A Two-Step Hydrogen Refueling Method and Its Application

Abstract

The present invention discloses a two-step hydrogen filling method and its application. A two-step hydrogen filling method, after solidifying hydrogen energy, is filled with hydride as an energy carrier, specifically comprising the following steps: hydrogen storage alloy material absorbs hydrogen in a hydride factory to form a safe, high-capacity hydride; then, the hydride is filled into a hydrogen energy device or hydrogen energy carrier through a hydrogen energy delivery system, and the dehydrogenated product is recovered and regenerated in a hydride factory. The present invention transforms the traditional hydrogen filling method of "hydrogen filling" into a solid-state hydrogen filling method of "hydrogen absorption → hydride filling → material recovery", thereby improving the safety and filling rate of the on-board hydrogen storage system and reducing the system cost.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen energy utilization, and in particular to a two-step hydrogen energy filling method and application thereof. Background Art

[0002] Under the global trend of green and low-carbon transformation, hydrogen, as a clean, efficient and renewable energy, has become the direction of change in a new round of energy technology. Countries and regions around the world are accelerating the layout of the entire industrial chain around hydrogen energy.

[0003] The storage and transportation of hydrogen is a bottleneck problem in the "production, storage, transportation and use" hydrogen energy industry chain. The technologies for hydrogen storage and transportation are mainly divided into the following three categories: gaseous storage and transportation, liquid storage and transportation, and solid storage and transportation. Among the various storage, transportation and filling technologies, high-pressure storage and transportation technologies are currently mainly used internationally and domestically. Although high-pressure hydrogen storage has the advantages of simple equipment structure, low energy consumption for preparation, and rapid charging and discharging, due to the low density of hydrogen, the high-pressure hydrogen storage density is low, the equipment is bulky, and the storage and transportation efficiency is low. Because the pressure is very high, there are safety risks such as easy leakage and explosion during storage and transportation. Compared with other hydrogen storage methods, solid-state hydrogen storage has good safety (hydrogen absorption / discharge platform <1MPa), high volume hydrogen storage density (>100kg / m 3 ) and good convenience (can absorb / release hydrogen at room temperature), and is suitable for fuel cell bicycles, forklifts, ships, portable backup power supplies, base stations and distributed energy supply.

[0004] Hydrogen refueling systems are fundamental to hydrogen energy applications, and the lack of suitable refueling methods is a major factor hindering the industrial application of solid-state hydrogen storage. Traditionally, hydrogen storage systems are refueled using "hydrogen gas refueling." This method has the disadvantages of poor safety, slow refueling, and high cost.

[0005] The above-mentioned hydrogen filling method requires applying a relatively high hydrogen pressure (about 5MPa) to enable the hydrogen storage alloy material to absorb hydrogen quickly and fully. However, due to the high hydrogen pressure during the hydrogen filling process, the hydrogen storage alloy material absorbs hydrogen, which is accompanied by heat release and volume expansion, and there is a high safety risk in the filling process. The hydrogen absorption reaction of the hydrogen storage alloy material requires a certain reaction time, and the accompanying heat release will cause the internal temperature to rise, the hydrogen absorption platform to rise, and the hydrogen filling rate to decrease. Finally, in order to resist the high pressure and volume expansion of the hydrogen absorption reaction, special high-pressure resistant hydrogen storage containers, valves and pipelines are required, which makes the cost of the hydrogen storage system high.

[0006] Hydrogen refueling in high-pressure gaseous, cryogenic liquid, or organic liquid hydrogen storage systems is performed in the corresponding physical state (gas, liquid, or organic solution). However, hydrogen refueling in solid-state hydrogen storage systems is performed as hydrogen gas, through a gas-solid reaction within the hydrogen storage container. Therefore, the problem of hydrogen refueling in solid-state hydrogen storage systems arises from the inconsistency between the hydrogen energy forms used for refueling and storage.

[0007] Therefore, in response to the above technical problems, how to achieve the unification of hydrogenation and hydrogen storage forms based on solid-state hydrogen storage technology and build a safe, efficient and low-cost solid-state hydrogen filling system is a technical problem that technical personnel in this field need to solve. Summary of the Invention

[0008] The present invention provides a two-step hydrogen filling method and its application. The present invention splits the hydrogen filling method of "hydrogen gas filling" and transforms it into a two-step solid-state hydrogen filling method of "hydrogen solidification → hydride filling", thereby improving the safety and filling rate of the on-board hydrogen storage system and reducing the system cost.

[0009] The purpose of the present invention is to propose a two-step hydrogen filling method, in which hydrogen energy is solidified and then filled with hydride as an energy carrier, specifically comprising the following steps: hydrogen storage alloy material absorbs hydrogen in a hydride plant to form safe, high-capacity hydride; then, the hydride is filled into a hydrogen energy device or a hydrogen energy carrier through a hydrogen energy delivery system, and the dehydrogenation product is recovered to the hydride plant for regeneration; the hydride plant includes a hydrogen absorption device for adding hydrogen storage alloy material and hydrogen to prepare hydride and a hydrogen storage device for storing hydride on a large scale; the hydrogen energy delivery system includes a transportation device equipped with a transfer tank for storing hydride / dehydrogenation material and a filling device for transporting hydride / dehydrogenation product between the hydride plant and each hydrogenation station, and the filling device is located in the hydrogenation station to fill the hydrogen energy device or hydrogen energy carrier with hydride and recover the dehydrogenation product.

[0010] The present invention proposes a two-step hydrogen filling method, which is characterized by dividing hydrogen filling into two steps: "hydrogen solidification → hydride filling", and specifically includes the following steps:

[0011] Hydrogen energy solidification: Hydrogen storage alloy materials absorb hydrogen in the hydride plant, solidifying the hydrogen energy to form safe and efficient hydride;

[0012] Hydride filling: Through the hydrogen energy transportation system, hydride is transported to the filling device of each hydrogenation station, and hydride is filled into various hydrogen energy devices or hydrogen energy carriers to realize solid-state filling of hydrogen energy, and hydrogen desorption products are collected.

[0013] Preferably, the hydrogen energy devices are small hydrogen fuel cell appliances such as hydrogen power banks, fans, and electric bicycles. The hydrogen energy vehicles are medium and large hydrogen fuel cell vehicles such as hydrogen buses, hydrogen trucks, and ships.

[0014] Preferably, the hydrogen storage alloy material is a TiMn2-based hydrogen storage alloy.

[0015] More preferably, the TiMn2-based hydrogen storage alloy is Ti 1-x Zrx Mn 1.98-y (V-Fe) y The alloys, wherein x=0-0.20 and y=0-0.6, have high hydrogen storage capacity (1.6-2.0 wt%), suitable hydrogen absorption / desorption platform, low hydrogen absorption / desorption platform hysteresis and good cycle stability.

[0016] The present invention also protects the application of the method in a distributed / on-route solid-state hydrogen energy filling method.

[0017] Preferably, the distributed solid-state hydrogen filling method comprises the following steps:

[0018] S1. The hydrogen storage alloy material undergoes a hydrogen absorption reaction in a hydride plant to solidify the hydrogen energy and form a safe and efficient hydride. Specifically, the hydrogen storage alloy material and high-pressure hydrogen are reacted in a hydrogen absorption device to prepare a hydride, and the obtained hydride is then stored in a hydrogen storage device on a large scale.

[0019] S2. The hydride is transported to the filling device through the hydrogen energy transportation system, and the hydride is injected into each filling device. The filling device injects hydride into the hydrogen energy device and collects the hydrogen desorption product.

[0020] Preferably, the solid hydrogen energy filling method along the way comprises the following steps:

[0021] S1. The hydrogen storage alloy material undergoes a hydrogen absorption reaction in a hydride plant to solidify the hydrogen energy and form a safe and efficient hydride. Specifically, the hydrogen storage alloy material and high-pressure hydrogen are reacted in a hydrogen absorption device to prepare a hydride, and the obtained hydride is then stored in a hydrogen storage device on a large scale.

[0022] S2. The hydride is transported to a hydrogen refueling station with a fixed-route hydrogen vehicle through a hydrogen transport system. The refueling device injects hydride into the hydrogen vehicle and collects the dehydrogenated product.

[0023] Compared with the prior art, the present invention has the following advantages: high safety, low cost, strong flexibility and fast filling:

[0024] 1) High Safety: Conducting the hydrogen absorption reaction within a hydride plant facilitates centralized control of risks associated with high-pressure hydrogen, heat release, and volume expansion. Outside the hydride plant, hydrogen energy exists as hydride, allowing for safe and efficient circulation and distribution, making it suitable for use in densely populated urban areas.

[0025] 2) Fast filling: The filling of hydride is a physical process. No hydrogen or heat exchange is required during the filling process. The filling rate of hydrogen energy is equal to the filling rate of hydride, which can achieve fast filling.

[0026] 3) Low cost: Since there will be no safety issues such as high-pressure hydrogen or expansion during the circulation process, only ordinary tanks are needed to seal and store hydrides, which can greatly reduce the system material requirements and costs.

[0027] 4) Strong flexibility: With the characteristics of asynchronous processing, the time-consuming hydrogen absorption reaction can be carried out in the hydrogen absorption device, while the filling device is charging the hydrogen vehicle / ship at the same time, without affecting each other. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Ti in Example 1 and Example 2 0.95 Zr 0.05 Mn 1.46 (V-Fe) 0.52 PCT curve of alloy material;

[0029] Figure 2 This is a schematic diagram of the layout of the two-step hydrogen filling method proposed in the present invention;

[0030] Figure 3 This is a schematic diagram of the layout of the distributed solid-state hydrogen energy filling method according to Example 1 of the present invention;

[0031] Figure 4 This is a schematic diagram of the layout of the solid-state hydrogen energy refueling method along the way according to Example 2 of the present invention. DETAILED DESCRIPTION

[0032] The present invention will be described in further detail below with reference to the examples. These examples are intended to illustrate the present invention only and are not intended to limit the scope of the present invention. The experimental methods in the following examples, for which specific conditions are not specified, are generally based on conventional conditions in the art or the conditions recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are deemed to be raw materials and reagents that can be obtained through commercial channels such as conventional markets. Any non-substantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of protection claimed in the present invention.

[0033] Example 1: Distributed solid-state hydrogen filling method

[0034] The schematic diagram of the distributed solid hydrogen filling method is as follows: Figure 3 As shown, it is used to charge hydrogen bicycles at random routes. The system consists of a hydride plant and a hydrogen transport system. The hydride plant has two hydrogen absorption devices and one hydrogen storage device, while the hydrogen transport system includes a hydride transport vehicle and four filling devices. 0.95 Zr 0.05 Mn 1.46 (V-Fe) 0.52 alloy) as a hydrogen storage material, with a hydrogen storage density of approximately 1.8wt%.

[0035] The hydrogen absorption device of the hydride plant can be loaded with 100kg of hydrogen storage alloy material, and hydrogen with a pressure of 5MPa is introduced. The amount of hydrogen solidified each time is 1.8kg H2; while the hydrogen storage device can hold 1000kg of hydrogen storage alloy and has a hydrogen storage capacity of 18kg H2. The hydride in the hydrogen storage device is transported to the hydrogen refueling station by a hydride transport vehicle. The filling device has a capacity of 100kg of hydrogen storage alloy and a hydrogen storage capacity of 1.8kg H2. Usually, 30g of H2 can provide 8 hours of battery life for a hydrogen bicycle (300W), so each hydrogen refueling station can provide charging services for 60 hydrogen bicycles.

[0036] The steps of the hydrogen bicycle step-by-step refueling method are as follows:

[0037] 1. 1000 kg of TiMn2-based hydrogen storage alloy absorbs hydrogen in batches in a hydride plant to form hydride (hydrogen storage capacity 7.2 kg H2) that can be safely and efficiently transported and stored;

[0038] 2. The hydride transporter transports the hydride to the hydrogenation station and injects 100kg of hydride (hydrogen storage capacity 7.2kg H2) into each hydrogenation unit. The hydrogenation unit injects 1.7kg of hydride (hydrogen storage capacity 30g H2) into the hydrogen bike and collects the dehydrogenated products;

[0039] In addition, hydrogen-powered household appliances such as hydrogen power banks and hydrogen-powered fans can also be charged safely and quickly using similar methods.

[0040] Example 2: Solid-state hydrogen refueling method along the way

[0041] The schematic diagram of the solid hydrogen filling method along the way is as follows Figure 4 As shown, it is used to charge hydrogen ships with fixed routes. It consists of a hydride plant and a hydrogen transportation system. The hydride plant has two hydrogen absorption devices and one hydrogen storage device, while the hydrogen transportation system includes a hydride transport vehicle and four filling devices. It uses TiMn2-based alloy (Ti 0.95 Zr 0.05 Mn 1.46 (V-Fe) 0.52 alloy material) as a hydrogen storage material, with a hydrogen storage density of approximately 1.8 wt%.

[0042] The hydrogen absorption device of the hydride plant can be loaded with 500kg of hydrogen storage alloy material, and hydrogen with a pressure of 5MPa is introduced. The amount of hydrogen solidified each time is 9.0kg H2; while the hydrogen storage device can hold 4000kg of hydrogen storage alloy and has a hydrogen storage capacity of 72kg H2. The hydride in the hydrogen storage device is transported to the hydrogen refueling stations distributed along the river by hydride transport vehicles. The filling device has a capacity of 2000kg of hydrogen storage alloy and a hydrogen storage capacity of 36kg H2. Usually, 36kg H2 can provide 8 hours of endurance for a hydrogen-powered small yacht (36kW), so each hydrogen refueling station can provide charging services for two hydrogen-powered small yachts.

[0043] The operating steps of the hydrogen ship step-by-step filling system are as follows:

[0044] 1. To improve hydrogen absorption efficiency, 4000 kg of LaNi5-based hydrogen storage alloy was divided into two batches and absorbed hydrogen separately in the hydrogen absorption device of the hydride plant to form hydride (hydrogen storage capacity 30 kg H2) that can be safely and efficiently transported;

[0045] 2. The hydride truck transports 4,000 kg of hydride to the hydrogenation unit in the hydrogenation station (with a hydrogen storage capacity of 30 kg H2). Each time, the hydrogenation unit injects 2,000 kg of hydride into the hydrogen-powered ship and collects the dehydrogenated products;

[0046] 3. After charging the two sub-hydrogen ships, the hydride in the hydrogenation unit is depleted. The hydride truck refills the hydrogenation station with hydride and recovers the dehydrogenated product, which is then sent to the hydride plant for re-absorption.

[0047] In addition, hydrogen buses and hydrogen trucks with fixed routes can also be charged safely and quickly in a similar way.

[0048] The above are merely preferred embodiments of the present invention. It should be noted that the above preferred embodiments should not be construed as limiting the present invention, and the scope of protection of the present invention should be determined by the scope defined in the claims. Persons skilled in the art will appreciate that improvements and modifications may be made without departing from the spirit and scope of the present invention, and such improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A two-step hydrogen filling method, characterized in that: After hydrogen energy is solidified, it is filled with hydride as an energy carrier, which specifically includes the following steps: hydrogen storage alloy material absorbs hydrogen in the hydride factory to form safe and high-capacity hydride, the hydrogen storage alloy material is TiMn2-based hydrogen storage alloy, the TiMn2-based hydrogen storage alloy is Ti 1-x Zr x Mn 1.98-y (V-Fe) y alloy, wherein x=0~0.20, y=0~0.6; then, the hydride is added to the hydrogen energy device or hydrogen energy vehicle through the hydrogen energy delivery system, and the dehydrogenation product is recovered to the hydride plant for regeneration; the hydride plant includes a hydrogen absorption device for adding hydrogen storage alloy material and hydrogen to prepare hydride and a hydrogen storage device for storing the hydride on a large scale; the hydrogen energy delivery system includes a transportation device provided with a transfer tank for storing hydride / dehydrogenation material and a filling device for transporting hydride / dehydrogenation product between the hydride plant and each hydrogenation station, and the filling device is located in the hydrogenation station to fill the hydrogen energy device or hydrogen energy vehicle with hydride and recover the dehydrogenation product.

2. The method according to claim 1, characterized in that The hydrogen energy devices are small hydrogen fuel cell appliances, including hydrogen energy power banks, fans and electric bicycles.

3. The method according to claim 1, characterized in that The hydrogen vehicles are medium and large hydrogen fuel cell vehicles, including hydrogen buses, hydrogen trucks and ships.

4. Application of the method according to claim 1 in a distributed / on-the-go solid-state hydrogen energy refueling method.

5. The use according to claim 4, characterized in that The distributed solid-state hydrogen energy filling method comprises the following steps: S1. In a hydride plant, hydrogen storage alloy materials absorb hydrogen in a hydrogen absorption device to form hydrides, which are then transported to a hydrogen storage device for large-scale storage. S2. The hydride is transported to each hydrogenation station through the hydrogen energy delivery system, the hydride is injected into the hydrogen energy device, and the hydrogen desorption product is collected.

6. The use according to claim 4, characterized in that The method for filling solid hydrogen along the way comprises the following steps: S1. In a hydride plant, hydrogen storage alloy materials absorb hydrogen in a hydrogen absorption device to form hydrides, which are then transported to a hydrogen storage device for large-scale storage. S2. The hydride is transported to a hydrogenation station with a fixed-route hydrogen vehicle through a hydrogen transport system, the hydride is injected into the hydrogen vehicle, and the dehydrogenated product is collected.

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