CN115744816B - Solid hydrogen-loaded material and preparation method and application thereof - Google Patents
Solid hydrogen-loaded material and preparation method and application thereof Download PDFInfo
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- CN115744816B CN115744816B CN202310033992.7A CN202310033992A CN115744816B CN 115744816 B CN115744816 B CN 115744816B CN 202310033992 A CN202310033992 A CN 202310033992A CN 115744816 B CN115744816 B CN 115744816B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to the technical field of solid-state loaded hydrogen, and particularly relates to a solid-state loaded hydrogen material, and a preparation method and application thereof. The preparation method of the solid-state hydrogen-loaded material comprises the following steps: soaking the load shell in an alkaline solution, washing with water, and drying; crushing the dried load shell to obtain superfine shell powder; heating the superfine shell powder at 500-800 deg.C; putting the obtained shell powder and silicon dioxide into a mixer, mixing uniformly, putting the mixed powder into a closed container, pouring purified water, stirring, sealing, filling hydrogen into water, filtering, and naturally drying to obtain hydrogen storage powder; and (3) putting the hydrogen storage powder into a hydrogen reaction furnace, and heating under the atmosphere of mixed gas of hydrogen and nitrogen to obtain the solid hydrogen-loaded material. The redox potential of water is reduced to be below-500 mV, hydrogen is released through hydrolysis and dissolved in water to form hydrogen-containing water, and the concentration of the water-soluble hydrogen can reach more than 1000 ppb.
Description
Technical Field
The invention belongs to the technical field of solid-state loaded hydrogen, and particularly relates to a solid-state loaded hydrogen material, and a preparation method and application thereof.
Background
Hydrogen therapy has become a novel and potentially breakthrough area of medicine. Hydrogen (H) 2 ) Proved to be an effective antioxidant for more than 150 disease models. Hydrogen has been ignored by medical researchers until 2007, ohsawa et al published a pioneering paper, suggesting that hydrogen has a potential health-promoting effect. Without affecting other ROS, they found that hydroxyl radicals are selectively scavenged, ultimately protecting cells from oxidative damage. Later, more researchers around the world have not only confirmed H 2 The treatment has no toxic effect, and has also found anti-inflammatory, anti-apoptosis and anti-allergic effects.
The ROS is Reactive Oxygen Species (ROS), which is a kind of one-electron reduction product of oxygen in vivo, and is generated by leaking out a respiratory chain and consuming about 2% of oxygen before electrons can be transferred to a terminal oxidase, and includes superoxide anion, hydrogen peroxide, hydroxyl radical, and nitrogen oxide, which are electron reduction products of oxygen.
As a novel antioxidant material, hydrogen has a very wide market prospect. For many years, japanese corporation has made oral hydrogen tablets from coral calcium materials containing hydrogen, and as in Japanese patent No. 4245655, japanese patent No. 4159598 and Japanese patent No. 4472022, it has described a method of holding hydrogen by using zeolite, coral, oyster shell, precipitated calcium carbonate and other materials as raw material powder carriers. The magnesium-based material is used for manufacturing the hydrogen hydrolysis tablet in countries such as the United states, canada and the like. China also uses hydrogen-containing shells as hydrogen-loaded materials, and magnesium-based shells are hydrogenated to form hydrogen-loaded magnesium hydride. For example, the powder carrying negative hydrogen ions in the Chinese invention patent and the preparation method thereof (the publication No. CN103710028B, the publication time is 2014.12.24), the hydrogen releasing material based on magnesium, the preparation method thereof and the method for preparing hydrogen by hydrolysis (the publication No. CN111646429A, the publication time is 2022.3.18). The products developed by the patent technologies have very large market space, and can be applied to various industries such as food, cosmetics, feed, medical dressing, chinese herbal medicine and the like.
During the process of using and researching the materials, the following problems are found: unsafe to store and transport, especially magnesium hydride materials; the hydrogen production amount is not high, for example, the shell type hydrogen-negative material is placed in 300mL of water, the oxidation-reduction potential is-235 mV, and the concentration of negative hydrogen ions is 237ppb. Therefore, the research and development team hopes to develop a solid-state hydrogen-loaded material with high safety hydrogen production, and a great deal of research and experimental work is done for the solid-state hydrogen-loaded material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a solid-state hydrogen-loaded material, which reduces the oxidation-reduction potential of water to be below-500 mV, enables the water to have stronger antioxidation function, releases hydrogen through hydrolysis, is dissolved in the water to form hydrogen-containing water, and has the water-soluble hydrogen concentration of over 1000 ppb.
The invention also aims to provide a preparation method of the solid-state hydrogen-loaded material, which can greatly increase the area of micro-channels of the solid-state hydrogen-loaded material by adding the nano-silica, and is beneficial to the adsorption and storage of hydrogen; the micron-scale shell powder material is mixed with the nano-scale silicon dioxide, the silicon oxide can coat the surface of the calcium carbonate powder or form a micro-core-shell structure, and the hydrogen filled into the micro-nano pores of the calcium carbonate can be locked in a solid-liquid hydrogen filling process; the two processes of solid-liquid high-pressure hydrogen adsorption and high-temperature curing hydrogen filling are combined, so that the hydrogen storage content and the material stability are greatly improved.
Another object of the present invention is to provide a use of the solid-state hydrogen-supporting material.
The technical scheme adopted by the invention is as follows:
the preparation method of the solid-state hydrogen-loaded material comprises the following steps:
(1) Soaking the load shell in alkaline solution, washing with water, and drying;
(2) Crushing the dried load shell to 50-300 meshes, and mechanically grinding to 800-1200 meshes to obtain superfine shell powder;
(3) Heating the superfine shell powder at 500-800 deg.C for 1-5h;
(4) Putting the shell powder obtained in the step (3) and silicon dioxide into a mixer to be mixed uniformly for 0.5-3h, wherein the silicon dioxide accounts for 10-50% of the total weight;
(5) Putting the uniformly mixed powder into a closed container, pouring purified water, stirring and sealing by a stirrer, then filling hydrogen into the water for 1-3 hours, filtering water, and naturally drying to obtain hydrogen storage powder;
(6) And putting the hydrogen storage powder into a hydrogen reaction furnace, and heating under the atmosphere of mixed gas of hydrogen and nitrogen at the temperature of 200-500 ℃ for 1-5h to obtain the solid hydrogen-loaded material.
The alkaline solution is one or a mixture of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, the alkaline concentration is 0.1-0.5mol/L, the soaking time is 3-10h, and the drying temperature is 50-100 ℃.
The load shell is one or more of oyster shell, coral calcium, scallop shell, clam shell, sea snail shell and mussel shell.
The shells of marine organisms are various, including oyster shells, coral calcium, scallop shells, clam shells, sea snail shells, mussel shells and the like, are wide in source and easy to purchase, and the main components of the shells are calcium carbonate (about 95 percent) and organic matters of 5 percent. The main purpose of the caustic wash is to remove dirt (sludge and fouling organisms) and residual slough from the shell surface.
Adopts a two-stage crushing process, firstly crushing to 50-300 meshes, and then mechanically grinding to 800-1200 meshes. The method mainly considers cost saving, has simple coarse crushing equipment and lower cost, firstly performs coarse crushing and then enters mechanical grinding, can improve the service efficiency of the equipment and reduce the cost.
The silicon dioxide is nano silicon dioxide with the size of 10-100nm.
The ultrafine powder and the silicon dioxide are mixed by a three-dimensional mixer for 0.5-3h. Because the superfine powder is micron-sized, the silicon dioxide is nano-sized, and the mass percentage of the silicon dioxide is 10-50%, the superfine powder and the silicon dioxide can be mixed more uniformly. The mixed powder can form silicon dioxide to coat the surface of the ultrafine powder, which is more beneficial to the realization of the subsequent process.
The volume ratio of the nitrogen to the hydrogen is (60-70): (40-30).
The hydrogen source is one or more of electrolyzed water hydrogen production, industrial hydrogen cylinders and metal hydrolysis hydrogen production.
The mass ratio of the powder to the purified water before stirring by the stirrer in the step (5) is (1-5): 1, the rotating speed of the stirrer is 60-200r/min, and the charging pressure is 1-3Mpa.
The solid hydrogen-loaded material is prepared by the preparation method.
The solid hydrogen-loaded material is applied to cosmetic additives, beverage additives, food additives, feed additives, plant growth regulators or drug additives.
The solid-state hydrogen-loaded material is compounded with the effervescent agent, so that the speed of releasing hydrogen in water by the solid-state hydrogen-loaded material is increased, the dissolution of the hydrogen-loaded material is accelerated, and the use effect of a hydrogen product prepared by adding the hydrogen-loaded material is facilitated.
The effervescent agent is prepared by compounding sodium bicarbonate and citric acid according to a mass ratio of 1.2 to 0.5-2h.
Compared with the prior art, the invention has the following beneficial effects:
(1) The oxidation-reduction potential of the water is reduced to be below-500 mV, so that the water has stronger anti-oxidation function;
(2) Hydrogen is released through hydrolysis and is dissolved in water to form hydrogen-containing water, the concentration of the water-soluble hydrogen can reach over 1000ppb, and drinking the hydrogen-containing water has better health effect;
(3) Reducing molecular groups of water, O 17 The half-peak width can reach below 50Hz, and the activity is better;
(4) Beneficial trace elements such as calcium, metasilicic acid, magnesium, potassium, zinc and the like can be dissolved out, and the content of metasilicic acid reaches 100mg/L through detection;
(5) By adding the nano silicon dioxide, the area of the micro-channel of the solid hydrogen-loaded material is greatly increased, which is beneficial to the adsorption and storage of hydrogen;
(6) The shell powder material is mixed with the nano-scale silicon dioxide, the silicon dioxide can coat the surface of the calcium carbonate powder or form a micro-core-shell structure, and the hydrogen filled into the calcium carbonate micro-nano holes can be locked in the solid-liquid hydrogen filling process;
(7) The stability of the silica gel can be remarkably improved by mixing the shell powder material with the silica;
(8) The hydrogen storage content and the material stability are greatly improved by combining the two processes of solid-liquid high-pressure hydrogen adsorption and high-temperature solidification hydrogen charging;
(9) Can be used as cosmetic additive, beverage additive, food additive, feed additive, plant growth regulator or pharmaceutical additive, and can be made into hydrogen-rich products with hydrogen releasing effect, such as food, feed, medicine, hydrogen water, and cosmetics.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
Soaking 100g of oyster shell in 0.1mol/L potassium hydroxide solution for 10h, taking out the oyster shell, drying at 50 ℃, crushing the dried shell to 50 meshes, mechanically grinding to 800 meshes to obtain superfine shell powder, heating the superfine shell powder at 500 ℃ for 5h, simultaneously adding the dried powder and nano-silica with the size of 50nm into a mixer, wherein the nano-silica accounts for 10% of the total mass, putting the uniformly mixed powder into a closed container, pouring purified water, stirring and sealing by a stirrer, wherein the mass ratio of the powder to the purified water is 3:1, the rotation speed of the stirrer is 150r/min, then preparing hydrogen by electrolyzing water, filling hydrogen into water, keeping the hydrogen filling pressure at 2MPa, maintaining for 2h, naturally airing after water filtration to obtain hydrogen storage powder, putting the hydrogen storage powder into a hydrogen reaction furnace, heating in the mixed gas atmosphere of hydrogen and nitrogen, wherein the volume ratio of nitrogen to hydrogen is 60, the heating temperature is 200 h, and the hydrogen loading time is 5h to obtain the solid-state material.
Example 2
Soaking 100g of scallop shell in a sodium hydroxide solution with the concentration of 0.3mol/L for 6 hours, taking out the scallop shell, drying at 80 ℃, crushing the dried shell to 200 meshes, mechanically grinding to 1000 meshes to obtain superfine shell powder, drying the superfine shell powder at 600 ℃ for 3 hours, simultaneously adding the dried powder and nano-silica with the size of 10nm into a mixer, wherein the nano-silica accounts for 30% of the total mass, putting the uniformly mixed powder into a closed container, pouring purified water, stirring and sealing by a stirrer, filling the powder and the purified water with the mass ratio of 1:1 and the rotation speed of the stirrer of 60r/min, filling hydrogen into water by an industrial hydrogen bottle, keeping the hydrogen filling pressure of 1MPa for 3 hours, naturally airing after water filtration to obtain the powder for storing hydrogen, putting the powder into a hydrogen reaction furnace, and heating in a mixed gas atmosphere of hydrogen and nitrogen, wherein the volume ratio of the nitrogen to the hydrogen is 65, the heating temperature is 300 ℃, and the hydrogen loading time is 3 hours, so as to obtain a solid-state hydrogen material.
Example 3
Mixing 100g of clam shell and conch shell, soaking in a sodium carbonate solution with the concentration of 0.5mol/L for 3h, taking out, drying at 100 ℃, crushing the dried shell to 300 meshes, mechanically grinding to 1200 meshes to obtain superfine shell powder, drying the superfine shell powder at 800 ℃ for 1h, simultaneously adding the dried powder and nano-silica with the size of 100nm into a mixer, adding the nano-silica into the mixer, adding the uniformly mixed powder into a closed container, pouring purified water, stirring and sealing by a stirrer, wherein the mass ratio of the powder to the purified water is 5:1, the rotation speed of the stirrer is 200r/min, then preparing hydrogen by metal hydrolysis, filling hydrogen into water, keeping the hydrogen filling pressure at 3MPa for 1h, naturally airing the water after filtering to obtain hydrogen storage powder, putting the hydrogen storage powder into a hydrogen reaction furnace, heating under the atmosphere of mixed gas of hydrogen and nitrogen, the volume ratio of nitrogen to hydrogen is 70, the heating temperature is 500 h, and obtaining the solid-state load material.
Comparative example 1
Soaking 100g of oyster shell in a sodium hydroxide solution with the concentration of 0.1mol/L for 6h, taking out the oyster shell, drying at 100 ℃, crushing the dried shell to 300 meshes, drying, putting the dried powder into a closed container, and heating in a mixed gas atmosphere of hydrogen and nitrogen, wherein the volume ratio of the nitrogen to the hydrogen is 95.
The solid hydrogen-loaded materials prepared in the examples and the comparative examples are detected by the following methods:
(1) And (3) detecting the concentration of water-soluble hydrogen and a negative potential: 100mg of powder of a solid-state hydrogen-loaded material is weighed and placed in 300mL of purified water, a KH888 dissolved hydrogen/negative potential test pen produced in Taiwan province of China is inserted into a container for inspection, and a numerical value is read.
(2) Skin irritation: according to the 2015 edition of cosmetic safety technical specifications, the rabbit was subjected to an acute skin irritation experiment.
（3）O 17 The half-peak width test method comprises the following steps: according to the general rule of JY/T007-1996 superconducting pulse Fourier transform nuclear magnetic resonance spectroscopy method, a BRUKER AVANCE DMX 500 nuclear magnetic resonance spectrometer is used for detection.
(4) Detecting the content of metasilicic acid: the detection is carried out according to a metasilicic acid detection method in the national standard GB 8538-2016.
The results of the measurements of the aqueous hydrogen concentration and the negative potential measurement for each of the examples and comparative examples are shown in table 1.
Acute skin irritation, O, of examples and comparative examples 17 The results of the measurement of the half-peak width and the content of metasilicic acid are shown in Table 2.
TABLE 2 acute skin irritation, O, of the examples and comparative examples 17 Detection results of half-peak width and metasilicic acid content
As can be seen from the detection results in tables 1 and 2, the hydrogen is released by hydrolysis and dissolved in water to form hydrogen-containing water, and the concentration of the water-soluble hydrogen can reach over 1000 ppb; can reduce water molecular group, O 17 The half-peak width can reach below 50Hz, and the activity is better; beneficial trace elements such as metasilicic acid and the like can be dissolved out, and the content of metasilicic acid reaches more than 100 mg/L.
Claims (7)
1. The preparation method of the solid-state hydrogen-loaded material is characterized by comprising the following steps of:
(1) Soaking the load shell in alkaline solution, washing with water, and drying;
(2) Crushing the dried load shell to 50-300 meshes, and mechanically grinding to 800-1200 meshes to obtain superfine shell powder;
(3) Heating the superfine shell powder at 500-800 deg.C for 1-5h;
(4) Putting the superfine shell powder obtained in the step (3) and silicon dioxide into a mixer to be mixed uniformly for 0.5-3h, wherein the silicon dioxide accounts for 10-50% of the total weight;
(5) Putting the uniformly mixed powder into a closed container, pouring purified water, stirring and sealing by a stirrer, then filling hydrogen into the water for 1-3h, filtering water, and naturally drying to obtain hydrogen storage powder;
(6) Putting the hydrogen storage powder into a hydrogen reaction furnace, and heating under the atmosphere of mixed gas of hydrogen and nitrogen at the temperature of 200-500 ℃ for 1-5h to obtain a solid hydrogen-loaded material;
the load shell is one or more of oyster shell, coral calcium, scallop shell, clam shell, sea snail shell and mussel shell.
2. The method for preparing the solid-state hydrogen-supported material according to claim 1, wherein the alkaline solution is one or more of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution and potassium carbonate solution, the alkaline concentration is 0.1-0.5mol/L, the soaking time is 3-10h, and the drying temperature is 50-100 ℃.
3. The method for preparing the solid-state hydrogen-supporting material according to claim 1, wherein the silica is nano-silica with a size of 10-100nm.
4. The method for preparing the solid-state hydrogen-supported material according to claim 1, wherein the volume ratio of the nitrogen gas to the hydrogen gas is (60-70): (40-30).
5. The method for preparing the solid-state hydrogen-loaded material according to claim 1, wherein the mass ratio of the powder to the purified water before stirring by the stirrer in the step (5) is (1-5): 1, the rotating speed of the stirrer is 60-200r/min, and the charging pressure is 1-3Mpa.
6. A solid hydrogen-supporting material, which is obtained by the production method according to any one of claims 1 to 5.
7. Use of the solid hydrogen-loaded material according to claim 6, for cosmetic additives, beverage additives, food additives, feed additives, plant growth regulators or pharmaceutical additives.
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| CN103710028B (en) * | 2013-12-31 | 2014-12-24 | 王绪珍 | Powder capable of supporting negative hydrogen ion and preparation method of powder |
| CN114848513B (en) * | 2022-06-07 | 2023-10-24 | 河北云悦生物科技有限公司 | Composite hydrogen-rich material and preparation method thereof |
| CN217377309U (en) * | 2022-06-30 | 2022-09-06 | 河北诺氢科技有限公司 | Solid hydrogen production equipment |
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