A magnesium-based solid hydrogen storage alloy in-situ hydrogen absorption and hydrolysis hydrogen production device and its application

Abstract

The present invention discloses a magnesium-based solid-state hydrogen storage alloy in-situ hydrogen absorption and hydrolysis hydrogen production device and its application. The device can achieve controllable hydrogen charging and hydrolysis hydrogen production of magnesium alloy materials within the same tank, which will greatly improve the efficiency of hydrolysis hydrogen production of magnesium hydrogen storage materials and reduce the manufacturing time of the system. The device can directly inject hydrogen into the magnesium alloy hydrogen production tank to cause the magnesium alloy to absorb hydrogen to generate a hydrogenated magnesium alloy. When hydrogen is subsequently needed, water is introduced to cause the hydrogenated magnesium alloy to hydrolyze and produce hydrogen. During this process, after the magnesium alloy absorbs hydrogen, it does not need to be removed and exposed to air, nor does it require further processing. The hydrogen absorption and hydrolysis hydrogen production of the magnesium alloy can be completed step by step within the same device, which greatly saves the manufacturing time and cost of the hydrolysis hydrogen production tank.

Description

Technical Field

[0001] The present invention belongs to the field of hydrogen preparation and storage equipment, and in particular relates to a magnesium-based solid hydrogen storage alloy in-situ hydrogen absorption and hydrolysis hydrogen production device and its application. Background Art

[0002] Energy is the foundation of human survival and development. Fossil fuels such as coal, oil, and natural gas are not only limited in reserves, but their excessive consumption can lead to serious environmental pollution and energy shortages. The primary strategy for addressing this issue is the development of clean, renewable, and green energy. Hydrogen energy is a highly anticipated emerging energy source of the 21st century. As one of the basic components of water, hydrogen offers numerous advantages over traditional fossil fuels, including high energy density, abundant resources, environmentally friendly products, and high safety. However, the large-scale use of hydrogen energy faces numerous challenges, including its production, storage, and transportation.

[0003] Solid-state hydrogen storage is a safe and efficient method of hydrogen storage with a high mass / volume hydrogen storage density. Magnesium is one of the most abundant light alloys on earth, and my country has very rich magnesium reserves. Magnesium hydride produced by hydrogenation of metallic magnesium has a high mass (7.6wt% H2) and volume (110kg H2 m -3 ) hydrogen storage density. Magnesium hydride can release hydrogen through thermal decomposition and hydrolysis. Thermal decomposition to release hydrogen is an endothermic reaction that requires high temperatures (≥300°C); hydrolysis, on the other hand, is an exothermic reaction that can proceed at room temperature and releases up to 15.2% hydrogen, twice that of thermal decomposition. Therefore, the technical route of hydrogen production by hydrolysis of magnesium hydride has attracted widespread research interest.

[0004] However, in previous magnesium hydride hydrolysis devices, the hydrogen absorption and hydrolysis steps of the magnesium alloy were completed separately, which greatly reduced the hydrolysis efficiency of the material. Moreover, as the hydrolysis reaction proceeded, the hydrolysis product Mg(OH)2 gradually coated the surface of the MgH2 particles, blocking the contact between MgH2 and water, thereby inhibiting the hydrolysis reaction. Therefore, there is still much room for research in improving the hydrogen storage and hydrolysis efficiency of magnesium solid-state hydrogen storage materials. Summary of the Invention

[0005] In view of the above-mentioned defects of the prior art, the inventors designed a hydrolysis hydrogen production tank, which can realize the simultaneous in-situ hydrogen absorption and hydrolysis hydrogen production of magnesium alloy, greatly improving the hydrolysis hydrogen production efficiency of magnesium alloy, thereby completing the present invention.

[0006] Therefore, in one aspect, the present invention provides a magnesium-based solid hydrogen storage alloy in-situ hydrogen absorption and hydrolysis hydrogen production device, the device comprising a stainless steel tank, an insulation layer provided on the inner side of the stainless steel tank, a water inlet pipe and a hydrogen pipe provided on the top of the stainless steel tank, a water flow valve provided on the water inlet pipe, and connected to a porous air guide pipe extending into the interior of the stainless steel tank, a hydrogen valve provided on the hydrogen pipe, and an electric heating wire wrapped around the outside of the porous air guide pipe.

[0007] Furthermore, the porous air duct is filled with porous material to prevent powder from entering the trachea.

[0008] Furthermore, a water pump is provided on the water inlet pipe to control the flow rate of water and thus the flow rate of hydrogen.

[0009] Furthermore, the stainless steel tank contains magnesium alloy particles.

[0010] Furthermore, the magnesium alloy is a magnesium-based hydrogen storage alloy, which can be selected from Mg-1Al-7Ni-1Ce-0.5Zr hydrogen storage alloy, Mg-0.5Ti-7Ni-2.5Co-0.5Ce hydrogen storage alloy, Mg-0.5Ti-7Ni-2Co-0.5Ce-0.5La hydrogen storage alloy, and Mg-0.5Ti-7Ni-1.5Co-0.5Ce-0.5La-0.5Nd hydrogen storage alloy.

[0011] Furthermore, the magnesium-based hydrogen storage alloy is prepared by the following method: heating and melting Mg under a protective atmosphere, and then sequentially adding one or more of Mg-Ti master alloy, Mg-Al master alloy, Mg-Ni master alloy, Mg-Co master alloy, Mg-Zr master alloy, Mg-Na master alloy, Mg-Ce master alloy, Mg-La master alloy, Mg-Nd master alloy, and Mg-Y master alloy, wherein the content of the master alloy is 0.01% to 30% by weight; after the raw materials are fully stirred and mixed, they are cooled to room temperature at a rate of 50K / min to prepare the magnesium-based hydrogen storage alloy, crushed and sieved in air, and then pressed to obtain magnesium alloy particles.

[0012] A master alloy is a special alloy with one or more elements added to a metal matrix to address issues such as the element's tendency to burn out, difficulty in melting due to its high melting point, and high density and segregation, or to improve alloy properties. It is an additive functional material. The Mg-X master alloy used in the present invention is a commercially available alloy with a magnesium matrix and a metal X added thereto. The metal X can be selected from Ti, Al, Ni, Co, Zr, Na, Ce, La, Nd, and Y.

[0013] In another aspect, the present invention provides a method for in-situ hydrogen absorption and hydrolysis production of hydrogen by a magnesium-based solid hydrogen storage alloy, the method comprising:

[0014] S0: adding magnesium alloy particles into the stainless steel tank;

[0015] S1: Close the hydrogen valve and water flow valve, turn on the electric heating, heat the tank to 100-400℃, open the hydrogen valve, fill it with 3MPa hydrogen, close the hydrogen valve, maintain it at this temperature for 2h, and then wait for the tank to cool to room temperature. During this process, the magnesium alloy absorbs hydrogen to form a composite hydrogen storage material mainly composed of MgH2;

[0016] S2: Turn on the electric heater and heat to 80-100°C, open the water flow valve, and let water flow into the porous gas guide tube through the water pump, open the hydrogen valve, and collect the hydrogen produced by hydrolysis;

[0017] S3: After the hydrolysis is completed, close the water flow valve and hydrogen valve.

[0018] Furthermore, in S1, the tank body is heated to 200-300°C, for example, 200°C, 250°C, or 300°C.

[0019] Furthermore, in S0, the magnesium alloy particles are magnesium-based hydrogen storage alloys, which can be selected from Mg-1Al-7Ni-1Ce-0.5Zr hydrogen storage alloy, Mg-0.5Ti-7Ni-2.5Co-0.5Ce hydrogen storage alloy, Mg-0.5Ti-7Ni-2Co-0.5Ce-0.5La hydrogen storage alloy, and Mg-0.5Ti-7Ni-1.5Co-0.5Ce-0.5La-0.5Nd hydrogen storage alloy.

[0020] Technical Effects

[0021] The magnesium-based solid hydrogen storage alloy in-situ hydrogen absorption and hydrolysis hydrogen production device of the present invention can realize the simultaneous in-situ hydrogen absorption and hydrolysis hydrogen production of the magnesium alloy. The heating wire is energized so that the temperature of the heating wire reaches the hydrogen absorption temperature of the magnesium alloy. Then, the hydrogen valve is opened to introduce hydrogen through the porous air guide pipe to saturate the magnesium alloy with hydrogen. Then, the hydrogen-absorbed magnesium alloy does not need to be taken out from the tank body. When hydrogen is needed, water can be directly injected into the tank body through the water flow valve to hydrolyze the magnesium hydride to produce hydrogen, which will greatly improve the hydrolysis hydrogen production efficiency of the magnesium alloy. The hydrogen generated by electrolysis of water is directly injected into the hydrogen production tank as a hydrogen source for the magnesium alloy to absorb hydrogen. When hydrogen is needed later, water is directly introduced to hydrolyze the hydrogenated magnesium alloy to produce hydrogen. In this process, no additional magnesium hydride alloy is required. After the magnesium alloy absorbs hydrogen, it does not need to be taken out and exposed to the air. The hydrogen absorption and hydrolysis hydrogen production of the magnesium alloy can be completed in the same device, which greatly saves manpower and material resources.

[0022] The present invention adds one or more alloying elements such as Ni, Ti, Co, Zr, La, Ce, Nd, Na, and Y. During the hydrogenation process of the magnesium alloy particles, hydrides such as LaH3, CeH3, NdH3, NaH, and ZrH2 are simultaneously formed, catalyzing the combined effects and significantly promoting the hydrolysis of MgH2. Simultaneously, the hydrolysis of LaH3 generates conductive ions, creating a synergistic effect. Furthermore, the lower hydrogen overpotential of Ni and Co makes them excellent cathode materials, forming a tiny galvanic cell between the dispersed Ni / Co and the metallic Mg, promoting the hydrolysis of MgH2. The addition of alloying elements improves the hydrolysis kinetics of magnesium hydride, and the other metal hydrides formed during the hydrogenation process of the magnesium alloy effectively prevent the formation of a Mg(OH)2 coating during the hydrolysis process.

[0023] The hydrogen flow rate is controlled by controlling the water flow rate using a water pump; the porous air duct is filled with porous material (the porous material includes a sintered plate or a ceramic membrane) to prevent powder from entering the air duct and thus preventing the duct from being blocked, so that the MgH2 hydrogen production rate can be stably controlled.

[0024] The addition of alloying elements improves the air stability of magnesium alloys. Hydrogen production tanks can be filled with hydrogen for sealed storage. By controlling the alloy composition, an anti-oxidation protective layer is formed on the surface of the magnesium-based hydrogen storage alloy. The resulting hydrolysis-hydrogen-generating magnesium alloy particles are air-stable and exhibit excellent hydrolysis kinetics, making them suitable for hydrogen supply equipment in humid environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a schematic structural diagram of the magnesium-based solid hydrogen storage alloy in-situ hydrogen absorption and hydrolysis hydrogen production device in Example 1 of the present invention;

[0026] Figure 2 This is the hydrogen absorption curve of the Mg-1Al-7Ni-1Ce-0.5Zr hydrogen storage alloy used in Example 1 of the present invention;

[0027] Figure 3 This is the hydrogen production curve of hydrolysis using the Mg-1Al-7Ni-1Ce-0.5Zr hydrogen storage alloy in Example 1 of the present invention.

[0028] Figure numerals: 1: stainless steel tank; 2: thermal insulation layer; 3: porous air duct; 4: magnesium alloy particles; 5: electric heating wire; 6: hydrogen valve; 7: water flow valve; 8: water inlet pipe; 9: hydrogen pipe. DETAILED DESCRIPTION

[0029] The following describes preferred embodiments of the present invention with reference to the accompanying drawings to make its technical content clearer and easier to understand. The present invention can be embodied in many different forms of embodiments, and the scope of protection of the present invention is not limited to the embodiments mentioned herein.

[0030] Example 1:

[0031] A magnesium-based solid hydrogen storage alloy in-situ hydrogen absorption and hydrolysis hydrogen production device, such as Figure 1 As shown, the device comprises a stainless steel tank (1), an insulating layer (2) is provided inside the stainless steel tank (1), a water inlet pipe (8) and a hydrogen pipe (9) are provided on the top of the stainless steel tank (1), a water flow valve (7) is provided on the water inlet pipe (8), and is connected to a porous air guide pipe (3) extending into the interior of the stainless steel tank (1), a hydrogen valve (6) is provided on the hydrogen pipe (9), and an electric heating wire (5) is wound around the porous air guide pipe (3). A water pump is provided on the water inlet pipe (8) for controlling the flow rate of water and thus controlling the flow rate of hydrogen.

[0032] The in-situ hydrogen absorption and hydrolysis hydrogen production process of the hydrolysis hydrogen production device includes the following steps:

[0033] S0: adding the magnesium alloy particles (4) Mg-1Al-7Ni-1Ce-0.5Zr hydrogen storage alloy prepared by crushing into a stainless steel tank (1);

[0034] S1: Close the hydrogen valve (6) and the water flow valve (7), turn on the electric heating, heat the tank to 200 ° C, open the hydrogen valve (6), fill it with 3MPa hydrogen, close the hydrogen valve (6), maintain it at this temperature and pressure for 2 hours, and then wait for the tank to cool to room temperature.

[0035] In this process, magnesium alloy absorbs hydrogen to form a composite hydrogen storage material mainly composed of MgH2. In this process, the hydrogen absorption curve of Mg-1Al-7Ni-1Ce-0.5Zr hydrogen storage alloy is as follows: Figure 2 As shown;

[0036] S2: Turn on the electric heating and heat to 80-100°C, open the water flow valve (7), and let water flow into the porous air guide tube (3) through the water pump. Open the hydrogen valve (6) and collect the hydrogen produced by hydrolysis. In this process, the hydrolysis hydrogen production curve of Mg-1Al-7Ni-1Ce-0.5Zr hydrogen storage alloy is as follows: Figure 3 As shown;

[0037] S3: After the hydrolysis is completed, the water flow valve (7) and the hydrogen valve (6) are closed.

[0038] Example 2:

[0039] The heating temperature of step S1 in Example 1 is adjusted to 250° C., and other conditions or parameters are consistent with Example 1. Compared with Example 1, the hydrogen absorption time is shortened and the hydrogen production rate is increased.

[0040] If S1 hydrogen absorption is carried out at a relatively low temperature, some magnesium alloys may not be fully hydrogenated, which will affect the subsequent hydrolysis and hydrogen production process. Therefore, during the S1 hydrogen absorption process, the heating temperature is controlled above 100°C, and as the heating temperature increases, the rate of S2 hydrogen production is accelerated.

[0041] Example 3:

[0042] The heating temperature of step S1 in Example 1 is adjusted to 300° C., and other conditions or parameters are consistent with Example 1. Compared with Example 1, the amount of hydrogen absorption increases, and the total amount of hydrogen production is improved.

[0043] It can be seen that appropriately increasing the heating temperature in step S1 is beneficial to the hydrogen absorption time, hydrogen absorption amount, and hydrogen production amount, but too high a heating temperature will cause the magnesium alloy to pulverize, agglomerate, and grow, thereby affecting its hydrogen absorption and subsequent hydrolysis and hydrogen production performance.

[0044] Preparation Example 1

[0045] The preparation process of the magnesium alloy particles (Mg-1Al-7Ni-1Ce-0.5Zr hydrogen storage alloy) in Example 1 is as follows: magnesium metal and magnesium-based master alloys, including Mg-Al master alloy, Mg-Ni master alloy, Mg-Ce master alloy, and Mg-Zr master alloy, are used as raw materials, and the addition amount of each metal is controlled. The magnesium-based hydrogen storage alloy is obtained by high-temperature smelting. First, Mg is heated and melted under a protective atmosphere, and then Mg-Al master alloy, Mg-Ni master alloy, Mg-Ce master alloy, and Mg-La master alloy are added in proportion. After the raw materials are fully stirred and mixed, they are cooled to room temperature at a rate of 50K / min to prepare Mg-1Al-7Ni-1Ce-0.5Zr hydrogen storage alloy, which is crushed and sieved in air and then pressed to obtain magnesium alloy particles.

[0046] Preparation Example 2

[0047] The preparation process for magnesium alloy particles (Mg-0.5Ti-7Ni-2.5Co-0.5Ce hydrogen storage alloy) is as follows: magnesium and magnesium-based master alloys are used as raw materials. The addition amount of various metals is controlled and the magnesium-based hydrogen storage alloy is obtained through high-temperature smelting. First, Mg is heated and melted under a protective atmosphere. Then, Mg-Ti master alloy, Mg-Ni master alloy, Mg-Co master alloy, and Mg-Ce master alloy are added in proportion. After the raw materials are thoroughly stirred and mixed, they are cooled to room temperature at a rate of 50K / min to prepare the Mg-0.5Ti-7Ni-2.5Co-0.5Ce hydrogen storage alloy. The alloy is then crushed and sieved in air and pressed to obtain magnesium alloy particles.

[0048] Preparation Example 3

[0049] The preparation process for magnesium alloy particles (Mg-0.5Ti-7Ni-2Co-0.5Ce-0.5La hydrogen storage alloy) is as follows: magnesium and magnesium-based master alloys are used as raw materials. The amount of each metal added is controlled, and the magnesium-based hydrogen storage alloy is obtained through high-temperature smelting. First, Mg is heated and melted under a protective atmosphere. Then, Mg-Ti master alloy, Mg-Ni master alloy, Mg-Co master alloy, Mg-Ce master alloy, and Mg-La master alloy are added in proportion. After the raw materials are thoroughly stirred and mixed, they are cooled to room temperature at a rate of 50K / min to prepare the Mg-0.5Ti-7Ni-2Co-0.5Ce-0.5La hydrogen storage alloy. The alloy is then crushed and sieved in air, and then pressed to obtain magnesium alloy particles.

[0050] Preparation Example 4

[0051] The preparation process for magnesium alloy particles (Mg-0.5Ti-7Ni-1.5Co-0.5Ce-0.5La-0.5Nd hydrogen storage alloy) is as follows: magnesium and magnesium-based master alloys are used as raw materials. The amount of each metal added is controlled to obtain the magnesium-based hydrogen storage alloy through high-temperature smelting. First, Mg is heated and melted under a protective atmosphere. Then, Mg, Ti, Mg-Ni master alloy, Mg-Co master alloy, Mg-Na master alloy, Mg-Ce master alloy, Mg-La master alloy, and Mg-Nd master alloy are added in proportion. After the raw materials are thoroughly stirred and mixed, they are cooled to room temperature at a rate of 50K / min to prepare the Mg-0.5Ti-7Ni-1.5Co-0.5Ce-0.5La-0.5Nd hydrogen storage alloy. The alloy is then crushed and sieved in air and pressed to obtain magnesium alloy particles.

[0052] In addition, during the preparation process of the above-mentioned hydrogen storage alloy, the Mg-Ce master alloy is selectively adjusted to a Mg-La master alloy, or the Mg-Ce master alloy is adjusted to a Mg-Nd master alloy, or the Mg-La master alloy is adjusted to a Mg-Nd master alloy, or the Mg-Ce master alloy is adjusted to a Mg-Nd master alloy. All the magnesium alloy particles prepared above can realize the simultaneous in-situ hydrogen absorption and hydrolysis hydrogen production of the magnesium alloy in the magnesium-based solid hydrogen storage alloy in-situ hydrogen absorption and hydrolysis hydrogen production device of the present invention. The heating wire is energized so that the heating wire temperature reaches the hydrogen absorption temperature of the magnesium alloy, and then the hydrogen valve is opened to introduce hydrogen through the porous air guide tube, so that the magnesium alloy is saturated with hydrogen. Subsequently, the hydrogen-absorbed magnesium alloy does not need to be taken out of the tank body. When hydrogen is needed, water can be directly injected into the tank body through the water flow valve, so that the magnesium hydride is hydrolyzed to produce hydrogen, which will greatly improve the hydrolysis hydrogen production efficiency of the magnesium alloy. The hydrogen generated by electrolysis of water is directly injected into the hydrogen production tank as a hydrogen source for the magnesium alloy to absorb hydrogen. When hydrogen is needed later, water is directly passed through to hydrolyze the hydrogenated magnesium alloy to produce hydrogen. In this process, no additional hydrogenated magnesium alloy is required, and the magnesium alloy does not need to be taken out and exposed to the air after absorbing hydrogen. The hydrogen absorption and hydrolysis of the magnesium alloy can be completed in the same equipment, which greatly saves manpower and material resources.

[0053] The preferred embodiments of the present invention have been described in detail above. It should be understood that numerous modifications and variations based on the concepts of the present invention are possible without inventive effort by those skilled in the art. Therefore, any technical solution that can be derived by one skilled in the art through logical analysis, reasoning, or limited experimentation based on the concepts of the present invention and the prior art should be within the scope of protection defined by the claims.

Claims

1. A magnesium-based solid hydrogen storage alloy in-situ hydrogen absorption and hydrolysis hydrogen production device, the device comprising a stainless steel tank, an insulating layer provided on the inner side of the stainless steel tank, a water inlet pipe and a hydrogen pipe provided on the top of the stainless steel tank, the water inlet pipe provided with a water flow valve and connected to a porous air guide pipe extending into the interior of the stainless steel tank, the hydrogen pipe provided with a hydrogen valve, an electric heating wire wrapped around the outer side of the porous air guide pipe, and magnesium alloy particles loaded in the stainless steel tank; the magnesium alloy is a magnesium-based hydrogen storage alloy selected from Mg-1Al-7Ni-1Ce-0.5Zr hydrogen storage alloy, Mg-0.5Ti-7Ni-2.5Co-0.5Ce hydrogen storage alloy, Mg-0.5Ti-7Ni-2Co-0.5Ce-0.5La hydrogen storage alloy, and Mg-0.5Ti-7Ni-1.5Co-0.5Ce-0.5La-0.5Nd hydrogen storage alloy.

2. The device according to claim 1, wherein The porous air guide tube is filled with porous material.

3. The device according to claim 1, wherein The water inlet pipe is provided with a water pump for controlling the flow rate of water and thus the flow rate of hydrogen.

4. The device according to claim 1, wherein The magnesium-based hydrogen storage alloy is prepared by the following method: heating and melting Mg under a protective atmosphere, then sequentially adding one or more of Mg-Ti master alloy, Mg-Al master alloy, Mg-Ni master alloy, Mg-Co master alloy, Mg-Zr master alloy, Mg-Na master alloy, Mg-Ce master alloy, Mg-La master alloy, Mg-Nd master alloy, and Mg-Y master alloy, wherein the content of the master alloy is 0.01% to 30% by weight; after fully stirring and mixing the raw materials, cooling to room temperature at a rate of 50K / min to prepare the magnesium-based hydrogen storage alloy, crushing and sieving in air, and then pressing to obtain magnesium alloy particles.

5. A method for in-situ hydrogen absorption and hydrolysis production of magnesium-based solid hydrogen storage alloy, the method comprising: S0: adding magnesium alloy particles into a stainless steel tank body, wherein the magnesium alloy particles are magnesium-based hydrogen storage alloys selected from Mg-1Al-7Ni-1Ce-0.5Zr hydrogen storage alloy, Mg-0.5Ti-7Ni-2.5Co-0.5Ce hydrogen storage alloy, Mg-0.5Ti-7Ni-2Co-0.5Ce-0.5La hydrogen storage alloy, and Mg-0.5Ti-7Ni-1.5Co-0.5Ce-0.5La-0.5Nd hydrogen storage alloy; S1: Close the hydrogen valve and water flow valve, turn on the electric heating, heat the tank to 100-400℃, open the hydrogen valve, fill it with 3MPa hydrogen, close the hydrogen valve, maintain it at the set temperature for 2-3h, and then wait for the tank to cool to room temperature. During this process, the magnesium alloy absorbs hydrogen to form a composite hydrogen storage material mainly composed of MgH2; S2: Turn on the electric heater and heat to 80-100°C, open the water flow valve, and let water flow into the porous gas guide tube through the water pump, open the hydrogen valve, and collect the hydrogen produced by hydrolysis; S3: After the hydrolysis is completed, close the water flow valve and hydrogen valve.

6. The method according to claim 5, wherein: In S1, the tank is heated to 200-300°C.

7. The method according to claim 5, wherein: In S1, the tank is heated to 200°C, 250°C or 300°C.

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