Solid-state hydrogen storage reactor with resistance self-heating

Abstract

The application provides a resistance self-heating type solid-state hydrogen storage reactor, and belongs to the technical field of hydrogen energy storage, comprising a solid-state hydrogen storage component, a heat management component and an electric heating component. The porous solid-state hydrogen storage material is a coal ash doped magnesium-based composite material, has a porous structure and intrinsic conductivity, and realizes rapid and uniform self-heating through Joule effect; heat exchange plates and hydrogen storage materials are alternately distributed, a closed loop heat management is formed by driving a heat exchange medium and a phase change material storage tank by a circulating pump, heat release recovery in the hydrogen storage stage and heat supply in the hydrogen release stage are realized; an electric heating unit supplements Joule heat through an external power supply, and a temperature control module is combined to realize real-time control of the operating state. The application solves the problems of traditional solid-state hydrogen storage, such as heat response lag, uneven temperature and high energy consumption, significantly improves the hydrogen storage / release rate, cycle stability and energy utilization efficiency, and is suitable for large-scale long-period hydrogen storage of renewable energy.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of hydrogen energy storage technology, in particular to a resistance self-heating type solid-state hydrogen storage reactor, which is suitable for large-scale and long-period hydrogen storage of renewable energy. BACKGROUND

[0002] Nowadays, the key to large-scale application of hydrogen energy lies in efficient hydrogen storage and transportation technology. Hydrogen storage and transportation technology mainly includes high-pressure gaseous hydrogen storage, cryogenic liquid hydrogen storage, organic liquid hydrogen storage and solid-state hydrogen storage technology. High-pressure gaseous hydrogen storage technology is the most mature, but it has low hydrogen storage density and poor safety. Liquid hydrogen storage technology has the disadvantages of high energy consumption, strict requirements for hydrogen storage devices and high cost. Organic liquid hydrogen storage technology is complex, has harsh dehydrogenation reaction conditions, high cost, low efficiency and other factors, which restrict its large-scale application. Solid-state hydrogen storage technology has the advantages of high volumetric hydrogen storage density, high hydrogen purity and high safety. In the metal hydride hydrogen storage technology of solid-state hydrogen storage technology, hydrogen gas and metal elements or alloys react to form metal hydride, realizing safe transportation of hydrogen energy under normal temperature and pressure. Solid-state hydrogen storage materials generate heat during the hydrogen storage and release process. The chemical reaction process of hydrogen and magnesium is as follows:

[0003] (1)

[0004] The metal magnesium hydrogen storage process releases heat, and if the reactor is not cooled in time, the hydrogen storage tank body is prone to thermal runaway. MgH2 has high thermal stability, and the hydrogen release enthalpy is 75 kJ / mol. MgH2 has slow hydrogen absorption and release kinetics at a temperature lower than 300℃, so the hydrogen release process needs to be continuously heated. Among them, magnesium-based solid-state hydrogen storage technology has the advantages of high hydrogen storage density (theoretical hydrogen storage capacity of 7.6 wt%), low raw material cost and high safety, and is concerned. However, solid-state hydrogen storage technology still faces the following technical bottlenecks: ① The hydrogen storage process releases heat, which causes the internal temperature of the reactor to rise rapidly, inducing material pulverization, thermal runaway and other risks; ② The hydrogen release needs to be continuously heated at a high temperature (~300℃), and the traditional external heating method has the problems of thermal response lag, high energy consumption and uneven temperature distribution. The above thermal management problems seriously restrict the improvement of the hydrogen storage and release rate, system cycle stability and energy conversion efficiency of the solid-state hydrogen storage system. SUMMARY

[0005] In view of the thermal management problem of the solid-state hydrogen storage reactor during the hydrogen storage and release process, the present application proposes a resistance self-heating type solid-state hydrogen storage reactor, which uses porous coal ash doped with magnesium-based solid-state hydrogen storage material to realize uniform heating. At the same time, the porous solid-state hydrogen storage material and the water-cooled plate are alternately distributed to suppress the material pulverization and thermal runaway during the hydrogen storage process.

[0006] To achieve the above object, the present application adopts the following technical solutions:

[0007] A resistance self-heating type solid-state hydrogen storage reactor, comprising a solid-state hydrogen storage component, a thermal management component and an electric heating component;

[0008] The solid-state hydrogen storage component comprises porous solid-state hydrogen storage materials arranged in an alternating stack, wherein the porous solid-state hydrogen storage materials are coal ash doped magnesium-based composite materials with a porosity of ≥40% and self-heating through the Joule effect;

[0009] The thermal management component comprises a circulating pump, a phase change material storage tank and a heat exchange plate, the phase change material storage tank forms a closed loop with the heat exchange plate through a pipeline, and the storage tank is filled with a composite phase change material;

[0010] The electric heating component comprises a positive electrode and a negative electrode connected to the porous solid-state hydrogen storage material, for generating auxiliary Joule heat through external power supply;

[0011] The reactor further comprises a temperature control module configured to monitor the temperature of the solid-state hydrogen storage component in real time, and to control the cooperative operation of the thermal management component and the electric heating component according to the upper temperature threshold of the hydrogen storage stage and the lower temperature threshold of the hydrogen release stage.

[0012] Further, the porous solid-state hydrogen storage material comprises coal ash and magnesium powder / magnesium-based alloy.

[0013] Further, the heat exchange plate is made of aluminum alloy or copper alloy.

[0014] Further, the temperature control module comprises:

[0015] A distributed temperature sensor is arranged in the interlayer gap of the porous solid-state hydrogen storage material and on the surface of the heat exchange plate.

[0016] In the hydrogen storage stage, when the temperature is ≥200℃, the circulating pump is started to transfer heat to the phase change material storage tank.

[0017] In the hydrogen release stage, the circulating pump is first started to heat the porous solid-state hydrogen storage material, and then the electric heating unit is activated until the temperature of the porous solid-state hydrogen storage material is ≥300℃.

[0018] Further, the electric heating component comprises an overload protection circuit which automatically cuts off the power supply when the current exceeds a set threshold.

[0019] Further, the heat exchange plate and the porous solid-state hydrogen storage material are arranged alternately, and the heat generated by the porous solid-state hydrogen storage material during the hydrogen storage process is carried away in time by the flow of the internal heat exchange fluid.

[0020] Further, by connecting the positive and negative power supply, the porous solid-state hydrogen storage material is heated by its resistance self-heating characteristics, and the stable release of hydrogen is maintained.

[0021] The application also provides a solid-state hydrogen storage method based on the above-mentioned resistance self-heating solid-state hydrogen storage reactor, comprising the following steps:

[0022] Hydrogen storage stage: hydrogen gas with a pressure of 1 MPa to 5 MPa is introduced into the reactor, and the hydrogen gas reacts with the porous solid-state hydrogen storage material to generate metal hydride, and the heat energy is stored in the phase change material storage tank through the heat management unit;

[0023] Hydrogen release stage: the heat management unit is started to transfer the heat of the phase change material storage tank to the porous solid-state hydrogen storage material, and the electric heating unit is used to supplement the heat, so that the material temperature is maintained at 280 DEG C to 320 DEG C.

[0024] The application also provides a heat recovery system based on the above-mentioned resistance self-heating solid-state hydrogen storage reactor, and the phase change material storage tank is connected to an external heat utilization device through a three-way valve for industrial waste heat recovery or regional heating.

[0025] The application also provides a preparation method of a porous solid-state hydrogen storage material for the above-mentioned resistance self-heating solid-state hydrogen storage reactor, comprising: mixing magnesium powder / magnesium alloy, coal ash slag, pore-forming agent and binder in proportion; after ball milling and compression molding, sintering at 400 DEG C to 600 DEG C for 2 hours to 6 hours to form a porous composite structure.

[0026] The application uses coal ash slag doping technology to construct a porous material, which improves the hydrogen diffusion rate and optimizes the current distribution uniformity. By using the intrinsic conductivity of the porous material, the material is rapidly self-heated by inducing Joule heat. In terms of reactor design, the alternating layered structure design of the porous solid-state hydrogen storage material and the water-cooled plate is adopted, and the risk of thermal runaway is suppressed by forced convection heat transfer.

[0027] During the hydrogen storage process, in order to prevent thermal runaway in the reactor, the temperature change in the reactor should be monitored, and when the temperature reaches the corresponding threshold, the circulating pump is opened, and the heat released by the porous solid-state hydrogen storage material in the reactor is absorbed by the heat exchange medium in the pipeline, and the corresponding heat is stored in the phase change material storage tank. During the hydrogen release process, since the process is an endothermic reaction, the circulating pump should be started, and the heat in the phase change material storage tank is taken away by the circulating medium, and the porous solid-state hydrogen storage material in the reactor is heated. If the heat stored in the phase change material storage tank is not enough, the electric heating mode can be started to continuously heat the porous solid-state hydrogen storage material by electric heating, so as to achieve the purpose of releasing hydrogen.

[0028] Beneficial effects:

[0029] 1. This invention utilizes the intrinsic Joule heating of magnesium-based porous solid hydrogen storage materials to achieve rapid and uniform heating, overcoming the problem of uneven temperature distribution in materials.

[0030] 2. This invention employs an alternating design of porous solid hydrogen storage materials and heat exchange plates to maintain the stability of the internal temperature field of the reactor through forced convection heat transfer, thereby preventing thermal runaway.

[0031] 3. This invention uses composite phase change materials to recover waste heat, further improving energy utilization efficiency. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of the structure of the self-heating solid hydrogen storage reactor based on resistance of the present invention.

[0033] In the figure, the attached labels are: 1-porous solid hydrogen storage material, 2-heat exchange plate, 3-positive power supply, 4-negative power supply, 5-hydrogen inlet and outlet, 6-circulation pump, 7-phase change material storage tank, 8-solid hydrogen storage reactor tank. Detailed Implementation

[0034] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0035] The self-heating solid hydrogen storage reactor of this invention mainly utilizes magnesium-based solid hydrogen storage materials for hydrogen storage. For example... Figure 1 As shown, this invention is used in conjunction with a phase change material storage tank to improve the energy utilization efficiency during hydrogen storage by recovering and utilizing the heat during the hydrogen release / storage process.

[0036] like Figure 1 As shown, the self-heating solid hydrogen storage reactor of the present invention includes a solid hydrogen storage reactor tank 8, a solid hydrogen storage component, a thermal management component, and an electric heating component. The solid hydrogen storage component includes a porous solid hydrogen storage material 1; the thermal management component includes a heat exchange plate 2, a circulation pump 6, and a phase change material storage tank 7; the electric heating component includes a positive power supply electrode 3 and a negative power supply electrode 4.

[0037] Porous solid hydrogen storage material 1 and heat exchange plate 2 are placed inside the solid hydrogen storage reactor tank 8. Porous solid hydrogen storage material 1 is connected to the positive terminal 3 and negative terminal 4 of the power supply via wires. Hydrogen inlet and outlet 5 are located at the top of the solid hydrogen storage reactor tank 8. Circulation pump 6 and phase change material storage tank 7 are connected to heat exchange plate 2 inside the solid hydrogen storage reactor tank 8 via pipelines.

[0038] The reactor further comprises a temperature regulation module configured to monitor the temperature of the solid-state hydrogen storage component in real time, and to control the cooperative operation of the heat management component and the electric heating component according to the upper temperature threshold of the hydrogen storage stage and the lower temperature threshold of the hydrogen release stage.

[0039] The temperature regulation module comprises:

[0040] Distributed temperature sensors arranged in the interlayer gaps of the porous solid-state hydrogen storage material 1 and on the surface of the heat exchange plate 2;

[0041] In the hydrogen storage stage, when the temperature is ≥200℃, the circulating pump 6 is started to transfer heat to the phase change material storage tank 7;

[0042] In the hydrogen release stage, the circulating pump 6 is first started to heat the porous solid-state hydrogen storage material 1, and then the electric heating unit is activated until the temperature of the porous solid-state hydrogen storage material 1 is ≥300℃.

[0043] The electric heating component includes an overload protection circuit that automatically cuts off the power supply when the current exceeds a set threshold.

[0044] Preferably, the porous solid-state hydrogen storage material 1 is used for the absorption and release of hydrogen, and the porous shape facilitates better contact between hydrogen and the solid-state hydrogen storage material.

[0045] Preferably, the heat exchange plate 2 and the porous solid-state hydrogen storage material 1 are arranged alternately, and the heat generated by the porous solid-state hydrogen storage material 1 during the hydrogen storage process is timely removed by the flow of the internal heat exchange fluid. The circulating pump 6 and the phase change material storage tank 7 are located outside the solid-state hydrogen storage reactor tank 8. The circulating pump 6 provides circulating power for the heat exchange fluid, and the heat exchange fluid exchanges heat with the porous solid-state hydrogen storage material 1 and the phase change material storage tank 7. During the hydrogen storage process, the porous solid-state hydrogen storage material 1 releases energy and the temperature rises. In order to maintain the stability of the temperature inside the solid-state hydrogen storage reactor tank 8, the circulating pump 6 needs to be turned on to timely transfer the heat generated by the porous solid-state hydrogen storage material 1 to the phase change material storage tank 7 through the internal heat exchange fluid. During the hydrogen release process, the porous solid-state hydrogen storage material 1 needs to be heated. At this time, the heat inside the phase change material storage tank 7 can be transferred to the porous solid-state hydrogen storage material 1 by turning on the circulating pump 6.

[0046] Preferably, the solid-state hydrogen storage reactor needs to continuously heat the porous solid-state hydrogen storage material 1 during the hydrogen release process, and the required heat comes partly from the phase change material storage tank 7 and partly from the electric heating. By connecting the positive electrode 3 and the negative electrode 4 of the power supply, the porous solid-state hydrogen storage material 1 is continuously heated using its inherent resistance heating characteristics, thereby maintaining the stable release of hydrogen.

[0047] The working process of the resistance self-heating type solid-state hydrogen storage reactor is as follows: the resistance self-heating type solid-state hydrogen storage reactor can realize hydrogen storage and hydrogen release; in the hydrogen storage process, hydrogen enters the inside of the solid-state hydrogen storage reactor tank 8 through the hydrogen inlet and outlet 5, then fully contacts the porous solid-state hydrogen storage material 1 in the inside of the solid-state hydrogen storage reactor tank 8 and generates a chemical reaction to generate a metal hydride, thereby realizing hydrogen storage. In the hydrogen storage process, the porous solid-state hydrogen storage material 1 and hydrogen have an exothermic reaction. In order to prevent thermal runaway in the inside of the solid-state hydrogen storage reactor tank 8, when it is monitored that the temperature in the inside of the solid-state hydrogen storage reactor tank 8 reaches a certain threshold value, the circulating pump 6 is opened in time, and the heat in the inside of the reactor is transmitted from the heat exchange plate 2 to the phase change material storage tank 7 by using the heat exchange fluid in the pipeline, thereby storing the heat in the hydrogen storage process. In the hydrogen release process, the porous solid-state hydrogen storage material 1 continuously absorbs heat, and in order to maintain the high temperature of the porous solid-state hydrogen storage material 1, the circulating pump 6 can be opened to transmit the heat in the inside of the phase change material storage tank 7 to the porous solid-state hydrogen storage material 1 by using the heat exchange fluid in the pipeline.

[0048] Specifically, in the hydrogen storage stage, hydrogen gas with a pressure of 1 MPa to 5 MPa is introduced into the reactor, the hydrogen gas reacts with the porous solid-state hydrogen storage material 1 to generate a metal hydride, and the heat release energy is stored in the phase change material storage tank 7 by the heat management unit.

[0049] In the hydrogen release stage, the heat management unit is started to transmit the heat of the phase change material storage tank 7 to the porous solid-state hydrogen storage material 1, and the electric heating unit is used to supplement the heat, so that the material temperature is maintained at 280 DEG C to 320 DEG C.

[0050] If a faster hydrogen release rate is desired, the positive electrode 3 and the negative electrode 4 of the power supply can be continuously powered, and the continuous and stable hydrogen release can be realized by using the joule heat continuously generated by the porous solid-state hydrogen storage material 1.

[0051] The present application can realize hydrogen storage and release, and further realize hydrogen energy storage. Through the recovery and utilization of heat in the hydrogen storage and release process, higher energy utilization efficiency can be realized. In order to realize more efficient and stable hydrogen release, the porous solid-state hydrogen storage material 1 can be continuously powered, and the joule heat characteristics of the porous solid-state hydrogen storage material 1 are used to realize continuous heating and stable hydrogen release.

[0052] The present application also provides a heat recovery system based on the above-mentioned reactor, and the phase change material storage tank 7 is connected to an external heat utilization device through a three-way valve, which is used for industrial waste heat recovery or regional heating.

[0053] The application further provides a preparation method of the porous solid hydrogen storage material, which is used in the above-mentioned solid hydrogen storage reactor with resistance self-heating, comprising the following steps: mixing magnesium powder / magnesium alloy, coal ash residue, pore-forming agent and binder according to a proportion; and sintering at 400-600 DEG C for 2-6 hours after ball milling and pressing forming, so as to form a porous composite structure.

[0054] The part of the application which is not described in detail belongs to the known technology of the person skilled in the art. The above-mentioned embodiments only describe the preferred embodiments of the application, and the preferred embodiments do not describe all the details and do not limit the application to the specific embodiments. Without departing from the design spirit of the application, various modifications and improvements of the technical solutions of the application made by the person skilled in the art should fall into the protection scope determined by the claims of the application.

Claims

1. A resistance-driven self-heating solid hydrogen storage reactor, characterized in that, include: Solid-state hydrogen storage components, thermal management components, and electric heating components; The solid hydrogen storage component includes a porous solid hydrogen storage material (1) arranged in alternating layers. The porous solid hydrogen storage material (1) is a magnesium-based composite material doped with coal ash slag, with a porosity ≥40%, and achieves self-heating through the Joule effect. The porous solid hydrogen storage material (1) is a porous composite structure formed by mixing magnesium powder / magnesium alloy, coal ash slag, pore-forming agent and binder in proportion, ball milling, pressing and molding, and sintering at 400°C to 600°C for 2 to 6 hours. The thermal management components include a circulating pump (6), a phase change material storage tank (7), and a heat exchange plate (2). The phase change material storage tank (7) forms a closed loop with the heat exchange plate (2) through a pipeline, and the storage tank is filled with composite phase change material. The electric heating component includes a positive power electrode (3) and a negative power electrode (4) connected to the porous solid hydrogen storage material (1) for generating auxiliary Joule heating by external power supply; The reactor also includes a temperature control module, configured to monitor the temperature of the solid hydrogen storage component in real time, and control the coordinated operation of the thermal management component and the electric heating component according to the upper temperature threshold of the hydrogen storage stage and the lower temperature threshold of the hydrogen release stage. The temperature control module includes: A distributed temperature sensor is disposed in the interlayer gap of the porous solid hydrogen storage material (1) and on the surface of the heat exchange plate (2); During the hydrogen storage stage, when the temperature is ≥200℃, the circulation pump (6) is started to transfer heat to the phase change material storage tank (7). During the hydrogen release phase, the circulating pump (6) is first started to heat the porous solid hydrogen storage material (1), and then the electric heating component is activated until the temperature of the porous solid hydrogen storage material (1) is ≥300℃.

2. The resistance self-heating solid hydrogen storage reactor according to claim 1, characterized in that, The heat exchange plate (2) is made of aluminum alloy or copper alloy.

3. The resistance self-heating solid hydrogen storage reactor according to claim 1, characterized in that, The electric heating component includes an overload protection circuit that automatically cuts off the power supply when the current exceeds a set threshold.

4. The resistance self-heating solid hydrogen storage reactor according to claim 1, characterized in that, The heat exchange plate (2) and the porous solid hydrogen storage material (1) are arranged alternately, and the heat generated by the porous solid hydrogen storage material (1) during the hydrogen storage process is removed in time by the flow of the heat exchange fluid inside.

5. The resistance self-heating solid hydrogen storage reactor according to claim 1, characterized in that, By connecting the positive terminal (3) and the negative terminal (4) of the power supply, the temperature is continuously increased by utilizing the resistance self-heating characteristics of the porous solid hydrogen storage material (1), thereby maintaining the stable release of hydrogen.

6. A method for solid-state hydrogen storage based on the resistance self-heating solid-state hydrogen storage reactor according to any one of claims 1-5, characterized in that, Includes the following steps: Hydrogen storage stage: Hydrogen gas with a pressure of 1 MPa to 5 MPa is introduced into the reactor. The hydrogen gas reacts with the porous solid hydrogen storage material (1) to generate metal hydride. At the same time, the exothermic energy is stored in the phase change material storage tank (7) through the thermal management component. Hydrogen release stage: The thermal management component is activated to transfer the heat from the phase change material storage tank (7) to the porous solid hydrogen storage material (1), and the heat is supplemented by the electric heating component to maintain the material temperature at 280°C to 320°C.

7. A heat recovery system based on the resistance self-heating solid hydrogen storage reactor according to any one of claims 1-5, characterized in that, The phase change material storage tank (7) is connected to an external heat utilization device via a three-way valve for industrial waste heat recovery or district heating.

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