Composite hydrate solid hydrogen storage systems and methods

Abstract

This invention discloses a composite hydrate solid hydrogen storage system and method. The system includes a reactor, a micro / nano bubble generator, a piston-type extrusion device, and a monitoring device. The inner wall of the reactor is coated with a hydrophobic coating and injected with a thermodynamic promoter. The micro / nano bubble generator converts the introduced hydrogen gas into micro / nano bubbles, and its outlet is connected to the reactor to introduce the micro / nano bubbles into the reactor to react with the thermodynamic promoter under low temperature and high pressure conditions to form a composite hydrate. The piston-type extrusion device scrapes off the composite hydrate adhering to the hydrophobic coating and compresses the composite hydrate in the reactor to obtain a solid hydrate hydrogen storage body. The monitoring device includes multiple electrodes arranged in the reactor at intervals along the vertical direction to monitor the distribution of the gas, liquid, and solid phases in the reactor. This improves hydrogen storage efficiency, increases the density and hydrogen storage density of the solidified hydrate, and achieves dynamic monitoring of the distribution of the gas, liquid, and solid phases in the reactor.

Description

Technical Field

[0001] This invention relates to the field of gas storage and transportation technology, specifically to a composite hydrate solid hydrogen storage system and method. Background Technology

[0002] Hydrogen is considered an ideal energy carrier due to its cleanliness and high efficiency. In recent years, my country has made continuous progress and breakthroughs in key technologies across the entire hydrogen energy production, storage, transportation, and application chain. Among these, safe and efficient storage technology is one of the key bottlenecks for the large-scale application of hydrogen energy. Solid-state hydrogen storage technology based on gas hydrates can physically encapsulate and store hydrogen in the form of hydrates at lower pressures and higher temperatures, offering advantages such as high safety and low energy consumption. However, this technology still faces challenges such as low hydrate hydrogen storage efficiency and a lack of online monitoring methods. Summary of the Invention

[0003] The main objective of this invention is to propose a composite hydrate solid hydrogen storage system and method to solve the above-mentioned problems.

[0004] To achieve the above objectives, the present invention proposes a composite hydrate solid-state hydrogen storage system, comprising:

[0005] A composite hydrate solid-state hydrogen storage system, characterized in that the composite hydrate solid-state hydrogen storage system comprises: A reaction vessel with a hydrophobic coating on its inner wall, and a thermodynamic accelerator is injected into the reaction vessel; A micro-nano bubble generator is used to convert introduced hydrogen gas into micro-nano bubbles. The outlet end of the micro-nano bubble generator is connected to the reaction vessel so that the micro-nano bubbles are introduced into the reaction vessel and react with the thermodynamic promoter under low temperature and high pressure conditions to form a composite hydrate. A piston-type extrusion device, disposed in the reactor, is used to scrape off the composite hydrate adhering to the hydrophobic coating and compress the composite hydrate inside the reactor to expel the liquid from the composite hydrate, thereby obtaining a solid hydrate hydrogen storage body; and, The monitoring device includes multiple electrodes disposed inside the reaction vessel and spaced apart in the vertical direction, for monitoring the distribution of gas, liquid and solid phases inside the reaction vessel.

[0006] Optionally, the micro / nano bubble generator is disposed inside the reaction vessel and located in the middle of the reaction vessel; The electrode is located on the lower side of the micro / nano bubble generator.

[0007] Optionally, the micro / nano bubble generator includes: The mounting base is arranged in a stepped shape, having a first step, a second step and a third step in sequence along the vertical direction. The first step is hollow and its peripheral sidewalls are hollow. A porous ceramic membrane is disposed on the step surface of the second step and is connected to the first step; and, A hydrogen pipeline has an input end connected to a hydrogen cylinder and an output end equipped with a pipe joint. The inner ring of the pipe joint is pressed onto the first step, and the outer ring of the pipe joint is fitted over the porous ceramic membrane, so that the hydrogen in the hydrogen cylinder flows sequentially through the hydrogen pipeline, the pipe joint, and the porous ceramic membrane to the bottom of the reactor to react with the thermodynamic promoter.

[0008] Optionally, the piston extrusion device includes: The piston rod is inserted into the reactor along the vertical direction and can move relative to the reactor along the vertical direction. A piston head, located at the bottom end of the piston rod and arranged in a disc shape, is used to compress the composite hydrate inside the reactor downwards. The piston head has a clearance hole extending through it along the vertical direction, corresponding to the micro / nano bubble generator. A scraping structure is provided on the outer peripheral wall of the piston head. The scraping structure extends circumferentially along the piston head and abuts against the inner peripheral wall of the reactor. It is used to scrape off the composite hydrates adhering to the hydrophobic coating.

[0009] Optionally, the piston head is provided with a plurality of drainage holes, which are located on the outer periphery of the clearance hole and are distributed at intervals along the circumference of the piston head. Each drainage hole is provided to penetrate the piston head in the vertical direction, and the channel of each drainage hole is inclined so as to allow the liquid in the composite hydrate to be discharged upward when the piston head compresses the composite hydrate downward.

[0010] Optionally, each of the electrode components includes multiple electrode plates, which are arranged sequentially along the circumference of the reactor and electrically connected to a data acquisition instrument located outside the reactor via enameled wire.

[0011] Optionally, the composite hydrate solid-state hydrogen storage system further includes: A temperature regulating device is used to regulate the temperature inside the reactor. Pressure regulating device for regulating the pressure inside the reactor; and, The control terminal is electrically connected to the piston extrusion device, the monitoring device, the temperature regulating device, and the pressure regulating device.

[0012] Optionally, the temperature regulating device includes: A water tank containing liquid and the aforementioned reaction vessel; A cooler for cooling the liquid; A heater for heating the liquid; and, A temperature sensor is installed in the reaction vessel to monitor the temperature inside the reaction vessel; The control terminal is electrically connected to the cooler, the heater, and the temperature sensor to control the working state of the cooler and the heater based on a comparison between the preset temperature stored in the terminal and the monitoring results of the temperature sensor.

[0013] Optionally, a liquid outlet is provided on the side wall of the reactor to allow the liquid squeezed out from the composite hydrate to flow out of the reactor. The pressure regulating device includes: A flow pump is installed at the inlet end of the reactor to regulate the flow rate of the thermodynamic promoter injected into the reactor. A pressure sensor, disposed in the reaction vessel, is used to monitor the pressure inside the reaction vessel; and, A solenoid valve is located at the liquid outlet; The control terminal is electrically connected to the flow pump, the pressure sensor, and the solenoid valve to control the working state of the flow pump and the working state of the solenoid valve based on the comparison between the preset pressure stored in the terminal and the monitoring results of the pressure sensor.

[0014] This invention also provides a composite hydrate solid-state hydrogen storage method, applicable to composite hydrate solid-state hydrogen storage systems, comprising the following steps: Step S100: Inject a thermodynamic accelerator into the reactor; Step S200: Hydrogen gas is converted into micro-nano bubbles through the micro-nano bubble generator and the micro-nano bubbles are injected into the reaction vessel; Step S300: Adjust the temperature and pressure inside the reactor so that the micro-nano bubbles and the thermodynamic promoter react under low temperature and high pressure conditions to form a composite hydrate, and use a monitoring device to monitor the distribution of gas phase, liquid phase and solid phase inside the reactor; Step S400: When the composite hydrate reaches a preset amount, drive the piston-type extrusion device to scrape off the composite hydrate adhering to the hydrophobic coating on the inner wall of the reactor and compress the composite hydrate in the reactor to expel the liquid in the composite hydrate and obtain a solid hydrate hydrogen storage body.

[0015] In the technical solution of this invention, the thermodynamic promoter can lower the thermodynamic energy barrier, enabling the formation of the composite hydrate under milder experimental conditions; the micro / nano bubble generator can disperse hydrogen into extremely dense micro / nano bubbles, which are more stably dispersed and denser in the hydrophobic environment formed by the hydrophobic coating, thus improving hydrogen storage efficiency; the piston-type extrusion device can periodically compress the composite hydrate in the reactor, expelling the liquid from the pores of the composite hydrate, thereby increasing the density of the hydrate solidification and the hydrogen storage density; simultaneously, the piston-type extrusion device can scrape off the composite hydrate adhering to the hydrophobic coating, achieving regeneration of the reaction space; and multiple electrode components can dynamically monitor the distribution of the gas, liquid, and solid phases in the reactor without interfering with the formation of the composite hydrate. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0017] Figure 1 A schematic diagram of an embodiment of the composite hydrate solid hydrogen storage system provided by the present invention; Figure 2 for Figure 1 A partial structural schematic diagram of the micro-nano bubble generator in a composite hydrate solid hydrogen storage system. Figure 3 for Figure 1 A schematic diagram of the piston extrusion device for a medium-composite hydrate solid hydrogen storage system; Figure 4 for Figure 3 Partial structural diagram; Figure 5 The flowchart illustrates the composite hydrate solid-state hydrogen storage method provided by this invention.

[0018] Explanation of icon numbers: 100. Composite hydrate solid-state hydrogen storage system; 1. Reactor; 11. Liquid outlet; 2. Micro-nano bubble generator; 21. Mounting base; 211. First step; 212. Second step; 213. Third step; 22. Porous ceramic membrane; 23. Hydrogen pipeline; 24. Pipe joint. 3. Piston-type extrusion device, 31. Piston rod, 32. Piston head, 321. Clearance hole, 322. Drainage hole, 33. Scraping structure; 4. Electrode components; 5. Hydrogen cylinder; 6. Temperature control device; 61. Water tank; 62. Cooler; 63. Heater; 7. Pressure regulating device; 71. Flow pump; 72. Pressure sensor; 73. Solenoid valve; 8. Control terminal; 9. Data acquisition instrument.

[0019] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0020] 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 a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0021] It should be noted that if the embodiments of the present invention involve directional indicators (such as up, down, left, right, front, back, etc.), the directional indicators are only used to explain the relative positional relationship and movement of the components in a certain specific posture (as shown in the figure). If the specific posture changes, the directional indicators will also change accordingly.

[0022] Furthermore, if the embodiments of this invention involve descriptions such as "first" or "second," these descriptions are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" or "second" may explicitly or implicitly include at least one of those features. Additionally, the meaning of "and / or" throughout the text includes three parallel solutions; for example, "A and / or B" includes solution A, solution B, or a solution where both A and B are satisfied simultaneously. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or impossible to implement, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by this invention.

[0023] Hydrogen is considered an ideal energy carrier due to its cleanliness and high efficiency. In recent years, my country has made continuous progress and breakthroughs in key technologies across the entire hydrogen energy production, storage, transportation, and application chain. Among these, safe and efficient storage technology is one of the key bottlenecks for the large-scale application of hydrogen energy. Solid-state hydrogen storage technology based on gas hydrates can physically encapsulate and store hydrogen in the form of hydrates at lower pressures and higher temperatures, offering advantages such as high safety and low energy consumption. However, this technology still faces challenges such as low hydrate hydrogen storage efficiency and a lack of online monitoring methods.

[0024] In view of this, the present invention provides a composite hydrate solid hydrogen storage system 100. Figures 1 to 4 This is an embodiment of the composite hydrate solid hydrogen storage system 100 provided by the present invention.

[0025] Please see Figures 1 to 4 The composite hydrate solid hydrogen storage system 100 includes a reaction vessel 1, a micro / nano bubble generator 2, a piston-type extrusion device 3, and a monitoring device. The inner wall of the reaction vessel 1 is coated with a hydrophobic coating, and a thermodynamic promoter is injected into the reaction vessel 1. The micro / nano bubble generator 2 is used to convert the introduced hydrogen gas into micro / nano bubbles. The outlet end of the micro / nano bubble generator 2 is connected to the reaction vessel 1 to introduce the micro / nano bubbles into the reaction vessel 1 and react with the thermodynamic promoter under low temperature and high pressure conditions to form a composite hydrate. The piston-type extrusion device 3 is located in the reaction vessel 1 and is used to scrape off the composite hydrate adhering to the hydrophobic coating and compress the composite hydrate in the reaction vessel 1 to expel the liquid in the composite hydrate and obtain a solid hydrate hydrogen storage body. The monitoring device includes multiple electrode elements 4, which are located in the reaction vessel 1 and distributed at intervals along the vertical direction to monitor the distribution state of the gas phase, liquid phase, and solid phase in the reaction vessel 1.

[0026] In the technical solution of this invention, the thermodynamic promoter can reduce the thermodynamic energy barrier, enabling the formation of the composite hydrate under milder experimental conditions; the micro / nano bubble generator 2 can disperse hydrogen into extremely dense micro / nano bubbles, which are more stably dispersed and denser in the hydrophobic environment formed by the hydrophobic coating, thus improving hydrogen storage efficiency; the piston-type extrusion device 3 can periodically compress the composite hydrate in the reactor 1, expelling the liquid from the pores of the composite hydrate, thereby increasing the density of the hydrate solidification and the hydrogen storage density. Simultaneously, the piston-type extrusion device 3 can scrape off the composite hydrate adhering to the hydrophobic coating, achieving reaction space regeneration; and multiple electrode components 4 can dynamically monitor the distribution of the gas, liquid, and solid phases within the reactor 1 without interfering with the formation of the composite hydrate.

[0027] It should be noted that the conductivity data inside the reactor 1 can be acquired in real time through the electrode components 4. Specifically, in one embodiment of the present invention, each electrode component 4 includes multiple electrode plates, which are arranged sequentially along the circumference of the reactor and electrically connected to a data acquisition instrument 9 located outside the reactor 1 via enameled wire. Thus, excitation current is applied to the multiple electrode components 4 according to a set timing sequence, the boundary voltage is measured, and the obtained voltage data is transmitted to the control terminal 8 via the data acquisition instrument 9. The data terminal then converts the voltage data into a conductivity distribution image inside the reactor 1 using an image reconstruction algorithm and displays it dynamically. More specifically, the electrode plates are attached to the inner wall of the reactor 1. Furthermore, the enameled wires connecting the electrode plates pass through two symmetrical interfaces opened on the side wall of the reactor 1, and the interfaces are potted with epoxy resin to achieve insulation and sealing.

[0028] More specifically, during the formation of the composite hydrate, the conductivity of the corresponding region will decrease significantly, thus allowing for visual observation of the entire process of the composite hydrate growing from the inner wall of the reactor 1 or the bubble interface until it expands. When the ERT image shows that the composite hydrate region no longer expands significantly, it can be determined that the amount of composite hydrate formed has reached the preset amount. Then, the driving piston extrusion device 3 will work to scrape off the composite hydrate adhering to the inner wall of the reactor 1 and compress the composite hydrate in the reactor 1, expelling the liquid from the composite hydrate to obtain a solid hydrate hydrogen storage body.

[0029] In another embodiment of the present invention, each of the electrode components 4 includes a ring body and a plurality of electrode plates. The ring body has a plurality of electrode slots, which are distributed at intervals along the circumference of the ring body. The plurality of electrode plates are correspondingly locked in the plurality of electrode slots and are electrically connected to a data acquisition instrument 9 located outside the reaction vessel 1 via an enameled wire.

[0030] Specifically, the plurality of electrode elements 4 are evenly spaced along the vertical direction. Further, based on the embodiment described above where "each electrode element 4 includes a ring body and a plurality of electrode plates," an elastic element is provided between two adjacent ring bodies, and an elastic element is provided between the bottom ring body and the bottom wall of the reactor, so that when the piston-type extrusion device 3 compresses the composite hydrate in the reactor 1, the plurality of ring bodies can be pressed down by force.

[0031] It should also be noted that, in this invention, the thermodynamic promoter can be tetrahydrofuran (THF), tetrabutylammonium bromide (TBAB), or tetrabutylammonium fluoride (TBAF), etc. More specifically, in one embodiment of this invention, the thermodynamic promoter is tetrahydrofuran (THF), which lowers the thermodynamic energy barrier and enables the formation of the composite hydrate under milder experimental conditions.

[0032] For details, please refer to Figure 1 The micro-nano bubble generator 2 is located inside the reactor 1 and in the middle of the reactor 1; the electrode 4 is located on the lower side of the micro-nano bubble generator 2.

[0033] For further details, please refer to Figure 1 and Figure 2 The micro / nano bubble generator 2 includes a mounting base 21, a porous ceramic membrane 22, and a hydrogen pipeline 23. The mounting base 21 is stepped, having a first step 211, a second step 212, and a third step 213 sequentially along the vertical direction. The first step 211 is hollow, and its peripheral sidewalls are perforated. The porous ceramic membrane 22 is disposed on the step surface of the second step 212 and is connected to the first step 211. The input end of the hydrogen pipeline 23 is connected to a hydrogen cylinder, and its output end is provided with a pipeline connector 24. The inner ring of the pipeline connector 24 is pressed onto the first step 211, and the outer ring of the pipeline connector 24 is fitted over the porous ceramic membrane 22, so that the hydrogen in the hydrogen cylinder flows sequentially through the hydrogen pipeline 23, the pipeline connector 24, and the porous ceramic membrane 22 to the bottom of the reactor 1 to react with the thermodynamic promoter.

[0034] Thus, the hydrogen pipeline 23, the pipeline joint 24, and the mounting base 21 together define the flow direction of the hydrogen, so that the hydrogen in the hydrogen cylinder flows through the pipeline joint 24 to the porous ceramic membrane 22, disperses into micro-nano bubbles with extremely high density, and sprays downwards to react with the thermodynamic promoter to form the composite hydrate under low temperature and high pressure conditions.

[0035] Furthermore, a flow meter is installed on the hydrogen pipeline 23 to measure the flow rate of hydrogen flowing into the reactor 1.

[0036] For details, please refer to Figure 3 and Figure 4The piston-type extrusion device 3 includes a piston rod 31, a piston head 32, and a scraping structure 33. The piston rod 31 is inserted into the reactor 1 along the vertical direction and can move relative to the reactor 1 along the vertical direction. The piston head 32 is located at the bottom end of the piston rod 31 and is arranged in a disc shape. It is used to compress the composite hydrate in the reactor 1 downwards. The piston head 32 has a clearance hole through it along the vertical direction corresponding to the micro-nano bubble generator 2. The scraping structure 33 is located on the outer peripheral wall of the piston head 32. The scraping structure 33 extends along the circumference of the piston head 32 and abuts against the inner peripheral wall of the reactor 1. It is used to scrape off the composite hydrate adhering to the hydrophobic coating.

[0037] Thus, when the amount of composite hydrate generated reaches a preset amount, the piston rod 31 is driven to move the piston head 32 reciprocally in the vertical direction to mechanically compress the soft composite hydrate deposition layer below, forcibly discharging the liquid THF solution retained in the pores of the composite hydrate. Simultaneously, as the piston head 32 moves downward, the scraping structure 33 can scrape off the composite hydrate adhering to the hydrophobic coating, completely removing the thin layer of hydrate adhering to the wall surface. Thus, after several reciprocating compression and scraping, a solid hydrate hydrogen storage body with low porosity and dense structure is finally obtained in the reactor 1.

[0038] It should be noted that when the piston head 32 moves along the vertical direction, the micro-nano bubble generator 2 can pass through the piston head 32 through the avoidance hole to avoid interfering with the piston head 32 and affecting the movement of the piston head 32.

[0039] For further details, please refer to Figure 4 The piston head 32 has multiple drainage holes 322, which are spaced apart circumferentially along the piston head 32. Each drainage hole 322 extends through the piston head 32 in the vertical direction, and the channel of each drainage hole 322 is inclined to allow the liquid in the composite hydrate to be discharged upward when the piston head 32 compresses the composite hydrate downward. In this way, the liquid THF solution squeezed out by the piston head 32 can be discharged upward through the drainage holes 322, avoiding a surge in pressure below the piston head 32.

[0040] Furthermore, a liquid outlet 11 is provided on the side wall of the reactor 1 to allow the solution discharged through the drainage hole 322 to flow out of the reactor 1.

[0041] Specifically, the piston-type extrusion device 3 further includes a driving component, which is drivenly connected to the piston rod 31 to drive the piston rod 31 to move relative to the reactor 1 in the vertical direction. More specifically, the driving component is a drive motor.

[0042] For details, please refer to Figure 1 The composite hydrate solid hydrogen storage system 100 further includes a temperature regulating device 6, a pressure regulating device 7, and a control terminal 8. The temperature regulating device 6 is used to regulate the temperature inside the reactor 1; the pressure regulating device 7 is used to regulate the pressure inside the reactor 1; and the control terminal 8 is electrically connected to the piston extrusion device 3, the monitoring device, the temperature regulating device 6, and the pressure regulating device 7.

[0043] Thus, the temperature and pressure inside the reactor 1 can be adjusted by controlling the temperature regulating device 6 and the pressure regulating device 7 through the control terminal 8, so that the micro-nano bubbles and the thermodynamic promoter can react under low temperature and high pressure conditions to form a composite hydrate.

[0044] It should be noted that, in this invention, the form in which the control terminal 8 is configured is not limited; it can be a computer, a tablet, a mobile phone, etc. Specifically, in one embodiment of this invention, the control terminal 8 is a computer.

[0045] Furthermore, in one embodiment of the present invention, the reaction vessel 1 is heated by a water bath to control the temperature. For details, please refer to [link to specific documentation]. Figure 1 The temperature regulating device 6 includes a water tank 61, a cooler 62, a heater 63, and a temperature sensor. The water tank 61 contains liquid and the reaction vessel 1. The cooler 62 is used to cool the liquid. The heater 63 is used to heat the liquid. The temperature sensor is located in the reaction vessel 1 and is used to monitor the temperature inside the reaction vessel 1. The control terminal 8 is electrically connected to the cooler 62, the heater 63, and the temperature sensor to control the working state of the cooler 62 and the heater 63 based on the comparison between the preset temperature stored in the terminal and the monitoring result of the temperature sensor.

[0046] Thus, the entire reactor 1 is immersed in a water tank 61 filled with circulating medium (i.e., liquid). The control terminal 8 dynamically adjusts the power of the cooler 62 or the heater 63 by comparing the preset temperature with the monitoring results of the temperature sensor (for example, by using a PID algorithm to compare), thereby heating or cooling the liquid in the water tank 61 and achieving precise temperature control of the entire reactor 1.

[0047] It should be noted that the temperature of the liquid in the water tank 61 can be controlled in real time within the water tank 61 or it can be adjusted before entering the water tank 61. For example, the temperature can be adjusted in real time within the storage tank 61 connected to the water tank 61 via a circulation pump, that is, the liquid in the storage tank 61 is input into the water tank 61 after the temperature of the liquid in the storage tank 61 reaches the preset temperature.

[0048] Furthermore, in one embodiment of the present invention, the temperature sensor is a PT100 platinum resistance sensor. More specifically, a dedicated temperature measuring interface is machined in the upper part of the side wall of the reaction vessel 1. A bottom-sealed temperature measuring sleeve is screwed onto the temperature measuring interface, with the bottom of the temperature measuring sleeve extending into the reaction vessel 1. The PT100 platinum resistance sensor is inserted into the temperature measuring sleeve, and the temperature-sensing end of the PT100 platinum resistance sensor is tightly fitted to the inner wall of the bottom of the temperature measuring sleeve. The cable of the PT100 platinum resistance sensor passes through the temperature measuring interface and is electrically connected to the control terminal 8. The control terminal 8 displays and records the core temperature value inside the reaction vessel 1.

[0049] Furthermore, the temperature measuring interface is located above the lowest compression position of the piston head 32, ensuring that the two do not interfere with each other in space.

[0050] For details, please refer to Figure 1 The side wall of the reactor 1 has a liquid outlet 11 (i.e., the liquid outlet 11 mentioned above) to allow the liquid squeezed out from the composite hydrate to flow out of the reactor 1; the pressure regulating device 7 includes a flow pump 71, a pressure sensor 72, and a solenoid valve 73. The flow pump 71 is located at the inlet end of the reactor 1 to regulate the flow rate of the thermodynamic promoter injected into the reactor 1; the pressure sensor 72 is located in the reactor 1 to monitor the pressure inside the reactor 1; the control terminal 8 is electrically connected to the flow pump 71, the pressure sensor 72, and the solenoid valve 73 to control the working state of the flow pump 71 and to control the working state of the solenoid valve 73 based on the comparison between the preset pressure stored in the flow pump 71 and the monitoring result of the pressure sensor 72.

[0051] In this way, the flow pump 71 can be controlled to continuously inject a constant flow rate of thermodynamic accelerator into the reactor 1. The pressure sensor 72 measures the pressure in the reactor 1 and transmits the pressure signal to the control terminal 8. The control terminal 8 calculates the difference between the actual pressure and the preset pressure, and uses a PID algorithm to calculate and output an electrical signal of a corresponding magnitude to control the opening of the solenoid valve 73, thereby controlling the pressure in the reactor 1 until the flow rate of the injected thermodynamic accelerator and the flow rate of the discharged liquid remain basically constant, and the pressure in the reactor 1 tends to stabilize.

[0052] Furthermore, in one embodiment of the present invention, the pressure sensor 72 is a piezoresistive pressure sensor. More specifically, the upper cover of the reactor 1 is machined with a pressure interface with internal threads, and the piezoresistive pressure sensor is directly screwed into this pressure interface through a connector with external threads machined at its lower end. During installation, a specified installation torque is applied to the threaded end of the piezoresistive pressure sensor, causing the 316 stainless steel isolation diaphragm at its front end to form a static high-pressure seal with the bottom surface of the interface through an elastic sealing gasket, thereby ensuring that the isolation diaphragm is directly connected to the reactor 1. At the same time, the electrical signal output by the internal chip of the piezoresistive pressure sensor is output through the interface and cable.

[0053] Specifically, the reactor 1 includes a vessel body, an upper cover, and a lower cover. Both the upper and lower covers are sealed with blind flanges. The upper cover is machined with a mechanical sealing cavity, a hydrogen inlet, and a pressure port. The piston rod 31 extends into the vessel body through the mechanical sealing cavity. The hydrogen pipeline 23 is connected to the micro / nano bubble generator 2 through the hydrogen inlet. The upper cover is made of 316 stainless steel through integral forging, and local reinforcement is applied to the areas where the mechanical sealing cavity, the hydrogen inlet, and the pressure port are located to ensure overall sealing reliability under multi-port conditions. The pressure port facilitates connection to a piezoresistive pressure sensor and also serves as the outlet for the sensor's connected wires.

[0054] Specifically, this invention also provides a composite hydrate solid-state hydrogen storage method, applicable to the composite hydrate solid-state hydrogen storage system described above. Please refer to [link to relevant documentation]. Figure 5 The composite hydrate solid-state hydrogen storage method includes the following steps: Step S100: Inject a thermodynamic accelerator into the reactor.

[0055] In this step, a thermodynamic accelerator of a predetermined concentration (such as an aqueous solution of tetrahydrofuran) is injected into the reactor through the inlet to a preset liquid level.

[0056] Step S200: Hydrogen gas is converted into micro-nano bubbles through the micro-nano bubble generator, and the micro-nano bubbles are injected into the reaction vessel.

[0057] More specifically, the flow rate of hydrogen from the hydrogen cylinder to the micro / nano bubble generator is controlled by a flow meter.

[0058] Step S300: Adjust the temperature and pressure inside the reactor so that the micro-nano bubbles and the thermodynamic promoter react under low temperature and high pressure conditions to form a composite hydrate, and use a monitoring device to monitor the distribution of gas phase, liquid phase and solid phase inside the reactor.

[0059] In this step, the temperature and pressure inside the reactor are adjusted by temperature and pressure regulating devices to keep the reactor in a low-temperature and high-pressure state. Meanwhile, during the interaction between the micro-nano bubbles and the thermodynamic promoter, the distribution of the gas, liquid, and solid phases inside the reactor is monitored by the monitoring device.

[0060] More specifically, in one embodiment of the present invention, the monitoring device includes four electrode components spaced apart along the vertical direction. Each electrode component includes multiple electrode plates sequentially distributed along the circumference of the reactor. The four electrode components are reliably connected to the multi-channel terminal block of the data acquisition instrument through a total of 64 enameled wires. The data acquisition instrument adopts an adjacent excitation-adjacent measurement mode, and the excitation current is a sinusoidal AC signal of 1-10mA and 1-100kHz.

[0061] Furthermore, the specific testing process for the electrode is as follows: For the 16 electrodes of the first layer of electrodes, a clockwise scan is performed: an excitation current is applied sequentially to adjacent pairs of electrodes, and the boundary voltage is measured between the remaining adjacent pairs of electrodes. After one round of scanning for a single layer, 104 independent voltage measurements are obtained. The data acquisition instrument is then controlled to repeat the above scanning process for the second, third, and fourth layers of electrodes according to the same logic. After completing four layers of cyclic scanning, a total of 416 independent boundary voltage measurements are obtained. These data constitute the electrical state information of the reactor at four different height sections at the current moment. The obtained 416 voltage measurements are transmitted to the control terminal. The control terminal calls the pre-calibrated and constructed three-dimensional sensitive field matrix and image reconstruction algorithm to reconstruct the voltage data into a three-dimensional conductivity distribution image inside the reactor. By setting a conductivity threshold, the image is segmented and identified, thereby quantitatively characterizing the distribution and changes of the gas phase, liquid phase, and complex hydrate solid phase in different regions of the reactor in real time and with visualization.

[0062] During the formation of complex hydrates, the electrical conductivity of the corresponding region decreases significantly, allowing for visual observation of the entire process of complex hydrate growth from the reactor sidewall or bubble interface to its expansion. When the ERT image shows that the complex hydrate region no longer expands significantly, it is determined that the formation of complex hydrates has reached the preset amount, and the process proceeds to the next stage.

[0063] Step S400: When the composite hydrate reaches a preset amount, drive the piston-type extrusion device to scrape off the composite hydrate adhering to the hydrophobic coating on the inner wall of the reactor and compress the composite hydrate in the reactor to expel the liquid in the composite hydrate and obtain a solid hydrate hydrogen storage body.

[0064] In this step, after repeated compression and scraping by the piston head, a solid hydrate hydrogen storage body with low porosity and dense structure is finally obtained in the reactor.

[0065] Furthermore, after slowly depressurizing the reactor, samples of the solid hydrate hydrogen storage medium can be taken or stored. Then, the liquid outlet is opened to discharge the liquid in the composite hydrate, and the piston head is reset to the initial position, completing one hydrogen storage cycle and preparing for the next cycle.

[0066] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention's specification and drawings under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A composite hydrate solid-state hydrogen storage system, characterized in that, The composite hydrate solid hydrogen storage system includes: A reaction vessel with a hydrophobic coating on its inner wall, and a thermodynamic accelerator is injected into the reaction vessel; A micro-nano bubble generator is used to convert introduced hydrogen gas into micro-nano bubbles. The outlet end of the micro-nano bubble generator is connected to the reaction vessel so that the micro-nano bubbles are introduced into the reaction vessel and react with the thermodynamic promoter under low temperature and high pressure conditions to form a composite hydrate. A piston-type extrusion device, disposed in the reactor, is used to scrape off the composite hydrate adhering to the hydrophobic coating and compress the composite hydrate inside the reactor to expel the liquid from the composite hydrate, thereby obtaining a solid hydrate hydrogen storage body; and, The monitoring device includes multiple electrodes disposed inside the reactor and spaced apart in the vertical direction, for monitoring the distribution of gas, liquid and solid phases inside the reactor.

2. The composite hydrate solid-state hydrogen storage system as described in claim 1, characterized in that, The micro-nano bubble generator is located inside the reactor and in the middle of the reactor. The electrode is located on the lower side of the micro / nano bubble generator.

3. The composite hydrate solid-state hydrogen storage system as described in claim 2, characterized in that, The micro / nano bubble generator includes: The mounting base is arranged in a stepped shape, having a first step, a second step and a third step in sequence along the vertical direction. The first step is hollow and its peripheral sidewalls are hollow. A porous ceramic membrane is disposed on the step surface of the second step and is connected to the first step; and, A hydrogen pipeline has an input end connected to a hydrogen cylinder and an output end equipped with a pipe joint. The inner ring of the pipe joint is pressed onto the first step, and the outer ring of the pipe joint is fitted over the porous ceramic membrane, so that the hydrogen in the hydrogen cylinder flows sequentially through the hydrogen pipeline, the pipe joint, and the porous ceramic membrane to the bottom of the reactor to react with the thermodynamic promoter.

4. The composite hydrate solid-state hydrogen storage system as described in claim 1, characterized in that, The piston-type extrusion device includes: The piston rod is inserted into the reactor along the vertical direction and can move relative to the reactor along the vertical direction. A piston head, located at the bottom end of the piston rod and arranged in a disc shape, is used to compress the composite hydrate inside the reactor downwards. The piston head has a clearance hole extending through it along the vertical direction, corresponding to the micro / nano bubble generator. A scraping structure is provided on the outer peripheral wall of the piston head. The scraping structure extends circumferentially along the piston head and abuts against the inner peripheral wall of the reactor. It is used to scrape off the composite hydrates adhering to the hydrophobic coating.

5. The composite hydrate solid-state hydrogen storage system as described in claim 4, characterized in that, The piston head is provided with a plurality of drainage holes, which are located on the outer periphery of the clearance hole and are distributed at intervals along the circumference of the piston head. Each drainage hole is arranged to penetrate the piston head in the vertical direction, and the channel of each drainage hole is inclined so as to allow the liquid in the composite hydrate to be discharged upward when the piston head compresses the composite hydrate downward.

6. The composite hydrate solid-state hydrogen storage system as described in claim 1, characterized in that, Each of the electrode components includes multiple electrode plates, which are arranged sequentially along the circumference of the reactor and electrically connected to a data acquisition instrument located outside the reactor via enameled wire.

7. The composite hydrate solid-state hydrogen storage system as described in claim 1, characterized in that, The composite hydrate solid hydrogen storage system also includes: A temperature regulating device is used to regulate the temperature inside the reactor. Pressure regulating device for regulating the pressure inside the reactor; and, The control terminal is electrically connected to the piston extrusion device, the monitoring device, the temperature regulating device, and the pressure regulating device.

8. The composite hydrate solid-state hydrogen storage system as described in claim 7, characterized in that, The temperature regulating device includes: A water tank containing liquid and the aforementioned reaction vessel; A cooler for cooling the liquid; A heater for heating the liquid; and, A temperature sensor is installed in the reaction vessel to monitor the temperature inside the reaction vessel; The control terminal is electrically connected to the cooler, the heater, and the temperature sensor to control the working state of the cooler and the heater based on a comparison between the preset temperature stored in the terminal and the monitoring results of the temperature sensor.

9. The composite hydrate solid-state hydrogen storage system as described in claim 7, characterized in that, The side wall of the reactor has a liquid outlet to allow the liquid squeezed out from the composite hydrate to flow out of the reactor. The pressure regulating device includes: A flow pump is installed at the inlet end of the reactor to regulate the flow rate of the thermodynamic promoter injected into the reactor. A pressure sensor, disposed in the reaction vessel, is used to monitor the pressure inside the reaction vessel; and, A solenoid valve is located at the liquid outlet; The control terminal is electrically connected to the flow pump, the pressure sensor, and the solenoid valve to control the working state of the flow pump and the working state of the solenoid valve based on the comparison between the preset pressure stored in the terminal and the monitoring results of the pressure sensor.

10. A method for solid-state hydrogen storage using composite hydrates, characterized in that, The composite hydrate solid-state hydrogen storage system according to any one of claims 1-9 includes the following steps: Step S100: Inject a thermodynamic accelerator into the reactor; Step S200: Hydrogen gas is converted into micro-nano bubbles through the micro-nano bubble generator and the micro-nano bubbles are injected into the reaction vessel; Step S300: Adjust the temperature and pressure inside the reactor so that the micro-nano bubbles and the thermodynamic promoter react under low temperature and high pressure conditions to form a composite hydrate, and use a monitoring device to monitor the distribution of gas phase, liquid phase and solid phase inside the reactor; Step S400: When the composite hydrate reaches a preset amount, drive the piston-type extrusion device to scrape off the composite hydrate adhering to the hydrophobic coating on the inner wall of the reactor and compress the composite hydrate in the reactor to expel the liquid in the composite hydrate and obtain a solid hydrate hydrogen storage body.

Images