Wide-temperature-zone slurry hydrogen storage continuous hydrolysis hydrogen production system based on interface reaction thermal coupling

Abstract

The invention discloses a wide-temperature-zone slurry hydrogen storage continuous hydrolysis hydrogen production system based on interface reaction thermal coupling. The system comprises a reactor, a feeding module, a collecting module and a heat exchanger, wherein the feeding module and the collecting module are respectively connected with the reactor; the feeding module is used for conveying water and a slurry hydrogen production material to the reactor, and a hydrogen production mixture is formed in the reactor; a multi-layer inclined plate structure is arranged in the reactor; the collecting module is used for collecting hydrogen generated by the reactor; the heat exchanger is used for carrying out heat exchange on water by utilizing heat of waste materials generated by reaction of the hydrogen production mixture to form water vapor and conveying the water vapor to the reactor. The reactor is internally provided with a multi-layer inclined plate structure, a hydrogen production mixture flows from top to bottom along the multi-layer inclined plate under the action of gravity and continuously performs a hydrogen release reaction, heat of waste generated by the reaction of the hydrogen production mixture is fully utilized to perform heat exchange on water to form water vapor, and mass and heat transfer is enhanced through a disturbance effect; the reaction efficiency and the energy utilization rate are obviously improved.

Description

Technical Field

[0001] The present invention relates to the technical field, and in particular to a wide temperature range slurry hydrogen storage and continuous hydrolysis hydrogen production system based on interface reaction thermal coupling. Background Art

[0002] As a clean and efficient secondary energy carrier, hydrogen energy has broad application prospects in transportation, industrial production, distributed energy and other fields. Hydrogen is mainly produced through chemical reactions, and improving the efficiency of hydrogen production reactions and reducing the difficulty of reactions are of great practical significance.

[0003] Public patents CN118598073A, CN118495469A, CN118495470A, CN118598072A and CN118702058A combine organic liquid hydrogen storage with metal microcrystalline hydrogen storage in slurry hydrogen production materials composed of nano-microcrystalline metal powders, organic liquid hydrides, etc., showing good theoretical hydrogen release and faster reaction rate at lower temperatures. However, the organic liquid hydrogen release process requires continuous heat supply, and the existing hydrogen production system mainly relies on external heating, which fails to achieve the cascade utilization of heat, resulting in low energy utilization efficiency. In addition, the existing hydrogen production system has insufficient gas-liquid two-phase contact, the reaction of metal microcrystalline materials with water is difficult to accurately control, and the hydrogen release of organic liquids is often incomplete, which seriously affects the overall hydrogen production efficiency. Summary of the invention

[0004] In order to solve the problems existing in the prior art, the present invention designs a reactor with a multi-layer inclined plate structure and fully utilizes the heat generated by the hydrogen production reaction to achieve cascade utilization of heat, improve gas-liquid contact efficiency, and optimize temperature control. It not only achieves a dual increase in hydrogen storage density and hydrogen production efficiency, but also significantly improves the energy utilization rate of the system.

[0005] In order to achieve the above-mentioned object, the present invention provides a wide temperature range slurry hydrogen storage continuous hydrolysis hydrogen production system based on interface reaction thermal coupling, comprising a reactor, a feed module and a collection module respectively connected to the reactor, and a heat exchanger; The feed module is used to transport water and slurry hydrogen production material to the reactor to form a hydrogen production mixture in the reactor; A multi-layer inclined plate structure is arranged inside the reactor; The collection module is used to collect hydrogen generated by the reactor; The heat exchanger is used to utilize the heat of the waste generated by the hydrogen production mixture reaction to perform heat exchange on water to form water vapor, and then transport the water vapor to the reactor.

[0006] Furthermore, the feed module comprises a water storage tank and a material storage tank respectively connected to the reactor, and the material storage tank is used to store slurry hydrogen production material; The heat exchanger has a feed inlet, a discharge inlet, a water inlet, and a gas outlet, and the feed inlet is connected to the reactor; The water storage tank is also connected to the reactor via the water inlet and the gas outlet.

[0007] Furthermore, the collection module includes a first separator, a membrane separator and a hydrogen storage tank which are sequentially connected to the reactor.

[0008] Furthermore, the gas outlet of the heat exchanger is connected to the reactor via an air inlet pipe; The first separator is also connected to the air intake duct.

[0009] Furthermore, the reactor and the first separator are connected via a buffer tank.

[0010] Furthermore, it also includes a processing module, the processing module includes a second separator connected to the outlet of the heat exchanger, and a first waste tank and a second waste tank respectively connected to the second separator; The first waste tank and the second waste tank are used to collect organic liquid waste and catalyst after the reaction respectively.

[0011] Furthermore, the water storage tank is connected to the reactor via a water inlet pipe, and a water pump is provided on the water inlet pipe.

[0012] Furthermore, an air pump is provided on the air intake pipe.

[0013] Furthermore, a heating component is also provided at the lower end of the reactor.

[0014] The present invention also provides a working method of the above hydrogen production system, comprising: transporting water and slurry hydrogen production material to a reactor to form a hydrogen production mixture in the reactor; The hydrogen production mixture falls under the multi-layer inclined plate structure of the reactor due to gravity and continuously releases hydrogen. During the hydrogen release reaction, the heat exchanger uses the heat of the waste generated by the hydrogen production mixture reaction to exchange heat with water to form water vapor, thereby enhancing mass transfer and heat transfer through the disturbance effect.

[0015] It should be noted that, in the present invention, the slurry hydrogen production material does not need to be strictly limited, and it can be composed of nano-microcrystalline metal, organic liquid and catalyst. Wherein, in terms of mass percentage, the contents of nanocrystalline metal, organic liquid and catalyst are 1-40wt.%, 50-95wt.%, and 1-25wt.% respectively; the nanocrystalline metal can be at least one of Na, K, Mg and Al with an average particle size of 100-1000nm; the organic liquid is at least one of the full hydrogenation products of aromatic compounds, the full hydrogenation products of heterocyclic compounds and the full hydrogenation products of liquid organic polyols, wherein the full hydrogenation product of the aromatic compound is at least one of cyclohexane, methylcyclohexane, dimethylcyclohexane, decane and decahydronaphthalene; the full hydrogenation product of the heterocyclic compound is at least one of full hydrogenated N-ethylcarbazole, full hydrogenated N-propylcarbazole, full hydrogenated N-methylindole, full hydrogenated N-ethylindole, and full hydrogenated quinoline; the full hydrogenation product of the liquid organic polyol is at least one of methanol, ethanol and isopropanol. The catalyst can be at least one of Pd-based and Pt-based catalysts.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The present invention arranges a multi-layer inclined plate structure inside the reactor. Water and slurry hydrogen-producing materials form a hydrogen-producing mixture, which flows from top to bottom along the multi-layer inclined plates under the action of gravity and continuously performs a hydrogen-releasing reaction. The heat of the waste generated by the reaction of the hydrogen-producing mixture is fully utilized to perform heat exchange with water to form water vapor. The mass transfer and heat transfer are enhanced through the disturbance effect, thereby achieving a significant improvement in the reaction efficiency and energy utilization rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0018] Figure 1 The schematic diagram of the structure of the wide temperature range slurry hydrogen storage and continuous hydrolysis hydrogen production system based on thermal coupling of interface reaction is shown; Figure 2 A schematic cross-sectional structure diagram of a reactor is shown; Description of reference numerals: 1. Reactor; 2. Water storage tank; 3. First storage tank; 4. Buffer tank; 5. First separator; 6. Membrane separator; 7. Hydrogen storage tank; 8. Heat exchanger; 9. Second separator; 10. First waste tank; 11. Second waste tank; 12. Water pump; 13. Air pump. DETAILED DESCRIPTION

[0019] In the description of the present invention, it should be understood that the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of this application, "plurality" means two or more, unless otherwise clearly and specifically defined.

[0020] In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection, a direct connection, or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0021] The following will be combined with the specific embodiments of the present invention and the drawings of the specification to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] Example like Figure 1As shown, a wide temperature range slurry hydrogen storage continuous hydrolysis hydrogen production system based on interfacial reaction thermal coupling includes a feed module, a reactor 1, a collection module, a processing module and a heat exchanger 8; the feed module and the collection module are respectively connected to the reactor 1. The feed module is used to transport water, slurry hydrogen production materials and catalysts to the reactor 1 to form a hydrogen production mixture in the reactor 1. Specifically, the feed module includes a water storage tank 2 and a material storage tank 3 and connected to the reactor 1 respectively. The material storage tank 3 and is used to store slurry hydrogen production materials. The water storage tank 2 is connected to the reactor 1 through a water inlet pipe, and a water pump 12 is provided on the water inlet pipe. The heat exchanger 8 has a feed port, a discharge port, a water inlet, and an air outlet, and the feed port is connected to the lower end of the reactor 1; the water storage tank 2 is also connected to the lower end of the reactor 1 through the water inlet and the air outlet, wherein the air outlet of the heat exchanger 8 is connected to the bottom of the reactor 1 through an air inlet pipe, and an air pump 13 is provided on the air inlet pipe; the heat exchanger 8 is used to use the heat of the waste generated by the hydrogen production mixture reaction to heat exchange water to form water vapor, and transport the water vapor to the reactor 1. The collection module is used to collect the hydrogen generated by the reactor 1, specifically, the collection module includes a buffer tank 4, a first separator 5, a membrane separator 6 and a hydrogen storage tank 7 connected to the reactor 1 in sequence, wherein the first separator 5 is also connected to the air inlet pipe. The processing module includes a second separator 9 connected to the discharge port of the heat exchanger 8, and a first waste tank 10 and a second waste tank 11 respectively connected to the second separator 9; the first waste tank 10 and the second waste tank 111 are respectively used to collect organic liquid waste and catalyst after the reaction.

[0023] like Figure 2 As shown, a multi-layer inclined plate structure is arranged inside the reactor 1, which not only increases the gas-liquid contact area, but also prolongs the residence time of the reactants in the reactor 1, creating favorable conditions for sufficient reaction. A heating component is also arranged at the lower end of the reactor 1. The upper section of the reactor 1 generates heat through the hydrolysis exothermic reaction of the nano-microcrystalline metal and water, and the heat generated is used to preheat the organic liquid hydride; an independent heating section is arranged at the lower part, and the reaction temperature is maintained in the optimal range through external heating to ensure sufficient hydrogen release of the organic liquid.

[0024] In this embodiment, the slurry hydrogen production material is a mixed slurry of 50wt.% N-propylcarbazole, 40wt.% Al powder with an average particle size of 100nm and 10wt.% Pd-based catalyst in terms of mass percentage. The preparation method of the slurry hydrogen production material can refer to the patent CN118495469A, which does not involve the improvement points of the present invention, and the present invention does not make any improvement. Continuous hydrolysis is adopted to produce hydrogen. During the hydrogen production reaction, water is continuously added in a flowing manner, and the amount of water does not need to be limited.

[0025] In this embodiment, the heating component only needs to use the combustible gas generated in real time by the reaction to burn and provide heat, so that the temperature of the heating section can reach the optimal temperature range of 100-200°C. Of course, it is not limited to this, and other heating forms can also be used, but it is necessary to ensure that the temperature of the heating section in the reactor 1 is 100-200°C.

[0026] The working principle of the hydrogen production system is as follows: A dual-path design is adopted for the transportation of water. The first path is pressurized by a water pump 12 and sprayed into the reactor 1 from the top. The second path is a heat recovery process, using the heat of the high-temperature waste generated by the hydrogen production mixture reaction to exchange heat with liquid water. On the one hand, it is used to cool the high-temperature waste, and on the other hand, it is used to preheat the liquid water or even directly vaporize it. It is introduced from the bottom of the reactor 1 through the air intake pipe. The gas disturbance of the water vapor enhances the contact with the slurry hydrogen production material, promotes the hydrogen release reaction of the organic liquid, and the full reaction of the nano-microcrystalline metal and water, thereby improving the overall reaction efficiency. After the slurry hydrogen production material and catalyst composed of nano-microcrystalline metal and organic liquid hydride are transported to the top of the reactor 1, they flow from top to bottom along the multi-layer inclined plate under the action of gravity. In the upper section of the reactor 1, the nano-microcrystalline metal and water undergo a violent exothermic reaction, which not only produces hydrogen, but also releases a large amount of heat that is used to preheat the organic liquid hydride in the slurry hydrogen production material. Since the heat provided by the reaction of nanocrystalline metal and water may not be sufficient to maintain the continuous and sufficient release of hydrogen from the organic liquid, a heating zone is specially arranged in the lower section of the reactor 1 to provide additional heat supply through an external heating device and to utilize the combustible gas separated from the membrane separator 6 for combustion heat, thereby ensuring that the reaction temperature is maintained in the optimal range of 100-200°C.

[0027] The gas produced by the reaction is transported to the buffer tank 4 for pressure buffering and phase stabilization, and then enters the separator for the first round of separation. During the separation process, high-temperature water vapor is extracted first and returned to the bottom of the reactor 1 through the air pump 13 and the air inlet pipe. The remaining gas separated by the separator is transported to the membrane separator 6, where it is deeply separated to obtain high-purity hydrogen. The separated hydrogen is transported to the hydrogen storage tank 7 for collection and storage, while the separated combustible gas (CO, CH4, etc.) is returned to the heating component at the lower end of the reactor 1 for combustion and heat supply, forming a complete heat energy recycling system. This multi-stage heat utilization scheme significantly improves the energy self-sufficiency and overall energy efficiency of the system. In addition, the high-purity hydrogen obtained after multi-stage separation of the reaction product has a high economic value, and the by-products are recycled as a heat source for the system, which realizes the full utilization of materials and reduces operating costs.

[0028] During the reaction interval, the hydrogen production system processes the generated waste. The waste is transported to the second separator 9, where the organic liquid waste and the catalyst residue are efficiently separated. The separated organic liquid waste is collected in the first waste tank 10, and the catalyst residue is transported to the second waste tank 11, thereby realizing the classified collection and management of the waste.

[0029] The experimental results show that after 5 hours of reaction, the degree of reaction conversion can be evaluated by waste analysis: the aluminum powder in the embodiment is completely hydrolyzed, and the conversion rate reaches 100%; the conversion rate of organic liquid N-propylcarbazole is about 92%.

[0030] Comparative Example Different from the embodiment, the comparative example only sprays water from the upper end of the reactor without using water vapor disturbance below. Under the same reaction time, the conversion rate of aluminum powder drops to about 75%, and the conversion rate of organic liquid N-propylcarbazole is only 53%.

[0031] In summary, the present invention arranges a multi-layer inclined plate structure inside the reactor, and water and slurry hydrogen-producing materials form a hydrogen-producing mixture, which flows from top to bottom along the multi-layer inclined plates under the action of gravity and continuously releases hydrogen. The heat of the waste generated by the reaction of the hydrogen-producing mixture is fully utilized to exchange heat with water to form water vapor, and the mass transfer and heat transfer are enhanced through the disturbance effect, thereby achieving a significant improvement in reaction efficiency and energy utilization.

[0032] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A wide temperature range slurry hydrogen storage and continuous hydrolysis hydrogen production system based on interface reaction thermal coupling, characterized in that: It includes a reactor, a feed module and a collection module respectively connected to the reactor, and a heat exchanger; The feed module is used to transport water and slurry hydrogen production materials to the reactor to form a hydrogen production mixture in the reactor; A multi-layer inclined plate structure is arranged inside the reactor; The collection module is used to collect hydrogen generated by the reactor; The heat exchanger is used to utilize the heat of the waste generated by the hydrogen production mixture reaction to perform heat exchange on water to form water vapor, and then transport the water vapor to the reactor.

2. The hydrogen production system according to claim 1, characterized in that: The feed module comprises a water storage tank and a material storage tank respectively connected to the reactor, and the material storage tank is used to store slurry hydrogen production materials; The heat exchanger has a feed inlet, a discharge inlet, a water inlet, and a gas outlet, and the feed inlet is connected to the reactor; The water storage tank is also connected to the reactor via the water inlet and the gas outlet.

3. The hydrogen production system according to claim 2, characterized in that: The collection module includes a first separator, a membrane separator and a hydrogen storage tank which are sequentially connected to the reactor.

4. The hydrogen production system according to claim 3, characterized in that: The gas outlet of the heat exchanger is connected to the bottom of the reactor through an air inlet pipe; The first separator is also connected to the air intake duct.

5. The hydrogen production system according to claim 3, characterized in that: The reactor and the first separator are connected via a buffer tank.

6. The hydrogen production system according to claim 2, characterized in that: Also included is a processing module, the processing module including a second separator connected to the outlet of the heat exchanger, and a first waste tank and a second waste tank respectively connected to the second separator; The first waste tank and the second waste tank are used to collect organic liquid waste and catalyst after the reaction, respectively.

7. The hydrogen production system according to claim 2, characterized in that: The water storage tank is connected to the reactor via a water inlet pipe, and a water pump is arranged on the water inlet pipe.

8. The hydrogen production system according to claim 4, characterized in that: An air pump is arranged on the air intake pipeline.

9. The hydrogen production system according to any one of claims 1 to 8, characterized in that: A heating component is also provided at the lower end of the reactor.

10. A working method using the hydrogen production system according to any one of claims 1 to 9, characterized in that: include, transporting water and slurry hydrogen production material to a reactor to form a hydrogen production mixture in the reactor; The hydrogen production mixture falls under the multi-layer inclined plate structure of the reactor due to gravity and continuously releases hydrogen. During the hydrogen release reaction, the heat exchanger uses the heat of the waste generated by the hydrogen production mixture reaction to exchange heat with water to form water vapor, thereby enhancing mass transfer and heat transfer through the disturbance effect.

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