Apparatus and method for in situ regeneration of metal hydride hydrolysis hydrogenation and hydrolysis products

Abstract

The present application relates to a kind of metal hydride hydrolysis hydrogen and hydrolysis product in-situ regeneration device and method, belong to hydrogen energy storage and release technical field.The device includes dynamic hydrogen nanobubble generation unit, reaction chamber, two-way flowable filter device, liquid storage tank connected in sequence;The top of the reaction chamber is provided with hydrogen inlet and outlet, solid inlet and outlet and pressure relief port, and the bottom is provided with liquid inlet and outlet;The dynamic hydrogen nanobubble generation unit is connected with the hydrogen inlet and outlet of reaction chamber by gas path;The dynamic hydrogen nanobubble generation unit includes gas compression circulation system and parameter monitoring feedback unit.The present application is integrated by hydrolysis hydrogen-hydride regeneration process unit, and utilizes dynamic hydrogen nanobubble method, for the first time in aqueous system realizes the efficient, low-temperature in-situ regeneration of metal hydride hydrolysis product (metal hydroxide), forms complete reversible hydrogen storage and release cycle.The method has the advantages of low energy consumption, good cycle stability, high device integration.

Description

Technical Field

[0001] This invention relates to the field of hydrogen energy storage and release technology, and in particular to an apparatus and method for in-situ regeneration of hydrogen from metal hydride hydrolysis and hydrolysis products. Background Technology

[0002] As a clean energy carrier, the controllable release and efficient regeneration of hydrogen are key to its large-scale application. Traditional metal hydrides mostly rely on high-temperature dehydrogenation (such as LiH, which requires 900°C to release hydrogen) or high-pressure regeneration (such as LiH, which requires 34MPa pressure for regeneration), which have problems such as high energy consumption, complex equipment, and poor cycle reversibility.

[0003] While existing technologies have explored the use of hydrolysis to release hydrogen, the regeneration of the hydrolysis product, hydroxide, is extremely difficult, making it impossible to form a closed-loop cycle. In recent years, numerous methods related to hydrogen storage and release using chemical hydrogen storage materials have been reported, but finding a method to enable these materials to continuously and stably release stored hydrogen and re-store it remains a top priority in this field.

[0004] Therefore, developing a device and method to achieve controlled hydrolysis of metal hydrides under mild conditions and to efficiently and in-situ regenerate the hydrolysis products into hydrides is of vital importance to promoting the development of solid-state hydrogen storage technology. Summary of the Invention

[0005] This invention aims to overcome the shortcomings of existing technologies where the products of hydrogenation from the hydrolysis of metal hydrides cannot be efficiently regenerated and reversible recycling is difficult to achieve. It provides an apparatus and method for in-situ regeneration of hydrogenation products from the hydrolysis of metal hydrides. By introducing dynamic hydrogen nanobubble generation technology, this invention achieves all functions of "hydrolysis hydrogenation" and "hydrogenation regeneration" within the same reaction unit, realizing for the first time efficient, low-temperature, and reversible recycling of metal hydrides in an aqueous system.

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

[0007] In a first aspect, the present invention provides an apparatus for in-situ regeneration of hydrogen from the hydrolysis of metal hydrides and the hydrolysis products. The apparatus includes a dynamic hydrogen nanobubble generating unit, a reaction chamber, a bidirectional flowable filter, and a storage tank connected in sequence. The top of the reaction chamber is provided with a hydrogen inlet / outlet, a solid inlet / outlet, and a pressure relief port, and the bottom is provided with a liquid inlet / outlet. The dynamic hydrogen nanobubble generating unit is connected to the hydrogen inlet / outlet of the reaction chamber via a gas path. The dynamic hydrogen nanobubble generating unit includes a gas compression circulation system and a parameter monitoring and feedback unit, the parameter monitoring and feedback unit being built into the reaction chamber. The reaction chamber and the bidirectional flowable filter are connected via a filter regulating valve. The storage tank is equipped with a bidirectional reciprocating pump, and the bottom of the storage tank is provided with a liquid inlet / outlet.

[0008] The core of the device for in-situ regeneration of hydrogen from metal hydride hydrolysis and its hydrolysis products provided by this invention is a reaction chamber integrating hydrogen release and regeneration functions. This reaction chamber, through an internal or external piping system, filtration unit, compressed gas circulation system, and storage tank, achieves directional material transfer, solid-liquid reaction and separation, and in-situ generation of hydrogen bubbles. The functions and connection sequence of each component are as follows:

[0009] (1) Reaction chamber: The main place for hydrolysis and hydrogenation regeneration reactions. It is equipped with solid inlet and outlet, liquid inlet and outlet, hydrogen inlet and outlet, and pressure relief port.

[0010] (2) Bidirectional flowable filter device and bidirectional reciprocating pump: connected to the reaction chamber through pipeline and filter regulating valve, used to perform solid-liquid separation of reaction slurry after hydrogen release step, and to return liquid containing hydrogen nanobubbles before regeneration step.

[0011] (3) Dynamic hydrogen nanobubble generating unit: This unit is connected to the reaction chamber and is used to periodically inject and extract hydrogen gas into the reaction chamber, thereby generating high-density, dynamically changing hydrogen nanobubbles in the liquid phase. This unit includes a gas compression circulation system and a parameter monitoring and feedback unit. The parameter monitoring and feedback unit is used to monitor parameters such as pressure, temperature, and hydrogen concentration in the reaction chamber in real time, and to provide feedback control to the gas compression circulation system to adjust the hydrogen inlet and outlet frequency, pressure amplitude, and bubble concentration.

[0012] (4) Storage tank: used to pump the aqueous solution before and after the hydrogen release reaction out of the storage tank (during hydrogen release) or into the storage tank (after regeneration).

[0013] The working principle and innovation of this device lie in its integration of the traditionally separate "hydrogen release" and "regeneration" process units into a single, switchable reaction chamber. In "hydrogen release mode," the reaction chamber acts as a hydrolysis reactor, where metal hydrides react with water to release hydrogen gas. After the reaction, in "regeneration mode," the reaction chamber switches to a hydrogenation reactor. A dynamic hydrogen nanobubble generation unit introduces hydrogen gas into the metal hydroxide slurry within the chamber, and through periodic pressure changes, disperses the hydrogen gas in the form of nanobubbles. These nanobubbles generate localized high temperatures and pressures, as well as a large number of highly reactive hydrogen atoms (·H), during their growth and collapse. This significantly promotes the reaction kinetics of the re-hydrogenation of metal hydroxides into metal hydrides under mild aqueous conditions, achieving closed-loop regeneration. A parameter monitoring and feedback unit ensures the controllability and optimization of the bubble generation process.

[0014] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The technical objectives and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0015] In some embodiments, the solid inlet and outlet of the reaction chamber are connected to external storage bins for adding hydride powder to the hydrogen release reaction chamber in batches or all at once before hydrogen release, or for discharging hydrolysis products from the hydrogen release reaction chamber after hydrogen release.

[0016] In some embodiments, the filter regulating valve is a V-type ball valve, used to pump the aqueous solution from the storage tank into the reaction chamber before the hydrogen release reaction or to pump the aqueous solution from the reaction chamber into the storage tank after the regeneration reaction.

[0017] In some embodiments, the gas compression circulation system includes a gas path connected to the hydrogen inlet and outlet of the reaction chamber, a pressure pump disposed on the gas path, and a pressure relief valve.

[0018] The pressure pump and pressure relief valve are controlled by the parameter monitoring and feedback unit to perform periodic pressurization and pressure relief operations.

[0019] In some embodiments, the hydrogen outlet of the reaction chamber is externally connected to a hydrogen purification device and / or a proton exchange membrane fuel cell module.

[0020] Secondly, the present invention provides a method for in-situ regeneration of hydrogen from hydrolysis of metal hydrides and hydrolysis products, wherein the method is performed using the apparatus for in-situ regeneration of hydrogen from hydrolysis of metal hydrides and hydrolysis products described in the first aspect.

[0021] In some embodiments, the method for in-situ regeneration of hydrogen from metal hydride hydrolysis and hydrolysis products includes the following steps:

[0022] (1) Feeding and water injection: The metal hydride powder is added to the reaction chamber through the solid inlet and outlet; the water in the storage tank is injected through the liquid inlet and outlet, and enters the reaction chamber through the bidirectional flowable filter under the action of the pump to mix with the metal hydride.

[0023] (2) Hydrolysis of hydrogen: Metal hydrides react with water to hydrolyze hydrogen, producing hydrogen gas and metal hydroxide slurry. The hydrogen gas is discharged through the hydrogen outlet.

[0024] (3) Solid-liquid separation: After the hydrogen release reaction is completed, the slurry is separated into solid and liquid by a two-way flowable filter device. The metal hydroxide solid is retained, and the filtrate is transferred to the storage tank or directly enters the next stage.

[0025] (4) In-situ regeneration: Liquid containing dynamic hydrogen nanobubbles is circulated into the metal hydroxide solid in the reaction chamber n times. The reaction is carried out under the action of dynamic hydrogen nanobubbles to obtain regenerated metal hydride, where n is a positive integer ≥1.

[0026] (5) Reversible cycle: Using the regenerated metal hydride as raw material, repeat steps (1) to (4) N times to realize the in-situ regeneration cycle of metal hydride hydrolysis hydrogenation and hydrolysis products, where N is a positive integer ≥1.

[0027] In some embodiments, in step (1), the flow rate of water entering the reaction chamber is controlled by a filter regulating valve.

[0028] In some embodiments, the temperature of the hydrolysis hydrogen reaction in step (2) is 20℃-90℃, for example, it can be 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃ or 90℃, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0029] This invention further controls the temperature of the hydrolysis hydrogen reaction to be between 20°C and 90°C. The temperature of the hydrolysis hydrogen reaction affects the hydrogen release rate; if the temperature of the hydrolysis hydrogen reaction is too high, an "explosive" hydrogen release may occur; if the temperature of the hydrolysis hydrogen reaction is too low, the hydrogen release is slow.

[0030] In some embodiments, the metal hydride includes any one or a combination of at least two of LiH, NaH, KH, CaH2, or MgH2. Typical but non-limiting combinations include combinations of LiH and NaH, NaH and KH, CaH2 and MgH2, KH and CaH2, LiH and CaH2, LiH and KH, or LiH, NaH, and KH.

[0031] In some embodiments, step (4) dynamic hydrogen nanobubbles are generated by a gas pressure circulation system; the gas pressure circulation system continuously regulates the pressure of hydrogen gas at a frequency of 0.5 min / time to 5 min / time, for example, it can be 0.5 min / time, 1 min / time, 2 min / time, 3 min / time, 4 min / time or 5 min / time, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0032] This invention further controls the hydrogen pressure regulation frequency to 0.5 min / time - 5 min / time. The hydrogen pressure regulation frequency affects the uniform distribution and high density of bubbles. If the hydrogen pressure regulation frequency is too high, the energy consumption and hydrogen consumption will be too high. If the hydrogen pressure regulation frequency is too low, the degree of hydrogenation will be insufficient.

[0033] In some embodiments, the initial pressure of the hydrogen is 8 atm-20 atm, for example, it can be 8 atm, 10 atm, 14 atm, 16 atm, 18 atm or 20 atm, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0034] In some embodiments, the temperature of the regeneration reaction in step (4) is 20°C-60°C, for example, it can be 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0035] The method for in-situ regeneration of metal hydrides through hydrolysis and the resulting hydrogen release and regeneration products provided by this invention enables efficient and reversible "hydrogen release-regeneration" cycling of metal hydrides. Furthermore, the regenerated hydride crystals have the same structure as the initial metal hydride, exhibiting a low hydrogen storage capacity decay rate; for example, LiH retains over 90% of its capacity after 15 cycles.

[0036] In some embodiments, the purity of the hydrogen is 98%-99.9%, for example, it can be 98%, 98.5%, 99%, 99.5% or 99.9%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0037] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0038] Compared with the prior art, the present invention has at least the following beneficial effects:

[0039] (1) This invention solves the problems of reliability of hydrogen release from hydrolysis and inability to regenerate and recycle in situ after hydrolysis in existing metal hydrogen storage materials. The device for hydrogen release from hydrolysis of metal hydrides and in situ regeneration of hydrolysis products provided by this invention utilizes a dynamic hydrogen nanobubble control method. At the same time, the device integrates two key process units: hydrogen release (hydrothermal hydrolysis hydrogen production) and hydrogen storage (hydride regeneration), realizing low-temperature, high-efficiency and reversible operation of the entire process.

[0040] (2) Process integration and closed-loop circulation: The dynamic hydrogen nanobubble control is deeply integrated into the whole chain of "hydrogen release-regeneration", and efficient reversible circulation of metal hydrides is realized for the first time in an aqueous system.

[0041] (3) Low temperature, high efficiency and energy saving: The dynamic hydrogen nanobubble method significantly improves the yield of active hydrogen atoms, enabling hydride synthesis and regeneration to be carried out efficiently at low temperature (≤100℃), and reducing overall energy consumption by more than 50%.

[0042] (4) Excellent cycle stability: The regenerated hydride crystal structure is consistent and the hydrogen storage capacity decay rate is low. For example, the capacity retention rate of LiH exceeds 90% after 15 cycles. Attached Figure Description

[0043] Figure 1 This is a schematic diagram of the apparatus for in-situ regeneration of hydrogen from metal hydride hydrolysis and hydrolysis products provided in Embodiment 1 of the present invention, wherein: 1. Reaction chamber; 2. Bidirectional flow-through filter device; 3. Storage tank; 4. Container support; 5. Hydrogen inlet and outlet; 6. Solid inlet and outlet; 7. Pressure relief port; 8. Liquid inlet and outlet; 9. Bidirectional reciprocating pump; 10. Filter regulating valve;

[0044] Figure 2 The XRD pattern of the metal hydroxide solid is obtained by step (2) of the method for in-situ regeneration of hydrogen from hydrolysis and hydrolysis products of metal hydride provided in Example 1 of this invention.

[0045] Figure 3 Thermogravimetric analysis curve of the metal hydride obtained after five cycles of the in-situ regeneration method of hydrogenation and hydrolysis products of metal hydride hydrolysis provided in Embodiment 1 of the present invention;

[0046] Figure 4 The XRD pattern of the metal hydride obtained after six cycles of the in-situ regeneration of hydrogen from hydrolysis and hydrolysis products provided in Embodiment 1 of the present invention, after each cycle of step (2). Detailed Implementation

[0047] 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.

[0048] The scope of this invention can be defined by lower and upper limits. The selected lower and upper limits define the boundaries of a specific range. The range defined in this way can be defined by the inclusion or exclusion of endpoints. Any endpoint can be independently selected for inclusion or exclusion, and all lower and upper limits can be arbitrarily combined to form new ranges. That is, any lower limit can be combined with any upper limit to form an effective range. For example, if the ranges of 60~120 and 80~110 are listed for specific parameters, it should be understood that the ranges of 60~110 and 80~120 also fall within the scope of this invention. In addition, if the minimum range values ​​1 and 2 are listed, and the maximum range values ​​3, 4 and 5 are also listed, then all ranges of 1~3, 1~4, 1~5, 2~3, 2~4 and 2~5 fall within the scope of this invention. In this invention, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0~5" means that all real numbers between 0 and 5 have been fully listed in this document, and "0~5" is only a shortened representation of this set of numerical combinations. When a parameter is expressed as an integer ≥2, it is equivalent to listing positive integers that meet the requirements, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, etc. When a parameter is expressed as an integer selected from "2~10", it is equivalent to listing any integer among 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0049] In this invention, "a combination of at least two" refers to a quantity greater than or equal to 2 unless otherwise specified. For example, "any one or a combination of at least two" means that any one of the listed items can be selected, or a combination of at least two of the listed items formed in a manner that does not conflict and enables the implementation of this invention. In this invention, unless otherwise specified, the features or solutions corresponding to "and / or" cover any one of two or more related listed items, as well as any and all combinations of the related listed items. The arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" means a set consisting of A, B, and combinations of A and B, where "containing A and / or B" can be understood, depending on the context of the statement, as containing A, containing B, or simultaneously containing both A and B. In this invention, "optional" means that the corresponding feature, component, step or solution is not necessary, that is, it is selected from either "with" or "without". If there are multiple "optional" limitations in a technical solution, unless otherwise specified and there is no technical conflict or mutual constraint, each "optional" limitation is independent and does not affect the others.

[0050] In this invention, technical features or solutions described using open-ended terms such as "comprising" or "including" do not exclude additional non-conflicting elements beyond the listed elements unless otherwise specified. They are considered to disclose both closed-ended features or solutions consisting solely of the listed elements and open-ended features or solutions that may include additional non-conflicting elements beyond the listed elements. For example, if A includes a1, a2, and a3, unless otherwise specified, this means that A can consist only of a1, a2, and a3, or it can include other non-conflicting elements based on a1, a2, and a3. This corresponds to the disclosure of technical solutions such as "A consists of a1, a2, and a3," "A is selected from a1, a2, and a3," and "A not only includes a1, a2, and a3, but may also include other non-conflicting elements." All embodiments and optional embodiments of this invention, unless otherwise specified and without technical conflict, can be combined to form new technical solutions, and such combinations fall within the scope of this invention. The term "embodiment" as used in this invention means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of the invention. The appearance of this phrase in various locations throughout the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments. Those skilled in the art will understand, explicitly and implicitly, that the embodiments described in this invention can be combined with other embodiments that do not conflict with the technology. The ordinal numbers "first," "second," "third," and "fourth," etc., used in the expressions "first aspect," "second aspect," "third aspect," and "fourth aspect" in this invention are for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly specifying the importance or quantity of the indicated technical features. They serve only as a non-exhaustive enumeration and do not constitute a closed limitation on quantity.

[0051] In this invention, the order in which the steps are written in the methods described in each embodiment does not imply a strict execution order. The actual execution order of each step should be determined based on its function and possible internal logic. Unless otherwise specified, all steps of this invention can be executed in the order they are written, or in any order without technical conflict. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) executed sequentially, or it may include steps (b) and (a) executed sequentially. If the method also includes step (c), then step (c) can be added to the method in any order without conflict, including but not limited to the execution order of steps (a), (b), and (c), steps (a), (c), and (b), steps (c), (a), and (b), etc.

[0052] Unless otherwise specified, all reagents and consumables used in the following examples and comparative examples were purchased from conventional reagent manufacturers in the art; unless otherwise specified, the experimental methods and techniques used were conventional methods and techniques in the art.

[0053] Example 1

[0054] This embodiment provides a device for in-situ regeneration of hydrogen from metal hydride hydrolysis and hydrolysis products, as shown in the schematic diagram below. Figure 1 As shown: The device includes a dynamic hydrogen nanobubble generating unit, a reaction chamber 1, a bidirectional flowable filter device 2, and a storage tank 3 connected in sequence; the top of the reaction chamber is provided with a hydrogen inlet / outlet 5, a solid inlet / outlet 6, and a pressure relief port 7, and the bottom is provided with a liquid inlet / outlet; the dynamic hydrogen nanobubble generating unit is connected to the hydrogen inlet / outlet 5 of the reaction chamber through a gas path; the dynamic hydrogen nanobubble generating unit includes a gas compression circulation system and a parameter monitoring and feedback unit; the parameter monitoring and feedback unit is built into the reaction chamber; the reaction chamber 1 and the bidirectional flowable filter device 2 are connected through a filter regulating valve 10; the storage tank is equipped with a bidirectional reciprocating pump 9, and the bottom of the storage tank is provided with a liquid inlet / outlet 8; the entire device is supported by a container support 4.

[0055] Using the apparatus provided in this embodiment, in-situ regeneration of hydrogen from metal hydride hydrolysis and its hydrolysis products is performed. The method for in-situ regeneration of hydrogen from metal hydride hydrolysis and its hydrolysis products includes the following steps:

[0056] (1) Feeding and water injection: LiH powder is added to reaction chamber 1 through solid inlet and outlet 6; water is injected into storage tank 3 through liquid inlet and outlet, and enters reaction chamber to mix with LiH under the action of bidirectional reciprocating pump 9 and bidirectional flowable filter device 2.

[0057] (2) Hydrolysis of hydrogen: Heating at 70°C, the metal hydride reacts with water to hydrolyze hydrogen, producing hydrogen gas and metal hydroxide slurry. The hydrogen gas is discharged through hydrogen outlet 5.

[0058] (3) Solid-liquid separation: After the hydrogen release reaction is completed, the slurry is separated into solid and liquid by a two-way flowable filter device. The metal hydroxide solid is retained, and the filtrate is transferred to the storage tank or directly enters the next stage.

[0059] (4) In-situ regeneration: The liquid containing dynamic hydrogen nanobubbles is circulated into the metal hydroxide solid in the reaction chamber 5-15 times, and the reaction is carried out under the action of dynamic hydrogen nanobubbles at 30℃ to obtain regenerated metal hydride.

[0060] The dynamic hydrogen nanobubbles are generated by a gas pressure circulation system. According to the data from the parameter monitoring feedback unit in the dynamic hydrogen nanobubble generator, the initial pressure of hydrogen is 11 atm, and the frequency of hydrogen pressure regulation in the gas pressure circulation system is 5 min / time.

[0061] (5) Reversible cycle: Using the regenerated metal hydride as raw material, repeat steps (1) to (4) to realize the in-situ regeneration cycle of metal hydride hydrolysis hydrogenation and hydrolysis products.

[0062] Step (2) yields the XRD pattern of the solid metal hydroxide as shown below. Figure 2 As shown in the figure, the solid product after hydrothermal decomposition is hydroxide (LiOH), which proves the clarity and feasibility of the regeneration path.

[0063] Thermogravimetric analysis curves of the metal hydride obtained after five cycles are shown below. Figure 3 As shown in the figure, the process is achieved through two steps: preliminary hydrothermal decomposition converts the reacted material into lithium hydroxide (LiOH), which is then regenerated into active LiH through treatment to restore its hydrogen production capacity;

[0064] After six cycles, the XRD patterns of the metal hydrides obtained after each step (2) are as follows: Figure 4 As shown, from Figure 4 As can be seen from the data, the LiH crystalline phase is retained, while the LiOH impurity is relatively small.

[0065] Example 2

[0066] Using the apparatus provided in Example 1, in-situ regeneration of hydrogen from metal hydride hydrolysis and its hydrolysis products is performed. The method for in-situ regeneration of hydrogen from metal hydride hydrolysis and its hydrolysis products includes the following steps:

[0067] (1) Feeding and water injection: NaH powder is added to the reaction chamber through the solid inlet and outlet; water is injected into the storage tank through the liquid inlet and outlet, and enters the reaction chamber to mix with NaH under the action of the bidirectional reciprocating pump and the bidirectional flowable filter device.

[0068] (2) Hydrolysis of hydrogen: When heated at 60°C, NaH reacts with water to hydrolyze hydrogen, producing hydrogen gas and metal hydroxide slurry. The hydrogen gas is discharged through the hydrogen outlet.

[0069] (3) Solid-liquid separation: After the hydrogen release reaction is completed, the slurry is separated into solid and liquid by a two-way flowable filter device. The metal hydroxide solid is retained, and the filtrate is transferred to the storage tank or directly enters the next stage.

[0070] (4) In-situ regeneration: Liquid containing dynamic hydrogen nanobubbles is circulated into the metal hydroxide solid in the reaction chamber 5-15 times, and reacted under the action of dynamic hydrogen nanobubbles at 20℃ to obtain regenerated metal hydride.

[0071] The dynamic hydrogen nanobubbles are generated by a gas pressure circulation system. According to the data from the parameter monitoring feedback unit in the dynamic hydrogen nanobubble generator, the initial pressure of hydrogen is 8 atm, and the frequency of hydrogen pressure regulation in the gas pressure circulation system is 3 min / time.

[0072] (5) Reversible cycle: Using the regenerated metal hydride as raw material, repeat steps (1) to (4) as needed to realize the in-situ regeneration cycle of metal hydride hydrolysis hydrogenation and hydrolysis products.

[0073] Example 3

[0074] Using the apparatus provided in Example 1, in-situ regeneration of hydrogen from metal hydride hydrolysis and its hydrolysis products is performed. The method for in-situ regeneration of hydrogen from metal hydride hydrolysis and its hydrolysis products includes the following steps:

[0075] (1) Feeding and water injection: MgH2 powder is added to the reaction chamber through the solid inlet and outlet; water is injected into the storage tank through the liquid inlet and outlet, and enters the reaction chamber to mix with MgH2 under the action of the bidirectional reciprocating pump and the bidirectional flowable filter device.

[0076] (2) Hydrolysis to hydrogen: When heated at 90°C, MgH2 reacts with water to hydrolyze to hydrogen, producing hydrogen gas and metal hydroxide slurry. The hydrogen gas is discharged through the hydrogen outlet.

[0077] (3) Solid-liquid separation: After the hydrogen release reaction is completed, the slurry is separated into solid and liquid by a two-way flowable filter device. The metal hydroxide solid is retained, and the filtrate is transferred to the storage tank or directly enters the next stage.

[0078] (4) In-situ regeneration: Liquid containing dynamic hydrogen nanobubbles is circulated into the metal hydroxide solid in the reaction chamber 5-15 times, and reacted under the action of dynamic hydrogen nanobubbles at 40℃ to obtain regenerated metal hydride.

[0079] The dynamic hydrogen nanobubbles are generated by a gas pressure circulation system. According to the data from the parameter monitoring feedback unit in the dynamic hydrogen nanobubble generator, the initial pressure of hydrogen is 20 atm, and the frequency of hydrogen pressure regulation in the gas pressure circulation system is 4 min / time.

[0080] (5) Reversible cycle: Using the regenerated metal hydride as raw material, repeat steps (1) to (4) as needed to realize the in-situ regeneration cycle of metal hydride hydrolysis hydrogenation and hydrolysis products.

[0081] Example 4

[0082] This embodiment provides a method for in-situ regeneration of hydrogen from hydrolysis of metal hydrides and hydrolysis products. The only difference from Embodiment 1 is that the temperature of the hydrogen hydrolysis reaction in step (2) is 0°C, while the other steps remain unchanged.

[0083] Example 5

[0084] This embodiment provides a method for in-situ regeneration of hydrogen from hydrolysis of metal hydrides and hydrolysis products. The only difference from Embodiment 1 is that the temperature of the hydrogen hydrolysis reaction in step (2) is 100°C, while the other steps remain unchanged.

[0085] Example 6

[0086] This embodiment provides a method for in-situ regeneration of hydrogen from metal hydride hydrolysis and hydrolysis products. The only difference from Embodiment 1 is that the dynamic hydrogen nanobubbles in step (4) are generated by a gas pressure circulation system; the pressure regulation frequency of the gas pressure circulation system for hydrogen is 10 min / time, and the other steps remain unchanged.

[0087] Example 7

[0088] This embodiment provides a method for in-situ regeneration of hydrogen from metal hydride hydrolysis and hydrolysis products. The only difference from Embodiment 1 is that the dynamic hydrogen nanobubbles in step (4) are generated by a gas pressure circulation system; the pressure regulation frequency of the gas pressure circulation system for hydrogen is 0.5 min / time, and the other steps remain unchanged.

[0089] Comparative Example 1

[0090] This comparative example provides a method for in-situ regeneration of hydrogen from metal hydride hydrolysis and hydrolysis products. The only difference from Example 1 is that in step (4), the hydrogen is introduced directly into the aqueous solution of the metal hydroxide precursor without passing through a dynamic hydrogen nanobubble generator.

[0091] test:

[0092] The hydrogen release and regeneration cycle tests were conducted on the metal hydride hydrolysis hydrogen release and hydrolysis product in-situ regeneration methods provided in the examples and comparative examples. The test results are shown in Table 1 below.

[0093] "Capacity retention rate of hydrolysis products" refers to the percentage of hydrogen storage capacity of the regenerated hydride relative to the initial hydride capacity, as measured by thermogravimetric analysis.

[0094] Table 1

[0095]

[0096] The test results show that:

[0097] (1) As can be seen from Examples 1-3, the in-situ regeneration device for hydrogenation and hydrolysis products of metal hydride provided by the present invention integrates two key process units: hydrogen release (hydrothermal hydrolysis hydrogen production) and hydrogen storage (hydride regeneration). At the same time, the dynamic hydrogen nanobubble control method is used to realize the efficient and reversible circulation of metal hydride in the aqueous system. The dynamic hydrogen nanobubble technology significantly improves the yield of active hydrogen atoms, enabling hydride synthesis and regeneration to be carried out efficiently at low temperature (≤100℃), thereby reducing the overall energy consumption by more than 50%. The regenerated hydride has a consistent crystal structure and a low hydrogen storage capacity decay rate.

[0098] (2) By comparing Example 1 with Example 4-5, it can be seen that the present invention further controls the temperature of the hydrolysis hydrogen reaction to 20℃-90℃. The temperature of the hydrolysis hydrogen reaction affects the hydrogen release rate. If the temperature of the hydrolysis hydrogen reaction is too high, an "explosive" hydrogen release may occur. If the temperature of the hydrolysis hydrogen reaction is too low, the hydrogen release will be slow.

[0099] (3) By comparing Example 1 with Example 6-7, it can be seen that the present invention further controls the hydrogen pressure regulation frequency to 0.5 min / time-5 min / time. The hydrogen pressure regulation frequency affects the uniform distribution and high density of bubbles. If the hydrogen pressure regulation frequency is too high, the energy consumption and hydrogen consumption will be too high. If the hydrogen pressure regulation frequency is too low, the degree of hydrogenation will be insufficient.

[0100] (4) As can be seen from Example 1 and Comparative Example 1, the present invention utilizes the dynamic hydrogen nanobubble control method to achieve efficient and reversible recycling of metal hydrides in an aqueous system; the dynamic hydrogen nanobubble method significantly improves the yield of active hydrogen atoms, enabling hydride synthesis and regeneration to proceed efficiently at low temperatures (≤100℃), thereby reducing overall energy consumption by more than 50%. Without the dynamic hydrogen nanobubble control method, no hydrogenation reaction would occur.

[0101] In summary, the metal hydride hydrolysis hydrogenation and in-situ regeneration device provided by this invention integrates two key process units: hydrogen release (hydrothermal hydrolysis hydrogen production) and hydrogen storage (hydride regeneration). Simultaneously, it utilizes a dynamic hydrogen nanobubble control method to achieve efficient and reversible cycling of metal hydrides in an aqueous system. The dynamic hydrogen nanobubble method significantly improves the yield of active hydrogen atoms, enabling hydride synthesis and regeneration to proceed efficiently at low temperatures (≤100℃), thereby reducing overall energy consumption by more than 50%. The regenerated hydrides exhibit a consistent crystal structure and a low hydrogen storage capacity decay rate.

[0102] The applicant declares that 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. An apparatus for in-situ regeneration of hydrogen from metal hydride hydrolysis and its hydrolysis products, characterized in that, The device includes a dynamic hydrogen nanobubble generating unit, a reaction chamber, a two-way flowable filtration device, and a liquid storage tank connected in sequence. The top of the reaction chamber is equipped with a hydrogen inlet / outlet, a solid inlet / outlet, and a pressure relief port, while the bottom is equipped with a liquid inlet / outlet. The dynamic hydrogen nanobubble generating unit is connected to the hydrogen inlet and outlet of the reaction chamber via a gas path. The dynamic hydrogen nanobubble generating unit includes a gas compression and circulation system and a parameter monitoring and feedback unit. The parameter monitoring and feedback unit is built into the reaction chamber; The reaction chamber and the bidirectional flow-through filter are connected by a filter regulating valve; The storage tank is equipped with a bidirectional reciprocating pump, and the bottom of the storage tank is provided with liquid inlet and outlet.

2. The apparatus according to claim 1, characterized in that, The solid inlet and outlet of the reaction chamber are connected to an external storage silo; And / or, the filter regulating valve is a V-type ball valve.

3. The apparatus according to claim 1 or 2, characterized in that, The gas compression and circulation system includes a gas path connected to the hydrogen inlet and outlet of the reaction chamber, a pressure pump installed on the gas path, and a pressure relief valve.

4. The apparatus according to any one of claims 1-3, characterized in that, The hydrogen outlet of the reaction chamber is connected to a hydrogen purification device and / or a proton exchange membrane fuel cell module.

5. A method for in-situ regeneration of hydrogen from hydrolysis of metal hydrides and hydrolysis products, characterized in that, The method for aqueous phase hydrogen release and in-situ regeneration of metal hydrides is carried out using the apparatus for aqueous phase hydrogen release and in-situ regeneration of metal hydrides as described in any one of claims 1-4.

6. The method according to claim 5, characterized in that, The method includes the following steps: (1) Feeding and water injection: The metal hydride powder is added to the reaction chamber through the solid inlet and outlet; water is injected into the storage tank through the liquid inlet and outlet, and enters the reaction chamber to mix with the metal hydride under the action of the bidirectional reciprocating pump and the bidirectional flowable filter device. (2) Hydrolysis of hydrogen: Metal hydrides react with water to hydrolyze hydrogen, producing hydrogen gas and metal hydroxide slurry. The hydrogen gas is discharged through the hydrogen outlet. (3) Solid-liquid separation: After the hydrogen release reaction is completed, the slurry is separated into solid and liquid by a two-way flowable filter device. The metal hydroxide solid is retained, and the filtrate is transferred to the storage tank or directly enters the next stage. (4) In-situ regeneration: Liquid containing dynamic hydrogen nanobubbles is circulated into the metal hydroxide solid in the reaction chamber n times. The reaction is carried out under the action of dynamic hydrogen nanobubbles to obtain regenerated metal hydride, where n is a positive integer ≥1. (5) Reversible cycle: Using the regenerated metal hydride as raw material, repeat steps (1) to (4) N times to realize the in-situ regeneration cycle of metal hydride hydrolysis hydrogenation and hydrolysis products, where N is a positive integer ≥1.

7. The method according to claim 5 or 6, characterized in that, The temperature for the hydrolysis of hydrogen in step (2) is 20℃-90℃.

8. The method according to any one of claims 5-7, characterized in that, The metal hydride includes any one or a combination of at least two of LiH, NaH, KH, CaH2, or MgH2.

9. The method according to any one of claims 5-8, characterized in that, The dynamic hydrogen nanobubbles mentioned in step (4) are generated by a gas pressure circulation system; the frequency of the gas pressure circulation system for regulating the hydrogen pressure is 0.5 min / time to 5 min / time; And / or, the initial pressure of the hydrogen is 8 atm-20 atm.

10. The method according to any one of claims 5-9, characterized in that, The temperature of the regeneration reaction in step (4) is 20℃-60℃.

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