Multi-medium composite slurry hydrogen storage material based on nanocrystalline metal powder and organic liquid hydride and its preparation method

Abstract

The application discloses a kind of based on nano microcrystalline metal powder and organic liquid hydride multi-medium composite slurry hydrogen storage material and its preparation method, and multi-medium composite slurry hydrogen storage material includes nano microcrystalline metal powder for hydrolysis heat production, hydrogen release endothermic organic liquid hydride and catalyst;Nano microcrystalline metal powder content is 1~40wt.%, and organic liquid hydride content is 50~95wt.%, and the content of catalyst is 1~25wt.%.The application combines the advantages of metal powder and organic liquid hydride, by covering metal powder in organic liquid hydride, on the one hand, the passivation problem of metal powder surface is solved, effectively isolates metal powder and air contact, prevents the formation of oxide;On the other hand, the heat generated by the reaction of metal and water is absorbed by organic liquid hydride, thereby improving the mass transfer efficiency, and reducing the energy loss in heat transfer process.

Description

Technical Field

[0001] This invention relates to a multi-media composite slurry hydrogen storage and production material and its preparation method, specifically a multi-media composite slurry hydrogen storage and production material based on nanocrystalline metal powder and organic liquid hydride and its preparation method, belonging to the field of hydrogen storage and production technology. Background Technology

[0002] With increasing energy demand and escalating environmental problems, the traditional fossil fuel energy supply model is becoming unsustainable. Hydrogen energy, as a clean and efficient green energy source, not only has high energy density but also produces only water when burned, making it an ideal alternative to traditional fossil fuels.

[0003] To achieve widespread application of hydrogen energy, the safe and efficient storage and production of hydrogen needs to be addressed. Hydrogen production from molten aluminum, as an emerging method, has attracted widespread attention due to its high hydrogen storage density and relatively simple production equipment.

[0004] In the existing technology, 1) patent CN114715846A effectively reduces the amount of rare metals used and the preparation cost by using aluminum-based oxides and chlorides as additives, while improving the purity of by-products after the hydrolysis hydrogen production reaction. The introduction of γ-Al2O3 and aluminum chloride as grinding aids not only improves the performance of aluminum powder but also accelerates the hydrolysis reaction rate. This material has good storage stability, is suitable for different environments, and can rapidly produce high-purity hydrogen at room temperature. However, chlorides are corrosive and require high-quality equipment. In addition, improper handling of chlorides can harm the environment.

[0005] 2) Patent CN114804020A creates a novel slurry-like hydrogen storage material by combining a liquid organic hydrogen carrier (LOHC) with the solid hydride hydrogen storage material NaAlH4. This material achieves a combination of high hydrogen storage capacity and low operating temperature. It effectively combines the advantages of LOHC and NaAlH4, increasing hydrogen storage capacity (over 5.0 wt%) and lowering the hydrogen absorption and desorption operating temperature (below 200°C), while ensuring relatively fast hydrogen absorption and desorption kinetics. The introduction of Ti-based and Ni-based catalysts further optimizes the hydrogen absorption and desorption process, allowing the operating temperature to be further reduced to 130°C. However, judging from the attached drawings of this patent, it takes nearly 10 hours to achieve complete hydrogen release, indicating that there is still significant room for improvement in the hydrogen storage capacity and hydrogen release rate of this material.

[0006] 3) CN117023512A combines hydrogen production from waste aluminum hydrolysis with hydrogen absorption from liquid organic hydrogen carrier (LOHC), achieving an integrated process of hydrogen production and storage. It uses intermittent dripping of strong alkaline solution to control the aluminum water reaction, allowing the hydrogen production from aluminum water and the hydrogen absorption reaction of LOHC to proceed simultaneously. In addition, a nickel-aluminum alloy catalyst is used to effectively resist the influence of alkaline water and gaseous impurities on the activity. However, this method uses a strong alkaline solution as the reaction medium, which places certain requirements on the equipment. Furthermore, this method utilizes the hydrogen absorption reaction of organic liquid rather than the hydrogen release reaction. Summary of the Invention

[0007] The purpose of this invention is to address the problems commonly found in existing metal hydrolysis and organic liquid hydride hydrogen production methods, such as corrosive reaction media, high equipment requirements, and slow hydrogen release rates. This invention provides a multi-media composite slurry hydrogen storage and production material based on nanocrystalline metal powder and organic liquid hydrides, characterized by a simple and mild reaction medium and a fast hydrogen release rate. The invention also provides a method for preparing this slurry hydrogen storage and production material. This material utilizes the large amount of heat released during metal hydrolysis to power the release of hydrogen from the organic liquid hydride, thereby achieving high hydrogen storage density and low-temperature, efficient, and continuous hydrogen storage and release.

[0008] The present invention achieves the above-mentioned objective through the following technical solution: a multi-media composite slurry hydrogen storage and production material based on nanocrystalline metal powder and organic liquid hydride, comprising nanocrystalline metal powder for hydrolysis heat generation and organic liquid hydride for hydrogen release and endothermic reaction; wherein the content of the nanocrystalline metal powder is 1-40 wt.%, the content of the organic liquid hydride is 50-95 wt.%, and the content of the catalyst is 1-25 wt.

[0009] As a further aspect of the present invention, the average particle size of the nanocrystalline metal powder ranges from 10 nm to 1000 nm.

[0010] As a further aspect of the present invention: the hydrogen release of the organic liquid hydride is between 3.0% and 13.0%; the heat of hydrogenation of the organic liquid hydride is in the range of 65 to 80 kJ / mol.

[0011] As a further embodiment of the present invention: the nanocrystalline metal powder is Na, Mg, Al and K.

[0012] As a further aspect of the present invention: the organic liquid hydride is a fully hydrogenated product of aromatic compounds, heterocyclic compounds and liquid organic polyols.

[0013] As a further embodiment of the present invention: the fully hydrogenated products of aromatic compounds are cyclohexane, methylcyclohexane, dimethylcyclohexane, decane, and decahydronaphthalene; the fully hydrogenated products of heterocyclic compounds are fully hydrogenated N-ethylcarbazole, fully hydrogenated N-propylcarbazole, fully hydrogenated N-methylindole, fully hydrogenated N-ethylindole, and fully hydrogenated quinoline; and the fully hydrogenated products of liquid organic polyols are methanol, ethanol, and isopropanol.

[0014] As a further aspect of the present invention: a catalyst is added to the hydrogen release reaction of the multi-media composite slurry hydrogen storage and production material; wherein the catalyst may be a Pd-based catalyst or a Pt-based catalyst.

[0015] A method for preparing a multi-media composite slurry hydrogen storage and production material based on nanocrystalline metal powder and organic liquid hydride, the method comprising the following steps:

[0016] S1. Place the mixture of nanocrystalline metal powder and organic liquid hydride into a ball mill jar;

[0017] S2. After putting the mixture described in step S1 into the ball mill jar, add grinding balls at a ball-to-material ratio of 3:1, introduce N2 as a protective gas, and adjust the speed of the ball mill to 300-800 r / min.

[0018] S3. Start the ball mill and maintain it under the conditions described in step S2 for 120-240 minutes. After the ball milling is completed, the multi-media composite slurry hydrogen storage and production material can be obtained.

[0019] As a further embodiment of the present invention: in step S1, the nanocrystalline metal powder and organic liquid hydride placed in the ball milling jar are in excess by 3% to 5% as ball milling loss.

[0020] As a further embodiment of the present invention, the preparation method is applied under temperature conditions of 150 to 300°C and pressure conditions of 0.1 to 0.5 MPa.

[0021] The beneficial effects of this invention are:

[0022] 1) This invention combines the advantages of metal powder and organic liquid hydride. By coating the metal powder in organic liquid hydride, the passivation problem of the metal powder surface is solved on the one hand, effectively isolating the metal powder from contact with air and preventing the formation of oxides; on the other hand, the heat generated by the reaction of metal powder with water is absorbed by organic liquid hydride, thereby improving mass transfer efficiency and reducing energy loss in the heat transfer process. This method not only improves the hydrogen yield, but also enhances the overall energy utilization efficiency of the system.

[0023] 2) Organic liquid hydrides, as additives and stabilizers, can improve the dispersibility of metal powders and form an adsorption layer on the surface of metal powders, preventing metal microcrystals from contacting air, avoiding the formation of oxide films, and shortening the induction period of the reaction.

[0024] 3) The large amount of heat released by the nanocrystalline metal hydrolysis reaction in the coupling reaction can be applied to the hydrogen release process of organic liquid hydrides. Compared with the traditional metal hydrolysis hydrogen production technology, it realizes dual hydrogen production of metal microcrystal hydrolysis and organic liquid hydrides, achieving a hydrogen release of 7.79 wt.%, and increasing the controllability of the hydrogen production system, reducing the risk of thermal runaway, and avoiding large-scale agglomeration of metal microcrystals. Attached Figure Description

[0025] Figure 1 This is an analysis diagram of the H2 yield curve of an embodiment of the present invention;

[0026] Figure 2 This is an analysis graph of the H2 generation rate curve in an embodiment of the present invention;

[0027] Figure 3 This is an analysis diagram of the H2 yield curve for the comparative example of this invention;

[0028] Figure 4 This is an analysis graph of the H2 generation rate curve for the comparative example of this invention;

[0029] Figure 5 This is a thermal coupling diagram of Embodiment 1 of the present invention;

[0030] Figure 6 This is a TEM analysis diagram of Embodiment 1 of the present invention. Detailed Implementation

[0031] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] This invention provides a multi-media composite slurry hydrogen storage and production material based on nanocrystalline metal powder and organic liquid hydride. The multi-media composite slurry hydrogen storage and production material includes nanocrystalline metal powder for hydrolysis heat generation and organic liquid hydride for hydrogen release and endothermic reaction.

[0033] The content of the nanocrystalline metal powder is 1-40 wt.%; the average particle size of the nanocrystalline metal powder ranges from 10 nm to 1000 nm; the nanocrystalline metal powder can be Na, Mg, Al or K.

[0034] The organic liquid hydride content is 50–95 wt.%; the hydrogen release of the organic liquid hydride is between 3.0% and 13.0%; the heat of hydrogenation of the organic liquid hydride is in the range of 65–80 kJ / mol; the organic liquid hydride includes the fully hydrogenated products of aromatic compounds, heterocyclic compounds or liquid organic polyols.

[0035] The fully hydrogenated products of aromatic compounds are cyclohexane, methylcyclohexane, dimethylcyclohexane, decane, and decahydronaphthalene; the fully hydrogenated products of heterocyclic compounds are fully hydrogenated N-ethylcarbazole, fully hydrogenated N-propylcarbazole, fully hydrogenated N-methylindole, fully hydrogenated N-ethylindole, and fully hydrogenated quinoline; the fully hydrogenated products of liquid organic polyols are methanol, ethanol, and isopropanol.

[0036] A catalyst is added to the hydrogen release reaction of the multi-media composite slurry hydrogen storage and production material. The catalyst can be a Pd-based catalyst or a Pt-based catalyst, and the catalyst content is 1-25 wt.%.

[0037] Example

[0038] Example 1: A method for preparing a composite slurry-based hydrogen storage and production material based on nanocrystalline metal powder and organic liquid hydride, the method comprising:

[0039] 1) Weigh the required nanocrystalline metal powder, catalyst, and organic liquid hydride and mix them to obtain a mixture;

[0040] 2) Place the mixture into a ball mill jar, add milling balls at a ball-to-material ratio of 3:1, and mill under N2 atmosphere at a speed of 300-800 r / min for 120-240 min. After the reaction is complete, separate the milling balls from the slurry (multi-media composite slurry hydrogen storage and production material).

[0041] 3) The obtained slurry and water are added to the reactor one after another. By controlling the water addition rate, the hydrogen release reaction can be carried out to realize the hydrogen release process of the multi-media slurry hydrogen storage and production material.

[0042] Two points need to be noted: First, the excess of 3% to 5% of the nanocrystalline metal powder and organic liquid hydride placed in the ball mill jar is considered as ball milling loss; second, this preparation method is applied under temperature conditions of 150 to 300°C and pressure conditions of 0.1 to 0.5 MPa.

[0043] Examples 2 to 6 all obtained slurries according to the preparation method of Example 1.

[0044] Specifically, in Examples 1 to 6, 6.0–9.5 g of the fully hydrogenated product (organic liquid hydride), 0.1–3.0 g of 10–1000 nm nanocrystalline metal powder, and 0.1–2.0 g of catalyst were weighed and added to a stainless steel ball mill jar. Grinding balls were added at a ball-to-material ratio of 3:1, and the mixture was ball-milled for 120–240 min under a N2 atmosphere. The ball milling speed was set to 300–800 r / min. After ball milling, the grinding balls were separated from the slurry to obtain the slurries of Examples 1 to 6, respectively. The specific conditions are shown in Table 1 below.

[0045] Table 1 is a detailed list of components in the slurry preparation process of Examples 1 to 6.

[0046]

[0047] Hydrogen release was evaluated based on the slurries obtained in Examples 1 to 6: 10g of slurry was introduced into the reactor, the hydrogen release temperature was maintained between 150 and 300°C for 10 minutes, 100ml of pure water was injected into the dehydrogenation device, and the change in the balance reading was observed. The drainage mass data was recorded using the balance, and the results were evaluated according to the formula:

[0048]

[0049] The mass of the wastewater is converted into the actual amount of hydrogen released.

[0050] The H2 yield curve of the slurry is as follows: Figure 1 As shown, the H2 generation rate is as follows Figure 2 As shown. The H2 yield of all slurries exceeded 70%, with the fastest H2 formation rate between 30 and 60 minutes, the maximum yield reaching 96.8%, and the maximum hydrogen release being 9.19%. The thermal coupling diagram and TEM image of Example 1 are shown below. Figure 5 and Figure 6 As shown.

[0051] Comparative examples, in Comparative Examples 1 to 6: 7.0–10.0 g of the fully hydrogenated product, 1.2–10.0 g of 10–1000 nm metal powder, and 0.3–0.5 g of catalyst were weighed and added to a stainless steel ball mill jar. Grinding balls were added at a ball-to-material ratio of 3:1. The mixture was ball-milled for 120–240 min under a nitrogen atmosphere, with the milling speed set to 300–800 r / min. After milling, the grinding balls were separated from the slurry to obtain the slurry. Specific conditions are shown in Table 2 below.

[0052] Table 2 shows the detailed composition of the slurry preparation process for Comparative Examples 1 to 6.

[0053]

[0054] Hydrogen release was evaluated based on the slurries obtained in Comparative Examples 1 to 6: 10g of slurry was introduced into the reactor, and the hydrogen release temperature was maintained between 150 and 300℃ for 10 minutes. 100ml of pure water was then injected into the dehydrogenation device, and the change in the balance reading was observed. The wastewater mass data was recorded using the balance, and the results were analyzed according to the formula:

[0055]

[0056] The mass of the wastewater is converted into the actual amount of hydrogen released.

[0057] The H2 yield curve of the slurry is as follows: Figure 3 As shown, the H2 generation rate is as follows Figure 4 As shown in the comparison example, no hydrogen release reaction occurs in the presence of only organic liquid, even in the presence of a catalyst. In the presence of only metal, the reaction has no induction period, and the time duration is extremely short, resulting in an extremely fast reaction rate, completing the hydrogen release reaction within 30 minutes.

[0058] Comparative Example 1 shows that although the system can release a large amount of hydrogen, it cannot achieve continuous hydrogen release over a long period. In Comparative Examples 2, 5, and 6, it was observed that the reactions in these samples failed to initiate due to a lack of necessary system heating. Even in the presence of a catalyst, insufficient heat supply prevented the triggering of the required chemical reactions. Furthermore, the analysis results of Comparative Examples 3 and 4 indicate that in the absence of a catalyst, the organic liquid in the system hardly participates in the reaction, resulting in extremely low hydrogen release efficiency for the entire system. Hydrogen release mainly relies on the reaction of some metals, but this process is inefficient and cannot meet the requirements of practical applications. Therefore, the presence of a catalyst is crucial for improving hydrogen release efficiency and achieving high-efficiency conversion.

[0059] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0060] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A multi-media composite slurry-based hydrogen storage and production material based on nanocrystalline metal powder and organic liquid hydride, characterized in that: The invention comprises nanocrystalline metal powder for hydrolysis heat generation and an organic liquid hydride for hydrogen release and endothermic reaction; wherein the content of the nanocrystalline metal powder is 1–40 wt.%, the content of the organic liquid hydride is 50–95 wt.%, and the content of the catalyst is 1–25 wt.%; the average particle size of the nanocrystalline metal powder ranges from 10 nm to 1000 nm; the hydrogen release of the organic liquid hydride is between 3.0% and 13.0%; the heat of hydrogenation of the organic liquid hydride ranges from 65 to 80 kJ / mol; and the nanocrystalline metal powder includes, but is not limited to, Na, Mg, Al, and K.

2. The multi-media composite slurry hydrogen storage and production material according to claim 1, characterized in that: The organic liquid hydrides include, but are not limited to, the fully hydrogenated products of aromatic compounds, heterocyclic compounds, and liquid organic polyols.

3. The multi-media composite slurry hydrogen storage and production material according to claim 2, characterized in that: The fully hydrogenated products of the aromatic compounds are cyclohexane, methylcyclohexane, dimethylcyclohexane, decane, and decahydronaphthalene; The perhydrogenation products of the heterocyclic compounds are perhydrogenated N-ethylcarbazole, perhydrogenated N-propylcarbazole, perhydrogenated N-methylindole, perhydrogenated N-ethylindole, and perhydrogenated quinoline; The fully hydrogenated products of the liquid organic polyol are methanol, ethanol, and isopropanol.

4. The multi-media composite slurry hydrogen storage and production material according to claim 1, characterized in that: A catalyst is added to the hydrogen release reaction of the multi-media composite slurry hydrogen storage and production material; wherein the catalyst includes, but is not limited to, Pd-based catalysts or Pt-based catalysts.

5. A method for preparing a multi-media composite slurry hydrogen storage and production material based on nanocrystalline metal powder and organic liquid hydride, comprising the multi-media composite slurry hydrogen storage and production material according to any one of claims 1 to 4, characterized in that, The preparation method includes the following steps: S1. Place the mixture of nanocrystalline metal powder and organic liquid hydride into a ball mill jar; S2. After putting the mixture described in step S1 into the ball mill jar, add grinding balls at a ball-to-material ratio of 3:1, introduce N2 as a protective gas, and adjust the speed of the ball mill to 300-800 r / min. S3. Start the ball mill and maintain it under the conditions described in step S2 for 120-240 minutes. After the ball milling is completed, the multi-media composite slurry hydrogen storage and production material is obtained.

6. The preparation method according to claim 5, characterized in that: In step S1, the nanocrystalline metal powder and organic liquid hydride placed in the ball mill jar are in excess by 3% to 5% as ball milling loss.

7. The preparation method according to claim 5, characterized in that: The preparation method is applied under temperature conditions of 150–300℃ and pressure conditions of 0.1–0.5 MPa.

Images