Green hydrogen storage container and manufacturing method thereof

Abstract

The invention provides a green hydrogen storage container and a manufacturing method of the green hydrogen storage container, and belongs to the field of hydrogen storage. The green hydrogen storage container comprises an inner shell, the inner layer of the inner shell is provided with an inert gas adsorption coating, the inert gas adsorption coating is made of an inert gas adsorption material, and the inert gas adsorption material takes iron as a main body and comprises one or more of potassium, magnesium, calcium, cobalt, aluminum oxide and silicon dioxide; and an inert gas molecular layer is arranged on the surface of the inert gas adsorption coating. The inert gas molecular layer in a chemical adsorption state forms a molecular-level blocking effect on hydrogen molecules close to the inert gas adsorption layer, so that the hydrogen molecules are limited to penetrate through the adsorption coating and enter a matrix of the inner shell, and the problem of hydrogen embrittlement of a cheap iron-based material during storage of high-pressure hydrogen is avoided; therefore, large-scale and low-cost storage of the high-pressure gaseous green hydrogen is realized.

Description

Technical Field

[0001] The present invention relates to the field of hydrogen storage, and in particular to a green hydrogen storage container and a method for manufacturing the green hydrogen storage container. Background Art

[0002] Converting renewable energy represented by solar energy and wind energy into storable green hydrogen (or further converting green hydrogen into easily liquefied green ammonia and green methanol) through photovoltaic / wind turbine power generation and water electrolysis to produce hydrogen, and then giving green hydrogen (or green ammonia and green methanol) energy properties, and applying them in energy-consuming fields such as thermal power generation, transportation, and high-temperature manufacturing is recognized as one of the important ways to solve global climate problems and support the green and sustainable transformation of energy.

[0003] Due to the significant regional endowment differences in the distribution of renewable energy resources around the world, in order to achieve cross-regional and even intercontinental green hydrogen energy trade activities, whether it is directly using green hydrogen as the final trade product, or using green hydrogen derivatives such as green ammonia and green methanol as the final trade products, high-density and large-volume caching methods are required on both the preparation and application sides of green hydrogen. Hydrogen is the gas with the smallest molecular weight and low density. The container volume required for large-scale atmospheric pressure storage is very large, the floor space is huge, and the cost is too high. Therefore, hydrogen storage is generally pressurized storage. Affected by its characteristics, it is very easy to cause hydrogen embrittlement and failure of common container materials during storage, which in turn causes hydrogen leakage and the possibility of causing large-scale explosion accidents. At present, laboratories and small-scale applications use carbon fiber wrapped bottle groups for high-pressure hydrogen storage, which is resistant to hydrogen embrittlement, but the cost is very expensive and difficult to promote on a large scale.

[0004] Therefore, developing a green hydrogen storage container and a pressurized hydrogen storage method that are resistant to hydrogen embrittlement is an issue that needs to be urgently addressed in the era of large-scale application of green hydrogen. Summary of the invention

[0005] An object of the present invention is to provide a green hydrogen storage container which can effectively reduce the risk of hydrogen embrittlement.

[0006] Another object of the present invention is to provide a method for manufacturing a green hydrogen storage container, which is used to manufacture a green hydrogen storage container.

[0007] The present invention is achieved in that: A green hydrogen storage container, characterized in that it comprises an inner shell, the inner layer of the inner shell is provided with an inert gas adsorption coating, the inert gas adsorption coating is made of an inert gas adsorption material, the inert gas adsorption material is mainly iron and contains one or more of potassium, magnesium, calcium, cobalt, aluminum oxide and silicon dioxide; The surface of the inert gas adsorption coating is provided with an inert gas molecule layer.

[0008] Furthermore, in the inert gas adsorption material, the iron content is between 70% and 95%, and the contents of potassium, magnesium, calcium, cobalt, aluminum oxide and silicon dioxide are 0.5-5%, 0.5-5%, 0.1-5%, 0.5-10%, 0.5-5% and 0.1-2%, respectively, and the sum of the mass percentages of all the materials is 100%.

[0009] Furthermore, the adsorbent iron in the inert gas exists in a microcrystalline structure, and the grain size is 5-500 nm.

[0010] Furthermore, the inert gas is nitrogen.

[0011] Furthermore, it also includes an outer shell, a sandwich layer is formed between the outer shell and the inner shell, and a heat insulating material is arranged in the sandwich layer.

[0012] Furthermore, the insulation layer material is one or more of foam plastics, aerogel, ultrafine glass wool and mineral wool.

[0013] Furthermore, the inner shell is made of carbon steel or austenitic stainless steel.

[0014] A method for manufacturing a green hydrogen storage container, for manufacturing the green hydrogen storage container, characterized in that it comprises the following steps: Nitrogen gas at a temperature of 30-100° C. and a pressure of 0.1-5 MPa is injected into the inner shell, where nitrogen molecules adsorb iron atoms in the inert gas adsorption coating, so that Fe atoms and nitrogen molecules form a strong chemical adsorption effect.

[0015] Furthermore, the inert gas adsorption coating is prepared on the substrate of the inner shell by a thermal spraying or cold spraying method.

[0016] Further, at a temperature of 30-50° C., the nitrogen pressure in the gas container is adjusted to below 0.1 MPa.

[0017] The beneficial effects of the present invention are: The green hydrogen storage container and the manufacturing method of the green hydrogen storage container obtained by the above-mentioned design of the present invention, when in use, the inner surface of the inner shell is provided with an inert gas adsorption coating, and the inert gas molecular layer in the chemical adsorption state forms a molecular-level barrier effect on the hydrogen molecules close to the inert gas adsorption layer, thereby limiting the hydrogen molecules from passing through the adsorption coating and entering the matrix of the inner shell, thereby avoiding the hydrogen embrittlement problem of cheap iron-based materials when storing high-pressure hydrogen, thereby realizing large-scale, low-cost storage of high-pressure gaseous green hydrogen. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0019] Figure 1 Schematic diagram of a green hydrogen storage container provided in an embodiment of the present invention.

[0020] Icon: 1-inner shell; 2-coating; 3-insulation layer; 4-cooling unit; 5-outer shell; 6-air inlet unit; 7-air outlet unit; 8-pressure gauge; 9-temperature sensor; 10-safety valve. DETAILED DESCRIPTION Example

[0021] like Figure 1 This embodiment provides a green hydrogen storage container and a manufacturing method. The green hydrogen storage container is a horizontal structure, and the whole is a horizontal cylindrical tank.

[0022] Specifically, the green hydrogen storage container includes an inner shell 1 and an outer shell 5, both of which are made of carbon steel. An interlayer is formed between the inner shell 1 and the outer shell 5, and an insulating material is arranged in the interlayer. The above-mentioned insulating material is one or more of foam plastics, aerogel, ultra-fine glass wool and mineral wool, which is used to reduce heat transfer and maintain the temperature of hydrogen in the storage tank stable.

[0023] Furthermore, an inert gas adsorption coating 2 is provided on the inner surface of the inner shell 1. The inert gas adsorption coating 2 is made of a material that can adsorb inert gas. The specific material is mainly iron and contains one or more of potassium, magnesium, calcium, cobalt, aluminum oxide and silicon dioxide.

[0024] Specifically, in the inert gas adsorption material, the content of iron is between 70% and 95%, and the contents of potassium, magnesium, calcium, cobalt, aluminum oxide and silicon dioxide are 0.5-5%, 0.5-5%, 0.1-5%, 0.5-10%, 0.5-5% and 0.1-2% respectively; and the adsorption material iron in the inert gas exists in a microcrystalline structure with a grain size of 5-500nm. The d orbital electrons of Fe atoms in Fe microcrystals are transferred to the π antibonding orbits of nitrogen molecules, so that Fe atoms and nitrogen molecules form a strong chemical adsorption effect, and the potassium, magnesium, calcium, cobalt, aluminum oxide and silicon dioxide present in Fe microcrystals play a role in promoting electron transfer and stabilizing the microcrystalline structure. The use of the above materials can form a strong chemical adsorption effect between the iron atoms in the inert gas adsorption coating 2 and the inert gas molecules, forming a molecular barrier effect on the hydrogen molecules close to the inert gas adsorption layer, thereby limiting the hydrogen molecules from passing through the adsorption coating 2 and entering the matrix of the inner shell 1, thereby avoiding the hydrogen embrittlement problem of the iron-based material when storing high-pressure hydrogen. In addition, since the cost of iron-based materials is relatively low, the overall manufacturing cost of the green hydrogen storage container can be reduced.

[0025] In this embodiment, the above-mentioned inert gas uses nitrogen, which has a relatively low cost; in other embodiments, other inert gases such as argon and neon may also be used.

[0026] In the specific operation, nitrogen with a temperature of 30-100°C and a pressure of 0.1-5 MPa is injected into the inner shell 1. In the inner shell 1, the nitrogen molecules adsorb the iron atoms in the inert gas adsorption coating 2, so that the Fe atoms and the nitrogen molecules form a strong chemical adsorption effect. Further, at a temperature of 30-50°C, the nitrogen pressure in the gas container is adjusted to below 0.1 MPa; then, hydrogen with a temperature below 50°C and a pressure above 10 MPa is injected into the gas storage container, thereby realizing large-scale, low-cost storage of high-pressure gaseous hydrogen.

[0027] Furthermore, the green hydrogen storage container is also provided with an air intake unit 6, an air outlet unit 7, a cooling unit 4, a pressure gauge 8, a temperature sensor 9 and a safety valve 10; wherein, the air intake unit 6 is arranged at one end of the green hydrogen storage container, and the air outlet unit 7 is arranged at the other end of the green hydrogen storage container; the cooling unit 4 is arranged on the air outlet pipe of the air outlet unit 7, and the pressure gauge 8, the temperature sensor 9 and the safety valve 10 are arranged on the top of the green hydrogen storage container.

[0028] The air inlet unit 6 introduces 1720 standard cubic meters of hydrogen into the inner shell with a volume of 50 cubic meters. Under the monitoring of the pressure gauge 8 and the temperature sensor 9, the hydrogen pressure in the inner shell is maintained at 40 MPa and the temperature is between 25-45°C. When the pressure exceeds 42 MPa, the safety valve 10 will open to release the pressure. The insulation layer 3 filled with foam plastic between the inner shell and the outer shell will isolate most of the external heat radiation, while the coating 2 of the inner shell 1 will isolate the corrosion of the inner shell material by hydrogen through the formed adsorption protective layer. When using hydrogen, the hydrogen enters the cooling unit 4 through the outlet unit 7, and enters the gas-using equipment after being cooled to.

[0029] It should be noted that in other embodiments, if the inner shell 1 is strong enough, the outer shell 5 may not be provided. In addition, the overall shape of the inner shell 1 and the outer shell 5 may be spherical or vertical, which can be selected according to actual conditions.

[0030] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A green hydrogen storage container, characterized in that: It comprises an inner shell, the inner layer of which is provided with an inert gas adsorption coating, the inert gas adsorption coating is made of an inert gas adsorption material, the inert gas adsorption material is mainly composed of iron and contains one or more of potassium, magnesium, calcium, cobalt, aluminum oxide and silicon dioxide; The surface of the inert gas adsorption coating is provided with an inert gas molecule layer.

2. The green hydrogen storage container according to claim 1, characterized in that: In the inert gas adsorption material, the iron content is between 70% and 95%, and the contents of potassium, magnesium, calcium, cobalt, aluminum oxide and silicon dioxide are 0.5-5%, 0.5-5%, 0.1-5%, 0.5-10%, 0.5-5% and 0.1-2% respectively, and the sum of the mass percentages of all the materials is 100%.

3. The green hydrogen storage container according to claim 1, characterized in that: The adsorbent material iron in the inert gas exists in a microcrystalline structure, and the grain size is 5-500nm.

4. The green hydrogen storage container according to claim 1, characterized in that: The inert gas is nitrogen.

5. The green hydrogen storage container according to claim 1, characterized in that: It also includes an outer shell, wherein a sandwich is formed between the outer shell and the inner shell, and a heat insulating material is arranged in the sandwich.

6. The green hydrogen storage container according to claim 5, characterized in that: The thermal insulation layer material is one or more of foam plastics, aerogel, ultra-fine glass wool and mineral wool.

7. The green hydrogen storage container according to claim 1, characterized in that: The inner shell is made of carbon steel or austenitic stainless steel.

8. A method for manufacturing a green hydrogen storage container, used to manufacture the green hydrogen storage container according to any one of claims 1 to 6, characterized in that: The following steps are involved: Nitrogen gas at a temperature of 30-100° C. and a pressure of 0.1-5 MPa is injected into the inner shell, where nitrogen molecules adsorb iron atoms in the inert gas adsorption coating, so that Fe atoms and nitrogen molecules form a strong chemical adsorption effect.

9. The method for manufacturing a green hydrogen storage container according to claim 7, characterized in that: The inert gas adsorption coating is prepared on the substrate of the inner shell by a thermal spraying or cold spraying method.

10. The method for manufacturing a green hydrogen storage container according to claim 7, characterized in that: At a temperature of 30-50° C., the nitrogen pressure in the gas container was adjusted to below 0.1 MPa.

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