubble capsule is used for the sustained release of hydrogen and the preparation of hydrogen-rich water.

[0065] Compared with the prior art, the present invention has the following beneficial effects:

[0066] (1) In this invention, hydrogen-generating particles are prepared by synergistic combination of hydrogen-generating agent, framework forming agent, organic acid and curved graphene, and coated with microporous capsule shell, so that the process of hydrogen generation and release is slow and continuous. Thus, the slow-release hydrogen microbubble capsule can continuously generate hydrogen. Under the multiple coating of framework forming agent, curved graphene and microporous capsule shell, the hydrogen-generating agent can be effective for 2 to 6 months, achieving the purpose of efficient hydrogen production and effective utilization. The production cost is low, the special processing equipment is mature and the operation is convenient.

[0067] (2) The slow-release hydrogen microbubble capsule of the present invention has microbubble characteristics. When preparing the skeleton structure, many nano-microporous structures are generated. Therefore, the hydrogen bubbles generated are very small and the surface area of ​​the bubbles increases exponentially. Therefore, the reaction interface of the bubbles is very large. The bubbles exist in water in the form of small molecules, reaching supersaturated hydrogen solubility, which can quickly penetrate into cells and be absorbed.

[0068] (3) The addition of curved graphene to this invention not only allows it to work synergistically with other raw materials to release hydrogen slowly and improve efficiency, but also has strong antibacterial, bactericidal and antioxidant effects. Under the combined action of hydrogen molecules, the antibacterial, bactericidal and antioxidant effects are significantly enhanced. The prepared slow-release microbubble hydrogen generator rod can be used in beauty and skin care, health care and other aspects, and has the effect of comprehensively improving human health and immune function. Attached Figure Description

[0069] Figure 1 This is a cross-sectional view of a slow-release hydrogen microbubble capsule in a specific embodiment of the present invention.

[0070] Figure 2 This is a vertical cross-sectional view of a slow-release hydrogen microbubble capsule in a specific embodiment of the present invention.

[0071] Figure 3 This is a hydrogen microbubble distribution diagram of the sustained-release hydrogen microbubble capsule prepared in Example 1 of the present invention.

[0072] Figure 4 This is a normal distribution diagram of the particle size of the curved graphene in the curved graphene solution of Example 3 of the present invention.

[0073] Figure 5 This is a schematic diagram of the slow-release hydrogen microbubble capsule of the present invention releasing hydrogen microbubbles to form a super electric field.

[0074] Among them, 1-hydrogen-generating particles; 2-microporous capsule shell. Detailed Implementation

[0075] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0076] Example 1

[0077] This embodiment provides a sustained-release hydrogen microbubble capsule, the structural schematic of which is shown below. Figure 1 and Figure 2 As shown, the sustained-release hydrogen microbubble capsule includes hydrogen-generating particles 1 and a microporous capsule shell 2 covering the surface of the hydrogen-generating particles 1. The diameter of the hydrogen-generating particles 1 is 2 mm, and the microporous capsule shell 2 is a hollow cylindrical capsule.

[0078] The raw materials for the hydrogen-generating particles 1, by weight, include:

[0079]

[0080] The raw materials for the microporous capsule shell 2, by weight, include:

[0081] 60 parts of high molecular weight polyethylene;

[0082] 30 parts zeolite;

[0083] 10 parts of curved graphene.

[0084] This embodiment also provides a method for preparing the above-mentioned sustained-release hydrogen microbubble capsules, including:

[0085] (1) Preparation of curved graphene: First, high-purity white coal was crushed and screened with a particle size of less than 100 μm. Then, coal tar was mixed and carbon rods were formed at 2 MPa. The carbon rods were graphitized at 900 °C for 2 h to obtain conductive carbon rods. Two identical conductive carbon rods were used as anode and cathode respectively and inserted into ultrapure water. A static potential of 30 V was applied between the two electrodes and the mixture was stirred rapidly. The solution was electrolyzed under stable voltage for 10 days to obtain a deep yellow solution. The solution was filtered and centrifuged at 22000 rpm for 30 min to remove impurities. Finally, a curved graphene solution with a solid content of 3‰ and a D50 of 20 nm was obtained.

[0086] (2) Preparation of hydrogenated granules 1: Magnesium dihydrogenide 40, calcium coral dihydrogenide 20, curved graphene 10, tourmaline 5, citric acid 10, zeolite 10, KDF powder 1, and hydroxypropyl methylcellulose 5 were mixed according to the mass ratio. The mixture was fully refined and extruded into granules using a granulator. After calcination at 120℃, the granules were solidified to obtain a diameter... Specification of hydrogen-generating particles 1;

[0087] (3) Preparation of microporous capsule shell 2: High molecular weight polyethylene (PE) with a molecular weight of 4 million, 200-mesh zeolite, and curved graphene with a D50 of 20 nm were selected and mixed according to the mass ratio of 60 parts of high molecular weight polyethylene, 30 parts of zeolite, and 10 parts of curved graphene. The mold was designed according to the required external shape and internal structure dimensions of this embodiment. The microporous capsule shell 2 was designed to be columnar in shape with a hollow interior to store the hydrogen-generating particles 1. After molding, the temperature was increased by gradient. First, the temperature was raised to 130°C and held for 1 hour. Then, the furnace temperature was raised to 160°C and held for 1 hour. Finally, the temperature was sintered at 180°C for 2 hours. After natural cooling to room temperature, the microporous capsule shell 2 was obtained.

[0088] (4) The hydrogen-generating particles 1 described in step (2) are loaded into the microporous capsule shell 2 described in step (3) and sealed to obtain a sustained-release hydrogen microbubble capsule.

[0089] The density distribution diagram of the hydrogen released by the sustained-release hydrogen microbubble capsules prepared in this embodiment is shown in the figure below. Figure 3 As shown, microbubbles are generated and released within the framework of nanopores, reaching a size of less than 100 nm; Figure 3 The microbubbles show the highest frequency at around 100nm, with a concentration of approximately 1.4 billion microparticles per milliliter.

[0090] Example 2

[0091] This embodiment provides a sustained-release hydrogen microbubble capsule, the structural schematic of which is shown below. Figure 1 and Figure 2 As shown, the sustained-release hydrogen microbubble capsule includes hydrogen-generating particles 1 and a microporous capsule shell 2 covering the surface of the hydrogen-generating particles 1. The diameter of the hydrogen-generating particles 1 is 5 mm, and the microporous capsule shell 2 is a hollow cylindrical capsule.

[0092] The raw materials for the hydrogen-generating particles 1, by weight, include:

[0093]

[0094] The raw materials for the microporous capsule shell 2, by weight, include:

[0095] 70 parts of high molecular weight polyethylene;

[0096] 25 parts zeolite;

[0097] Five parts of curved graphene.

[0098] This embodiment also provides a method for preparing the above-mentioned sustained-release hydrogen microbubble capsules, including:

[0099] (1) Preparation of curved graphene: First, high-purity white coal was crushed and screened with a particle size of less than 100 μm. Then, coal tar was mixed and carbon rods were formed at 3 MPa. The carbon rods were graphitized at 900 °C for 2 h to obtain conductive carbon rods. Two identical conductive carbon rods were used as anode and cathode respectively and inserted into ultrapure water. A static potential of 40 V was applied between the two electrodes and the mixture was stirred rapidly. The solution was electrolyzed under stable voltage for 12 days to obtain a deep yellow solution. The solution was filtered and centrifuged at 22000 rpm for 30 min to remove impurities. Finally, a curved graphene solution with a solid content of 4‰ and a D50 of 10 nm was obtained.

[0100] (2) Preparation of hydrogenated granules 1: Magnesium dihydrogenide 35, calcium coral dihydrogenide 20, curved graphene 5, tourmaline 5, citric acid 8, zeolite 12, KDF powder 2, and hydroxypropyl methylcellulose 10 were mixed according to the mass ratio. The mixture was fully refined and extruded into granules using a granulator. After calcination at 140℃, the granules were solidified to obtain a diameter... Specification of hydrogen-generating particles 1;

[0101] (3) Preparation of microporous capsule shell 2: High molecular weight polypropylene (PP) with a molecular weight of 4 million, 200-mesh zeolite, and curved graphene with a D50 of 10 nm were selected and mixed according to the mass ratio of 70% high molecular weight polypropylene, 25% zeolite, and 5% curved graphene. The mold was designed according to the required external shape and internal structure dimensions of this embodiment. The microporous capsule shell 2 was designed to be columnar in shape with a hollow interior to store hydrogen-generating particles 1. After molding, the temperature was increased by gradient. First, the temperature was raised to 140°C and held for 1.5 h. Then, the furnace temperature was raised to 180°C and held for 1 h. Finally, the temperature was sintered at 200°C for 3 h. After natural cooling to room temperature, the microporous capsule shell 2 was obtained.

[0102] (4) The hydrogen-generating particles 1 described in step (2) are loaded into the microporous capsule shell 2 described in step (3) and sealed to obtain a sustained-release hydrogen microbubble capsule.

[0103] Example 3

[0104] This embodiment provides a sustained-release hydrogen microbubble capsule, the structural schematic of which is shown below. Figure 1 and Figure 2 As shown, the sustained-release hydrogen microbubble capsule includes hydrogen-generating particles 1 and a microporous capsule shell 2 covering the surface of the hydrogen-generating particles 1. The diameter of the hydrogen-generating particles 1 is 8 mm, and the microporous capsule shell 2 is a hollow cylindrical capsule.

[0105] The raw materials for the hydrogen-generating particles 1, by weight, include:

[0106]

[0107]

[0108] The raw materials for the microporous capsule shell 2, by weight, include:

[0109] 75 parts of composite polymer PE / PTFE copolymer;

[0110] 20 parts zeolite;

[0111] Five parts of curved graphene.

[0112] This embodiment also provides a method for preparing the above-mentioned sustained-release hydrogen microbubble capsules, including:

[0113] (1) Preparation of curved graphene: First, high-purity white coal was crushed and screened to a particle size of less than 100 μm. Then, coal tar was mixed and carbon rods were formed at 5 MPa. The carbon rods were then graphitized at 900 °C for 2 h to obtain conductive carbon rods. Two identical conductive carbon rods were used as the anode and cathode, respectively, and inserted into ultrapure water. A static potential of 60 V was applied between the two electrodes, and the mixture was stirred rapidly. After 15 days of steady-state electrolysis, a deep yellow solution was obtained. The solution was filtered, centrifuged at 22000 rpm for 30 min to remove impurities, and finally, a curved graphene solution with a solid content of 5‰ and a D50 of 4.18 nm was obtained. The normal distribution of the particle size of the curved graphene in the solution is shown in the figure. Figure 4 As shown;

[0114] (2) Preparation of hydrogenated granules 1: Magnesium dihydrogenide 30, calcium coral dihydrogenide 30, curved graphene 8, tourmaline 4, citric acid 8, zeolite 8, KDF powder 3, and hydroxypropyl methylcellulose 12 were mixed according to the mass ratio. The mixture was fully refined and extruded into granules using a granulator. After calcination at 150℃, the granules were solidified to obtain a diameter... Specification of hydrogen-generating particles 1;

[0115] (3) Preparation of microporous capsule shell 2: A composite polymer PE / PTFE copolymer with a molecular weight of 5 million (a copolymer system of 10% PE and 90% PTFE), 200-mesh zeolite, and curved graphene with a D50 of 4.18 nm were selected and mixed according to the mass ratio of 75% composite polymer PE / PTFE copolymer, 20% zeolite, and 5% curved graphene. The mixture was then molded. The mold was designed according to the required external shape and internal structure dimensions of this embodiment. The microporous capsule shell 2 was designed to be columnar in shape with a hollow interior to store the hydrogen-generating particles 1. After molding, the temperature was gradually increased. First, the temperature was raised to 150°C and held for 2 hours. Then, the furnace temperature was raised to 200°C and held for 1 hour. Finally, the mixture was sintered at 220°C for 4 hours and allowed to cool naturally to room temperature to obtain the microporous capsule shell 2.

[0116] (4) The hydrogen-generating particles 1 described in step (2) are loaded into the microporous capsule shell 2 described in step (3) and sealed to obtain a sustained-release hydrogen microbubble capsule.

[0117] Example 4

[0118] Except for replacing the hydrogenated coral calcium and tourmaline with equal parts of magnesium dihydrogenate, everything else was the same as in Example 1;

[0119] The total number of hydrogen-producing agents in this embodiment is the same as in Example 1.

[0120] Example 5

[0121] Except for replacing 1 part of KDF powder with 1 part of zeolite, everything else is the same as in Example 1.

[0122] Example 6

[0123] Except for replacing the proportion of raw materials for hydrogen-generating particles 1, everything else is the same as in Example 3;

[0124] The raw materials for the hydrogen-generating particles 1, by weight, include:

[0125]

[0126]

[0127] Comparative Example 1

[0128] Except for the absence of curved graphene, everything else is the same as in Example 1.

[0129] Comparative Example 2

[0130] Except for the absence of zeolite and hydroxypropyl methylcellulose, everything else is the same as in Example 1.

[0131] Performance testing:

[0132] The sustained-release hydrogen microbubble capsules prepared in the embodiments and comparative examples of the present invention were immersed in a pure aqueous solution with a resistivity of 10 megohms. After two hours, the dissolved hydrogen concentration of the solution reached 1600 ppb, and the microbubble density reached its peak. The test was stopped when the hydrogen concentration was lower than the dissolved hydrogen concentration by 300 ppb. The sustained-release time of hydrogen was recorded, and the results are shown in Table 1.

[0133] Table 1

[0134]

[0135]

[0136] As can be seen from Examples 1-6 above, in this invention, hydrogen-generating particles 1 are prepared by synergistic use of raw materials such as hydrogen-generating agents, framework forming agents, organic acids, and curved graphene. The hydrogen-generating particles 1 are then encapsulated in a microporous capsule shell 2. Water molecules permeate into the interior through the micropores on the capsule, react with the hydrogen-generating particles 1, and generate hydrogen molecules. These hydrogen molecules then overflow through the micropores on the capsule and permeate into the aqueous solution, greatly increasing the dissolved hydrogen concentration in the aqueous solution. This achieves the purpose of ultra-long-term slow release of hydrogen molecules and preparation of supersaturated hydrogen-rich water.

[0137] The sustained-release hydrogen microbubble capsules prepared by this invention generate microbubbles during operation and release them within the framework of nanopores, achieving a size below 100 nm. For example... Figure 3 As shown, the frequency of microbubbles is highest around 100 nm, with a concentration of approximately 1.4 billion microparticles per milliliter. This invention discovered during the formation of nanobubbles that when microbubbles reach a certain particle size, due to various reasons such as ionization, ion adsorption, ion substitution, and triboelectric contact, a large number of negative charges accumulate on the surface of the microbubble particles. Because charged particles attract particles with opposite charges in the dispersion system, ions near the particle surface are strongly bound, while ions at greater distances form a loose electron cloud. Due to the capacitance principle, a symmetrical ionization layer is formed at the interface, creating a spherical super-electric field around each particle. Furthermore, it attracts ions with opposite charges in the solution to adhere tightly to the interface and move with it, such as... Figure 5 As shown, the generation and accumulation of this super electric field potential plays a crucial role in the stability of the dispersion system. This stable dispersion system significantly increases the hydrogen molecule content and stability in the water, enabling the hydrogen-rich water to reach a supersaturated state of hydrogen and efficiently utilizing hydrogen molecules.

[0138] A comparison of Examples 1 and 4 shows that the synergistic effect of magnesium dihydrogenide, calcium cyanamide, and tourmaline as hydrogen-producing agents in this invention achieves better sustained-release and hydrogen production effects, resulting in highly efficient sustained-release of hydrogen. Although Example 4 uses the same number of hydrogen-producing agents as Example 1, the specific combination of the three hydrogen-producing agents in Example 1 promotes catalysis and achieves the best hydrogen production efficiency, significantly improving the efficiency of the sustained-release hydrogen microbubble capsules.

[0139] A comparison between Example 1 and Example 5 shows that the porous material, KDF powder, and hydroxypropyl methylcellulose used in this invention can exert a better synergistic effect. In Example 5, KDF powder was replaced with an equal amount of zeolite porous material, which did not have a synergistic effect and did not have the functions of dechlorination, removal of soluble heavy metals, and antibacterial properties. Therefore, compared with Example 5, Example 1 has better overall performance.

[0140] Comparing Example 1 and Example 6, it is evident that the raw materials for the hydrogen-generating particles 1 in this invention have an optimal ratio. Within this ratio range, the synergistic effect between the raw materials can be further enhanced. In Example 6, all raw materials are within the optimal proportion range, resulting in a longer sustained-release time and a higher microbubble density.

[0141] By comparing Example 1 with Comparative Examples 1-2, it can be seen that none of the raw materials for hydrogen-producing particles in this invention can be omitted. In Comparative Example 1, the release time was significantly reduced and the microbubble density was also greatly reduced because curved graphene was not added. In Comparative Example 2, the release performance and microbubble density were also significantly reduced because the skeleton forming agent was not added.

[0142] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A sustained-release hydrogen microbubble capsule, characterized in that, The sustained-release hydrogen microbubble capsule includes hydrogen-generating particles and a microporous capsule shell covering the surface of the hydrogen-generating particles. The raw materials of the hydrogen-generating particles include hydrogen-generating agents, framework forming agents, organic acids, and curved graphene. The hydrogen-generating agent is a combination of magnesium dihydrogenide, calcium coral dihydrogenide, and tourmaline. The skeleton forming agent is a combination of porous materials, KDF powder and hydroxypropyl methylcellulose; The raw materials for the hydrogen-generating particles, by weight, include: 40-50 parts of magnesium dihydrogenate; 15-25 parts of hydrogenated coral calcium; Tourmaline 5-10 portions; Organic acids 5-25 parts; 10-20 parts of porous material; 1-5 parts of KDF powder; 5-10 parts of hydroxypropyl methylcellulose; 5-15 parts of curved graphene; The curved graphene is prepared in the following manner: Carbon rods are obtained by mixing white coal and coal tar, and then carbonized and graphitized to obtain conductive carbon rods. Two of the conductive carbon rods are placed in ultrapure water as anode and cathode, respectively, and subjected to voltage-stabilized electrolysis to obtain a mixed solution. The mixed solution is filtered and centrifuged to obtain a curved graphene solution, which includes curved graphene.

2. The sustained-release hydrogen microbubble capsule according to claim 1, characterized in that, The porous material includes any one or a combination of at least two of zeolite, montmorillonite, and diatomite.

3. The sustained-release hydrogen microbubble capsule according to claim 1, characterized in that, The organic acids include citric acid and / or malic acid.

4. The sustained-release hydrogen microbubble capsule according to claim 1, characterized in that, The raw materials for the microporous capsule shell include high molecular polymers, porous materials, and curved graphene.

5. The sustained-release hydrogen microbubble capsule according to claim 4, characterized in that, The polymer includes any one or at least two composite materials of polyethylene, polyamide, polypropylene, and polytetrafluoroethylene.

6. The sustained-release hydrogen microbubble capsule according to claim 4, characterized in that, The raw materials for the microporous capsule shell, by weight, include: 55-85 parts of polymer; 20-40 parts of porous material; 5-15 parts of curved graphene.

7. The sustained-release hydrogen microbubble capsule according to claim 1, characterized in that, The microporous capsule shell is a hollow cylindrical capsule or a hollow spherical capsule.

8. A method for preparing a sustained-release hydrogen microbubble capsule according to any one of claims 1-7, characterized in that, The preparation method includes: (1) The hydrogen-generating agent, the skeleton forming agent, the organic acid and the curved graphene are mixed and granulated, and the resulting particles are calcined to obtain hydrogen-generating particles; (2) The hydrogen-generating particles described in step (1) are loaded into a microporous capsule shell and encapsulated to obtain a sustained-release hydrogen microbubble capsule; The curved graphene described in step (1) is prepared as follows: Carbon rods are obtained by mixing white coal and coal tar, and then carbonized and graphitized to obtain conductive carbon rods. Two of the conductive carbon rods are placed in ultrapure water as anode and cathode, respectively, and subjected to voltage-stabilized electrolysis to obtain a mixed solution. The mixed solution is filtered and centrifuged to obtain a curved graphene solution, which includes curved graphene.

9. The preparation method according to claim 8, characterized in that, The pressure at which the white coal and coal tar are mixed is 1~5 MPa.

10. The preparation method according to claim 8, characterized in that, The two conductive carbon rods are identical conductive carbon rods.

11. The preparation method according to claim 8, characterized in that, The white coal is pre-crushed and screened before being mixed, and the particle size of the screened white coal is less than 100 μm.

12. The preparation method according to claim 8, characterized in that, The static potential of the voltage-stabilized electrolyzer is 10~60V.

13. The preparation method according to claim 8, characterized in that, The solid content of the curved graphene solution is 2-6‰.

14. The preparation method according to claim 8, characterized in that, The D50 particle size of the curved graphene in the curved graphene solution is 5~20nm.

15. The preparation method according to claim 8, characterized in that, The calcination temperature in step (1) is 120~150℃.

16. The preparation method according to claim 8, characterized in that, The diameter of the hydrogen-generating particles is 1~10 mm.

17. The preparation method according to claim 8, characterized in that, The microporous capsule shell in step (2) is prepared as follows: A microporous capsule shell is obtained by mixing a polymer, a porous material, and curved graphene, molding the mixture, and then sintering it.

18. The preparation method according to claim 17, characterized in that, The sintering temperature is 160~240℃, and the sintering time is 1~4h.

19. The preparation method according to claim 17, characterized in that, After molding and before sintering, a gradient temperature increase is performed.

20. The preparation method according to claim 19, characterized in that, The gradient heating is performed in the following manner: Heat to 130~155℃, hold for 1~2 hours, then heat to 160~240℃ and hold.

21. The preparation method according to claim 8, characterized in that, The preparation method includes: (1) After crushing and screening the white coal to a particle size of less than 100 μm, coal tar is added at 1~5 MPa to obtain carbon rods, which are then subjected to carbonization and graphitization treatment to obtain conductive carbon rods. Two identical conductive carbon rods are placed in ultrapure water as anode and cathode respectively. A static potential of 10~60V is applied between the anode and cathode and stirred. After voltage stabilization and electrolysis, a mixed solution is obtained. The mixed solution is filtered and centrifuged to obtain a curved graphene solution with a solid content of 2~6‰. The D50 particle size of the curved graphene in the curved graphene solution is 5~20 nm. (2) The hydrogen-generating agent, the skeleton forming agent, the organic acid and the curved graphene described in step (1) are mixed and granulated, and the resulting particles are calcined at 120~150℃ to obtain hydrogen-generating particles with a diameter of 1~10mm. (3) Mix the polymer, porous material and curved graphene, heat to 130~155℃, keep warm for 1~2h, then heat to 160~240℃ and keep warm, and sinter at 160~240℃ for 1~4h to obtain microporous capsule shell; (4) The hydrogen-generating particles described in step (2) are loaded into the microporous capsule shell described in step (3) and sealed to obtain a sustained-release hydrogen microbubble capsule.

22. The application of a sustained-release hydrogen microbubble capsule as described in any one of claims 1-7, characterized in that, The slow-release hydrogen microbubble capsules are used for the slow release of hydrogen and the preparation of hydrogen-rich water.

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