A hydrogen storage test device and method based on Sieverts method
By designing the coordination between the branch pipeline and the vacuum pump and the disassembly interface structure of the reaction chamber in the hydrogen storage test device, the problems of poor sealing and difficulty in hydrogen pressure adjustment in the prior art are solved, and the accurate hydrogen release curve determination of the hydrogen storage material is achieved and Efficient performance detection.
Patent Information
- Application Number
- CN202210336704.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-03-31
- Publication Date
- 2025-01-07
- Estimated Expiration
- 2042-03-31
AI Technical Summary
The existing hydrogen storage test device has poor sealing at high temperatures, and the hydrogen discharge curve is difficult to accurately measure, and the hydrogen pressure in the hydrogen pipeline cannot be adjusted secondaryly, resulting in an increase in the hydrogen discharge reaction system, affecting the measurement accuracy.
A hydrogen storage test device based on Sieverts method is designed, including a reaction system, a gas pipeline system and a data acquisition system. Through the cooperation of the branch pipeline and the vacuum pump, the secondary adjustment of the hydrogen pressure is achieved, and a disassembly interface is set up at the upper end of the reaction chamber. and filtering devices ensure sealing and precise determination.
Multi-circulation hydrogen absorption and release tests for safe and reliable hydrogen storage materials in different temperature ranges are achieved, and the impact of hydrogen release on the hydrogen pressure of the hydrogen discharge reaction system is overcome, ensuring the accurate determination of the hydrogen discharge curve and efficient detection of hydrogen storage performance.
Smart Images
Figure CN114778378B_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of hydrogen storage material performance detection, and relates to a novel hydrogen storage testing device and method based on the Sieverts method. Background Art
[0002] As a clean energy, hydrogen has the highest energy density per unit mass except for nuclear energy and is considered to be one of the most promising energy carriers. The efficient production, safe storage and transportation, and rational application of hydrogen are the three key links in the development and utilization of hydrogen energy. With the increasing maturity of hydrogen production technology and the rapid development of fuel cell technology, safe, efficient and economical hydrogen storage and transportation technology has become a bottleneck restricting the hydrogen energy economy. At present, the storage methods of hydrogen mainly include high-pressure gas, cooling liquid and solid material hydrogen storage. High-pressure gas hydrogen storage has a low density and is subject to the risk of leakage and explosion; the ultra-low temperature containers for cooling liquid hydrogen storage are extremely expensive, and the energy consumed by hydrogen liquefaction and storage can account for 30% to 45% of the total hydrogen storage energy.
[0003] In comparison, solid material hydrogen storage uses the physical adsorption and chemical bonding of hydrogen to store hydrogen, and has the advantages of high volume hydrogen storage density and good safety. The mass and volume hydrogen storage density of some solid materials can even be higher than that of cooled liquid hydrogen storage, and have good application prospects. They are expected to replace high-pressure gas hydrogen storage and cooled liquid hydrogen storage in specific fields, thereby achieving safe, economical and efficient storage of hydrogen. For example, MgH2 hydrogen storage material has the advantages of high theoretical hydrogen storage density (mass hydrogen storage density 7.6wt.%), good reversibility of hydrogen absorption and desorption, and abundant resources. However, the dehydrogenation temperature of MgH2 is too high, and the hydrogen absorption and desorption rate is slow, which makes it difficult to meet the needs of hydrogen storage applications. It is necessary to further optimize the composition and structure to improve the hydrogen storage performance of the material. It can be seen that in the field of scientific research and product development, it is of great theoretical and practical significance to test the hydrogen absorption and desorption performance of hydrogen storage materials.
[0004] The test of hydrogen absorption and desorption performance of solid hydrogen storage materials can be divided into mass method and volume method, which respectively test the hydrogen absorption and desorption performance of materials by the change of sample mass and the change of pipeline gas volume. Its main parameters include reaction temperature and hydrogen pressure. Due to the small atomic number of hydrogen, the mass method test has a large error; due to the large volume of hydrogen per unit mass, the volume method test has the advantages of accurate results and easy implementation. A hydrogen storage test device based on the Sieverts method (also known as the isochoric method) is usually used to characterize the hydrogen storage performance of the material. The device changes the temperature and hydrogen pressure conditions of the hydrogenation and dehydrogenation reactions, and uses the ideal gas equation PV=ZnRT to achieve the determination and calculation of the isothermal hydrogen absorption and desorption curve. For the existing manual hydrogen storage test device, the loading and unloading procedures of the reaction chamber are cumbersome, and the sealing ring is easy to deform and leak at high temperature. More importantly, the hydrogen pressure required for hydrogen storage material dehydrogenation is usually only 0-0.1MPa. Since the hydrogen pressure of the gas pipeline cannot be adjusted twice during a single reaction of ordinary devices, the hydrogen released by the reaction causes the hydrogen pressure of the gas pipeline to increase significantly, making it difficult to accurately determine the dehydrogenation curve. Summary of the invention
[0005] Purpose of the Invention
[0006] In order to make up for the technical deficiencies of the above-mentioned existing hydrogen storage testing devices and the problem that the hydrogen desorption curve of hydrogen storage materials is difficult to accurately measure, the present invention provides a hydrogen storage testing device and method based on the Sieverts method, which is safe and reliable, easy to operate, and can complete multi-cycle hydrogen absorption and desorption testing of hydrogen storage materials in different temperature ranges.
[0007] Technical Solution
[0008] A hydrogen storage test device based on Sieverts method, comprising a reaction system, a gas pipeline system, a data acquisition system, a gas source pipeline, an exhaust collection pipeline and a vacuum pump, wherein the gas pipeline system comprises a main gas pipeline and a branch gas pipeline, one end of the main gas pipeline is connected to the reaction system, a third filtering device and a ninth throttle valve are arranged between the main gas pipeline and the reaction system, the other end of the main gas pipeline is respectively connected to the gas source pipeline, the exhaust collection pipeline and the vacuum pump, the gas source pipeline is formed by connecting a pipeline connected to a hydrogen source and a pipeline connected to an argon source in parallel, the exhaust collection pipeline is formed by connecting a pipeline connected to a gas collection device and a pipeline connected to an exhaust device in parallel, a first filter is arranged between the main gas pipeline and the gas source pipeline The filter device is provided with a second throttle valve, a third throttle valve, a fifth throttle valve and a sixth throttle valve respectively on the pipeline connected to the hydrogen source, the pipeline connected to the argon source, the pipeline connected to the gas collecting device and the pipeline connected to the exhaust device. A seventh throttle valve is provided between the main gas pipeline and the vacuum pump. The main gas pipeline is provided with a fourth throttle valve, a second filter device and a temperature sensor. The middle part of the main gas pipeline is connected to one end of the branch gas pipeline and the high-pressure container. The high-pressure container is connected to a high-pressure sensor. The branch gas pipeline is provided with a first throttle valve and a low-pressure container. The low-pressure container is connected to a low-pressure sensor. The other end of the branch gas pipeline is connected to the vacuum pump. An eighth throttle valve is provided between the branch gas pipeline and the vacuum pump. A thermocouple is provided in the reaction system. The thermocouple, the high-pressure sensor, the low-pressure sensor and the temperature sensor are all connected to the data acquisition system signal.
[0009] Furthermore, the reaction system includes a heating furnace and a reaction chamber, the main body of the reaction chamber is located inside the heating furnace, a resistance wire is provided inside the heating furnace, the gap between the heating furnace and the reaction chamber is filled with a thermal insulation sealing layer, a plurality of thermocouples are evenly arranged at the bottom of the inner furnace of the heating furnace, the upper end of the reaction chamber is connected to the third filter device and the ninth throttle valve through a first disassembly interface, and the upper ends of the third filter device and the ninth throttle valve are connected to the main gas pipeline through a second disassembly interface.
[0010] Furthermore, the first disassembly interface includes a first sealing nut, the upper end of the reaction chamber is threadedly connected to the first sealing nut, the first sealing nut is also fixed to the lower end of the connecting pipe, a copper gasket is provided between the upper end of the reaction chamber and the lower end of the connecting pipe, and the connecting pipe is used to connect the third filter device and the ninth throttle valve.
[0011] Furthermore, the second disassembly interface includes a second sealing nut, and the connecting pipeline between the third filter device and the upper end of the ninth throttle valve is connected to the main pipeline. The connection between the main pipeline and the connecting pipeline is a structure with a larger diameter at the upper end and a smaller diameter at the lower end. The second sealing nut is threadedly connected to the upper end of the connecting pipeline between the third filter device and the upper end of the ninth throttle valve, and an aluminum gasket is arranged inside the second sealing nut between the connecting pipeline between the third filter device and the upper end of the ninth throttle valve and the main pipeline, and a spring gasket is also arranged between the upper end of the second sealing nut and the main pipeline.
[0012] Furthermore, the adjustable temperature range in the reaction system is from room temperature to 500°C, and the temperature deviation is ≤0.1°C; the total volume of the connecting pipeline and the reaction chamber is 25mL, the reaction chamber is made of 304 stainless steel, and is in the shape of a circular tube with a closed lower end. The volume of the reaction chamber is 15mL, the total volume of the main pipeline including the high-pressure container is 500mL, the volume of the high-pressure container is 300mL, the total volume of the branch pipeline including the low-pressure container is 1000mL, and the volume of the low-pressure container is 900mL.
[0013] Furthermore, the data acquisition system includes a computer, a display instrument and a data collector, the thermocouple, the high-pressure sensor, the low-pressure sensor and the temperature sensor are all connected to the data collector signal, the data collector is electrically connected to the display instrument, and the display instrument is electrically connected to the computer.
[0014] A hydrogen storage test method using the hydrogen storage test device based on the Sieverts method as described:
[0015] a) Loading of hydrogen storage material sample: the first throttle valve, the second throttle valve, the third throttle valve, the fourth throttle valve, the fifth throttle valve, the sixth throttle valve, the seventh throttle valve, the eighth throttle valve and the ninth throttle valve are in a closed state, firstly, the hydrogen storage material sample is loaded into the reaction chamber, the first disassembly interface is assembled and tightened to seal, and the second disassembly interface is assembled and tightened to seal;
[0016] b) Leak detection of the gas pipeline system: first open the first throttle valve, the fourth throttle valve and the ninth throttle valve, and then open the vacuum pump and the seventh throttle valve in sequence to evacuate the gas pipeline system; then close the seventh throttle valve and the vacuum pump in sequence, and then open the argon source and the third throttle valve in sequence, fill the gas pipeline with argon to 1MPa, and use an argon detector to check whether the first disassembly interface and the second disassembly interface are leaking; if there is a leak, close the third throttle valve and the argon source in sequence, open the sixth throttle valve to exhaust to the standard atmospheric pressure, close the sixth throttle valve, unscrew the second disassembly interface and the first disassembly interface in sequence, repeat steps a) and b) until there is no leak, and perform the operation of no leak; if there is no leak, open the sixth throttle valve to exhaust to the standard atmospheric pressure, close the sixth throttle valve, open the vacuum pump and the seventh throttle valve in sequence, and evacuate the gas pipeline system; finally, close the seventh throttle valve and the vacuum pump in sequence, and prepare to perform the performance test of the hydrogen storage material sample;
[0017] c) Isothermal hydrogen absorption performance test: the first throttle valve, the second throttle valve, the third throttle valve, the fourth throttle valve, the fifth throttle valve, the sixth throttle valve, the seventh throttle valve, the eighth throttle valve and the ninth throttle valve are in a closed state. First, the temperature of the heating furnace is set for heating and heat preservation. Then, the hydrogen source and the second throttle valve are opened in sequence, and hydrogen is filled into the main pipeline system to the required hydrogen pressure. At this time, the hydrogen pressure is higher than the reaction hydrogen pressure. Then, the fourth throttle valve and the ninth throttle valve are opened in sequence, and the isothermal hydrogen absorption curve is measured, and the data acquisition system records the data;
[0018] d) Isothermal hydrogen desorption performance test: After the hydrogen storage material sample has completed hydrogen absorption, an isothermal hydrogen desorption performance test is performed. The first throttle valve, the second throttle valve, the third throttle valve, the fourth throttle valve, the fifth throttle valve, the sixth throttle valve, the seventh throttle valve, the eighth throttle valve and the ninth throttle valve are in a closed state. First, the fourth throttle valve and the ninth throttle valve are opened, and the hydrogen source and the second throttle valve are opened in sequence at the same time to increase the hydrogen pressure of the reaction system to the value required for the hydrogen storage material sample to remain stable. The second throttle valve and the hydrogen source are closed in sequence, and the heating furnace temperature is set to heat and keep warm. Then, the ninth throttle valve is closed, and the sixth throttle valve is opened for exhaust. After the exhaust is completed, the vacuum pump and the seventh throttle valve are opened in sequence to perform the main The pipeline is evacuated; then the seventh throttle valve and the vacuum pump are closed in turn, and the first throttle valve and the ninth throttle valve are opened in turn, and the isothermal hydrogen desorption curve is measured, and the data acquisition system records the data; since the hydrogen pressure required for hydrogen desorption of the hydrogen storage material sample is relatively low, usually only 0-0.1MPa, the hydrogen desorption of the hydrogen storage material sample causes the hydrogen pressure of the reaction system to increase significantly, resulting in changes in the hydrogen desorption environment, and the hydrogen desorption curve is difficult to accurately measure; at this time, it is necessary to close the first throttle valve and temporarily use the main pipeline to measure the hydrogen desorption curve; at the same time, open the vacuum pump and the eighth throttle valve in turn, adjust the hydrogen pressure of the branch pipeline, close the eighth throttle valve and the vacuum pump in turn, open the first throttle valve, and continue to use the entire pipeline to measure the isothermal hydrogen desorption curve.
[0019] e) Unloading of hydrogen storage material samples: After the isothermal hydrogen absorption / desorption performance test is completed, the samples need to be taken out for further analysis;
[0020] For the isothermal hydrogen absorption sample in step c), after the hydrogen absorption test is completed, the hydrogen pressure of the reaction system is increased to the value required for the hydrogen storage material to remain stable, and then the reaction chamber is cooled to room temperature, and the sixth throttle valve is opened for exhaust; after the exhaust is completed, the sixth throttle valve is closed, and the vacuum pump and the eighth throttle valve are opened in sequence to perform vacuum treatment; then the argon source and the third throttle valve are opened in sequence, and after argon is filled into the main line to 0.1MPa, the third throttle valve and the argon source are closed in sequence, and the ninth throttle valve and the fourth throttle valve are closed at the same time, and the second disassembly interface and the first disassembly interface are unscrewed in sequence.
[0021] For the isothermal hydrogen desorption sample in step d), after the hydrogen desorption test is completed, the vacuum pump and the eighth throttle valve are opened in sequence to carry out vacuum treatment. After the vacuum treatment is completed, the eighth throttle valve and the vacuum pump are first closed in sequence to cool the reaction chamber to room temperature; then the argon source and the third throttle valve are opened in sequence, and after argon is filled into the main line to 0.1MPa, the third throttle valve and the argon source are closed in sequence, and the ninth throttle valve and the fourth throttle valve are closed at the same time, and the second disassembly interface and the first disassembly interface are unscrewed in sequence.
[0022] Furthermore, in step c) and step d), the heat preservation time after heating in the heating furnace is greater than or equal to 2 hours.
[0023] Furthermore, in a reaction system with constant volume, the amount of hydrogen absorbed and desorbed by the sample is calculated by the ideal gas equation: PV=ZnRT, and then the isothermal hydrogen absorption and desorption curve is obtained; wherein P is the pressure of hydrogen in the reaction system, V is the volume of the reaction system and pipeline used in the corresponding test, Z is the compression factor of hydrogen, n is the amount of substance involved in the reaction of hydrogen, R is the gas constant, and T is the thermodynamic temperature of the environment surrounding the reaction system.
[0024] Advantages and effects
[0025] The device of the present invention is safe and reliable, simple in structure and easy to operate. By designing a separate branch pipeline on the gas pipeline of the hydrogen storage test device to connect the main pipeline and the vacuum pump respectively, the secondary adjustment of the hydrogen pressure of the reaction system during a single hydrogen release process is realized, thereby overcoming the influence of hydrogen release on the hydrogen pressure of the hydrogen release reaction system. Among them, a low-pressure container and a low-pressure sensor are arranged on the branch pipeline, and throttle valves are arranged at both ends. Through the use of the throttle valve and the vacuum pump, the hydrogen pressure of the hydrogen release reaction system is adjusted, and then the accurate determination of the isothermal hydrogen release curve of the hydrogen storage material is realized. By arranging two disassembly interfaces and a filtering device at the upper end of the reaction chamber, the difficult problem that the hydrogen storage test is difficult to carry out under high temperature conditions and the material sample is easily inhaled into the gas pipeline is solved. Among them, the sealing gasket close to the end of the reaction chamber is a copper gasket, and the sealing gasket close to the end of the gas pipeline is an aluminum gasket. The sealing effect of this structure is good in different temperature ranges, and the cyclic hydrogen storage performance test of the hydrogen storage material in the range of RT to 500°C can be realized. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] The present invention is further described below in conjunction with the accompanying drawings and specific implementation methods. The protection scope of the present invention is not limited to the following description.
[0027] Figure 1 It is a structural schematic diagram of a hydrogen storage test device based on the Sieverts method;
[0028] Figure 2 It is a structural schematic diagram of the reaction chamber and the first disassembly interface;
[0029] Figure 3This is a structural schematic diagram of the second disassembly interface.
[0030] Description of reference numerals: 1. Hydrogen source, 2. Argon source, 3. First filter device, 4. Second filter device, 5. Third filter device, 6. First throttle valve, 7. Second throttle valve, 8. Third throttle valve, 9. Fourth throttle valve, 10. Fifth throttle valve, 11. Sixth throttle valve, 12. Seventh throttle valve, 13. Eighth throttle valve, 14. Ninth throttle valve, 15. First disassembly interface, 16. Second disassembly interface, 17. Reaction chamber, 18. Heating furnace, 19. 1. High-pressure container, 20. Low-pressure container, 21. High-pressure sensor, 22. Low-pressure sensor, 23. Thermocouple, 24. Temperature sensor, 25. Vacuum pump, 26. Gas collecting device, 27. Exhaust device, 28. Computer, 29. Display instrument, 30. Data acquisition device, 31. Thermal insulation sealing layer, 32. First sealing nut, 33. Copper gasket, 34. Connecting pipeline, 35. Second sealing nut, 36. Aluminum gasket, 37. Resistance wire, 38. Spring gasket. DETAILED DESCRIPTION
[0031] like Figure 1 , Figure 2 and Figure 3As shown, a hydrogen storage test device based on the Sieverts method includes a reaction system, a gas pipeline system, a data acquisition system, a gas source pipeline, an exhaust pipeline and a vacuum pump 25. The gas pipeline system includes a main gas pipeline and a branch gas pipeline. One end of the main gas pipeline is connected to the reaction system. A third filtering device 5 and a ninth throttle valve 14 are provided between the main gas pipeline and the reaction system. The other end of the main gas pipeline is respectively connected to the gas source pipeline, the exhaust pipeline and the vacuum pump 25. The gas source pipeline is formed by connecting a pipeline connected to a hydrogen source 1 and a pipeline connected to an argon source 2 in parallel. The exhaust pipeline is formed by connecting a pipeline connected to a gas collecting device 26 and a pipeline connected to an exhaust device 27 in parallel. A first filtering device 3 is provided between the main gas pipeline and the gas source pipeline. The pipeline connected to the hydrogen source 1, the pipeline connected to the argon source 2, the pipeline connected to the gas collecting device 26 and the pipeline connected to the exhaust device 27 are respectively provided with a second throttle valve 14. A seventh throttle valve 12 is provided between the main gas pipeline and the vacuum pump 25, and a fourth throttle valve 9, a second filter device 4 and a temperature sensor 24 are provided on the main gas pipeline. The first filter device 3, the second filter device 4 and the third filter device 5 used in this example are filters of Shanghai Xitai Fluid Technology Co., Ltd., model UF-K6. The middle part of the main gas pipeline is connected to one end of the branch gas pipeline and a high-pressure container 19, and the high-pressure container 19 is connected to a high-pressure sensor 21. The branch gas pipeline is provided with a first throttle valve 6 and a low-pressure container 20, and the low-pressure container 20 is connected to a low-pressure sensor 22. The purpose of setting the high-pressure container 19 and the low-pressure container 20 is to set an independent reaction system volume module, which increases the overall volume capacity of the gas pipeline system on the one hand, facilitates the increase of the volume of the gas pipeline during the hydrogen desorption performance test, and stabilizes the hydrogen pressure of the hydrogen desorption test. The other end of the branch gas pipeline is connected to the vacuum pump 25, and an eighth throttle valve 13 is provided between the branch gas pipeline and the vacuum pump 25. A thermocouple 23 is provided in the reaction system, and the thermocouple 23, the high pressure sensor 21, the low pressure sensor 22 and the temperature sensor 24 are all connected to the data acquisition system signal. The reaction system includes a heating furnace 18 and a reaction chamber 17, the main body of the reaction chamber 17 is located inside the heating furnace 18, a resistance wire 37 is provided in the heating furnace 18, and the gap between the heating furnace 18 and the reaction chamber 17 is filled with a thermal insulation sealing layer 31, and the thermal insulation sealing layer 31 is preferably asbestos. A plurality of thermocouples 23 are evenly arranged at the bottom of the inner furnace of the heating furnace 18, and the upper end of the reaction chamber 17 is connected to the third filter device 5 and the ninth throttle valve 14 through the first disassembly interface 15, and the upper ends of the third filter device 5 and the ninth throttle valve 14 are connected to the main gas pipeline through the second disassembly interface 16.
[0032] The first disassembly interface 15 includes a first sealing nut 32, the upper end of the reaction chamber 17 is threadedly connected with the first sealing nut 32, the lower end of the connecting pipeline 34 is also fixed inside the first sealing nut 32, a copper gasket 33 is provided between the upper end of the reaction chamber 17 and the lower end of the connecting pipeline 34, and the connecting pipeline 34 is used to connect the third filter device 5 and the ninth throttle valve 14. The second disassembly interface 16 includes a second sealing nut 35, the connecting pipeline 34 at the upper end of the third filter device 5 and the ninth throttle valve 14 is connected to the main pipeline, and the connection between the main pipeline and the connecting pipeline 34 is a structure with a large diameter at the upper end and a small diameter at the lower end, the second sealing nut 35 is threadedly connected to the upper end of the connecting pipeline 34 at the upper end of the third filter device 5 and the ninth throttle valve 14, and an aluminum gasket 36 is provided inside the second sealing nut 35 between the connecting pipeline 34 at the upper end of the third filter device 5 and the ninth throttle valve 14 and the main pipeline, and a spring gasket 38 is also provided between the upper end of the second sealing nut 35 and the main pipeline. Due to different ambient temperatures, the first disassembly interface 15 and the second disassembly interface 16 are sealed using a copper gasket 33 and an aluminum gasket 36 respectively.
[0033] The adjustable temperature range in the reaction system is from room temperature to 500°C, and the temperature deviation is ≤0.1°C; the total volume of the connecting pipeline 34 and the reaction chamber 17 is 25mL, and the reaction chamber 17 is made of 304 stainless steel and is in the shape of a round tube with a closed lower end. The volume of the reaction chamber 17 is 15mL, which is used to place hydrogen storage material samples; the first filter device 3, the second filter device 4 and the third filter device 5 filter the hydrogen storage samples with a particle size greater than 5μm and prevent them from entering the gas pipeline, which can effectively prevent the hydrogen storage samples from entering the gas pipeline. The total volume of the main pipeline including the high-pressure container 19 is 500mL, and the volume of the high-pressure container 19 is 300mL. The total volume of the branch pipeline including the low-pressure container 20 is 1000mL, and the volume of the low-pressure container 20 is 900mL. The high-pressure container 19 is mainly used for testing hydrogen absorption performance. The hydrogen pressure in the working environment is usually higher than 1 MPa, and the upper pressure limit of the high-pressure container 19 is 5 MPa. The low-pressure container 20 is used for testing hydrogen release performance. The hydrogen pressure in the working environment is usually 0-0.1 MPa.
[0034] The data acquisition system includes a computer 28, a display instrument 29 and a data acquisition device 30. The data acquisition device 30 used in this example is a 6100 series product of Shanghai Yijie Automation Technology Co., Ltd. The thermocouple 23, the high pressure sensor 21, the low pressure sensor 22 and the temperature sensor 24 are all connected to the data acquisition device 30 by signal. The data acquisition device 30 is electrically connected to the display instrument 29, and the display instrument 29 is electrically connected to the computer 28. The signal collected by the data acquisition device 30 is sent to the display instrument 29 and the data is recorded in the computer 28. The display instrument is used to display the hydrogen pressure of the main pipeline and the branch pipeline and the temperature inside the reaction chamber and the external environment.
[0035] The main gas pipeline, high-pressure container 19 and high-pressure sensor 21 can withstand a hydrogen pressure range of 0 to 5 MPa; the branch gas pipeline is used for the isothermal hydrogen desorption curve measurement of the hydrogen storage material. For the hydrogen absorption test, the first throttle valve 6 and the eighth throttle valve 13 are always closed, and the volume of the pipeline system is 500 mL at this time; for the hydrogen desorption test, the first throttle valve 6 is opened to connect the main pipeline with the branch pipeline, and the volume of the pipeline system is 1000 mL at this time. Since the hydrogen desorption reaction of the hydrogen storage material is usually carried out in the hydrogen pressure range of 0 to 0.1 MPa, the hydrogen released by the reaction has a greater impact on the hydrogen pressure of the pipeline system, which is not conducive to the accurate measurement of the hydrogen desorption curve of the hydrogen storage material under fixed conditions. The device involved in the present invention can temporarily close the first throttle valve 6 during the hydrogen desorption process, open the vacuum pump 25 and the eighth throttle valve 13, and adjust the hydrogen pressure of the branch pipeline. During the adjustment process, the hydrogen desorption curve is temporarily measured by the main gas pipeline. After the adjustment is completed, the vacuum pump 25 and the eighth throttle valve 13 are closed, the first throttle valve 6 is opened, and the dehydrogenation curve is continued to be measured by the main pipeline and the branch pipeline. Therefore, the device can accurately measure the dehydrogenation curve of the hydrogen storage material by adjusting the hydrogen pressure of the dehydrogenation reaction system.
[0036] The purpose of setting the low-pressure container 20 can be attributed to the following reasons:
[0037] ① By closing and opening the throttle valve 6, the volume of the hydrogen absorption and desorption reaction system can be adjusted. The change in the volume of the reaction system can expand the hydrogen storage material system to be tested and adapt to the hydrogen absorption and desorption performance test of materials with different hydrogen storage performances. On the other hand, since the hydrogen pressure of the hydrogen desorption performance test is usually low, the hydrogen pressure change of the reaction system during the desorption process is more obvious. By increasing the volume of the reaction system, the hydrogen pressure change of the system during the desorption process can be reduced, and thus the accurate test of hydrogen absorption and desorption performance can be achieved in the same hydrogen absorption and desorption cycle.
[0038] ② Since the hydrogen pressure of the reaction system is usually low during the dehydrogenation process, the release of hydrogen has a greater impact on the hydrogen pressure of the reaction system. By closing the first throttle valve 6 and using a vacuum pump to discharge part of the hydrogen to adjust the hydrogen pressure of the system, the hydrogen pressure of the reaction system can be adjusted in real time and repeatedly. During the period when the first throttle valve 6 is closed, the dehydrogenation curve of the hydrogen storage material can still be measured using the main pipeline. When only the ideal gas equation is used for calculation,
[0039] The corresponding system volume V1 can be used to achieve accurate characterization of the hydrogen absorption and desorption performance of the hydrogen storage material.
[0040] ③ It provides a new idea for accurately measuring the hydrogen absorption and desorption curves of hydrogen storage materials. According to the test requirements of the hydrogen storage experiment, by further changing the volume and number of low-pressure containers, it can accurately test the hydrogen absorption and desorption performance for different needs, and has extremely high universality.
[0041] A hydrogen storage test method using a hydrogen storage test device based on the Sieverts method:
[0042] a) Loading of hydrogen storage material sample: for different hydrogen storage materials, the sample mass is different. Taking the material with a hydrogen storage capacity of 5wt.% as an example, it is recommended that the sample mass is 400mg-500mg. The first throttle valve 6, the second throttle valve 7, the third throttle valve 8, the fourth throttle valve 9, the fifth throttle valve 10, the sixth throttle valve 11, the seventh throttle valve 12, the eighth throttle valve 13 and the ninth throttle valve 14 are in a closed state. First, the hydrogen storage material sample is loaded into the reaction chamber 17, the first disassembly interface 15 is assembled and tightened to seal, and the second disassembly interface 16 is assembled and tightened to seal;
[0043] b) Leak detection of the gas pipeline system: first open the first throttle valve 6, the fourth throttle valve 9 and the ninth throttle valve 14, and then open the vacuum pump 25 and the seventh throttle valve 12 in sequence to evacuate the gas pipeline system; then close the seventh throttle valve 12 and the vacuum pump 25 in sequence, and then open the argon source 2 and the third throttle valve 8 in sequence, fill the gas pipeline with argon to 1MPa, and use an argon gas detector to check whether the first disassembly interface 15 and the second disassembly interface 16 are leaking; if there is a leak, close the third throttle valve 8 and the argon source 2 in sequence, open After the sixth throttle valve 11 is exhausted to the standard atmospheric pressure, the sixth throttle valve 11 is closed, the second disassembly interface 16 and the first disassembly interface 15 are unscrewed in sequence, and steps a) and b) are repeated until there is no air leakage, and the air leakage operation is performed; if there is no air leakage, the sixth throttle valve 11 is opened to exhaust to the standard atmospheric pressure, and then the sixth throttle valve 11 is closed, and the vacuum pump 25 and the seventh throttle valve 12 are opened in sequence to evacuate the gas pipeline system; finally, the seventh throttle valve 12 and the vacuum pump 25 are closed in sequence, and the performance test of the hydrogen storage material sample is prepared;
[0044] c) Isothermal hydrogen absorption performance test: adjust the heating furnace 18 to the height of the reaction chamber to ensure that the hydrogen storage material sample can be fully heated so that it can fully absorb or release hydrogen; the first throttle valve 6, the second throttle valve 7, the third throttle valve 8, the fourth throttle valve 9, the fifth throttle valve 10, the sixth throttle valve 11, the seventh throttle valve 12, the eighth throttle valve 13 and the ninth throttle valve 14 are in a closed state, first set the temperature of the heating furnace 18 for heating and insulation, the insulation time of the heating furnace 18 after heating is greater than or equal to 2 hours, then open the hydrogen source 1 and the second throttle valve 7 in turn, fill the main pipeline system with hydrogen to the required hydrogen pressure, at which time the hydrogen pressure is higher than the reaction hydrogen pressure, then open the fourth throttle valve 9 and the ninth throttle valve 14 in turn, measure the isothermal hydrogen absorption curve, and the data acquisition system records the data;
[0045] d) Isothermal hydrogen release performance test: After the hydrogen storage material sample has completed hydrogen absorption, an isothermal hydrogen release performance test is performed. The first throttle valve 6, the second throttle valve 7, the third throttle valve 8, the fourth throttle valve 9, the fifth throttle valve 10, the sixth throttle valve 11, the seventh throttle valve 12, the eighth throttle valve 13 and the ninth throttle valve 14 are in a closed state. First, the fourth throttle valve 9 and the ninth throttle valve 14 are opened, and the hydrogen source 1 and the second throttle valve 7 are opened in sequence at the same time to increase the hydrogen pressure of the reaction system to the value required for the hydrogen storage material sample to remain stable. The second throttle valve 7 and the hydrogen source 1 are closed in sequence, and the temperature of the heating furnace 18 is set to heat and keep warm. The insulation time of the heating furnace 18 after heating is greater than or equal to 2 hours, and then the ninth throttle valve 14 is closed, and the sixth throttle valve 11 is opened for exhaust; after the exhaust is completed, the second throttle valve 7 and the hydrogen source 1 are opened in sequence. Open the vacuum pump 25 and the seventh throttle valve 12 to evacuate the main pipeline; then close the seventh throttle valve 12 and the vacuum pump 25 in turn, open the first throttle valve 6 and the ninth throttle valve 14 in turn, start measuring the isothermal dehydrogenation curve, and the data acquisition system records the data; since the hydrogen pressure required for dehydrogenation of the hydrogen storage material sample is relatively low, usually only 0 to 0.1 MPa, the dehydrogenation of the hydrogen storage material sample significantly increases the hydrogen pressure of the reaction system, resulting in changes in the dehydrogenation environment, and the dehydrogenation curve is difficult to accurately measure; at this time, it is necessary to close the first throttle valve 6 and temporarily use the main pipeline to measure the dehydrogenation curve; at the same time, open the vacuum pump 25 and the eighth throttle valve 13 in turn, adjust the hydrogen pressure of the branch pipeline, close the eighth throttle valve 13 and the vacuum pump 25 in turn, open the first throttle valve 6, and continue to use the entire pipeline to measure the isothermal dehydrogenation curve;
[0046] e) Unloading of hydrogen storage material samples: After the isothermal hydrogen absorption / desorption performance test is completed, the samples need to be taken out for further analysis;
[0047] For the isothermal hydrogen absorption sample in step c), after the hydrogen absorption test is completed, the hydrogen pressure of the reaction system is increased to the value required for the hydrogen storage material to remain stable, and then the reaction chamber is cooled to room temperature, and the sixth throttle valve 11 is opened for exhaust; after the exhaust is completed, the sixth throttle valve 11 is closed, and the vacuum pump 25 and the eighth throttle valve 13 are opened in sequence to perform vacuum treatment; then the argon source 2 and the third throttle valve 8 are opened in sequence, and after argon is filled into the main line to 0.1MPa, the third throttle valve 8 and the argon source 2 are closed in sequence, and the ninth throttle valve 14 and the fourth throttle valve 9 are closed at the same time, and the second disassembly interface 16 and the first disassembly interface 15 are unscrewed in sequence.
[0048] For the isothermal dehydrogenation sample in step d), after the dehydrogenation test is completed, the vacuum pump 25 and the eighth throttle valve 13 are opened in sequence to perform a vacuum treatment. After the vacuum treatment is completed, the eighth throttle valve 13 and the vacuum pump 25 are first closed in sequence to cool the reaction chamber to room temperature; then the argon source 2 and the third throttle valve 8 are opened in sequence, and after argon is filled into the main line to 0.1 MPa, the third throttle valve 8 and the argon source 2 are closed in sequence, and the ninth throttle valve 14 and the fourth throttle valve 9 are closed at the same time, and the second disassembly interface 16 and the first disassembly interface 15 are sequentially unscrewed.
[0049] In a reaction system with a constant volume, the amount of hydrogen absorbed and desorbed by the sample is calculated by the ideal gas equation: PV = ZnRT. The hydrogen storage data of the hydrogen storage material at different times are obtained by a computer 28, and then an isothermal hydrogen absorption and desorption curve is obtained; wherein, P is the pressure of hydrogen in the reaction system, V is the volume of the reaction system and pipeline used in the corresponding test, Z is the compression factor of hydrogen, n is the amount of substance participating in the reaction of hydrogen, R is the gas constant (8.3145 J / mol K), and T is the thermodynamic temperature of the environment surrounding the reaction system.
[0050] Obviously, the above-mentioned embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the embodiments of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made on the basis of the above description. It is impossible to list all the embodiments here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.
Claims
1. A hydrogen storage test device based on Sieverts method, characterized in that: The invention comprises a reaction system, a gas pipeline system, a data acquisition system, a gas source pipeline, an exhaust and gas collecting pipeline, and a vacuum pump (25). The gas pipeline system comprises a main gas pipeline and a branch gas pipeline. One end of the main gas pipeline is connected to the reaction system. A third filtering device (5) and a ninth throttle valve (14) are provided between the main gas pipeline and the reaction system. The other end of the main gas pipeline is respectively connected to the gas source pipeline, the exhaust and gas collecting pipeline, and the vacuum pump (25). The gas source pipeline is formed by connecting a pipeline connected to a hydrogen source (1) and a pipeline connected to an argon source (2) in parallel. The exhaust and gas collecting pipeline is formed by connecting a pipeline connected to a gas collecting device (26) and a pipeline connected to an exhaust device (27) in parallel. A first filtering device (3) is provided between the main gas pipeline and the gas source pipeline. The pipeline connected to the hydrogen source (1), the pipeline connected to the argon source (2), the pipeline connected to the gas collecting device (26), and the pipeline connected to the exhaust device (27) are respectively provided with a second throttle valve. (7), a third throttle valve (8), a fifth throttle valve (10) and a sixth throttle valve (11); a seventh throttle valve (12) is provided between the main gas pipeline and the vacuum pump (25); a fourth throttle valve (9), a second filter device (4) and a temperature sensor (24) are provided on the main gas pipeline; a middle portion of the main gas pipeline is connected to one end of the branch gas pipeline and the high-pressure container (19); the high-pressure container (19) is connected to a high-pressure sensor (21); the branch gas pipeline is provided with a first throttle valve (6) and a low-pressure container (20); the low-pressure container (20) is connected to a low-pressure sensor (22); the other end of the branch gas pipeline is connected to the vacuum pump (25); an eighth throttle valve (13) is provided between the branch gas pipeline and the vacuum pump (25); a thermocouple (23) is provided in the reaction system; the thermocouple (23), the high-pressure sensor (21), the low-pressure sensor (22) and the temperature sensor (24) are all connected to the data acquisition system signal; The reaction system comprises a heating furnace (18) and a reaction chamber (17); the main body of the reaction chamber (17) is located inside the heating furnace (18); a resistance wire (37) is provided inside the heating furnace (18); a gap between the heating furnace (18) and the reaction chamber (17) is filled with a thermal insulation sealing layer (31); a plurality of thermocouples (23) are evenly arranged at the bottom of the inner furnace of the heating furnace (18); the upper end of the reaction chamber (17) is connected to the third filter device (5) and the ninth throttle valve (14) via a first disassembly interface (15); and the upper ends of the third filter device (5) and the ninth throttle valve (14) are connected to the main gas pipeline via a second disassembly interface (16); The first disassembly interface (15) comprises a first sealing nut (32), the upper end of the reaction chamber (17) being threadedly connected to the first sealing nut (32), the lower end of the connecting pipe (34) being fixed inside the first sealing nut (32), a copper gasket (33) being provided between the upper end of the reaction chamber (17) and the lower end of the connecting pipe (34), the connecting pipe (34) being used to connect the third filtering device (5) and the ninth throttle valve (14); The second disassembly interface (16) comprises a second sealing nut (35), a connecting pipeline (34) at the upper end of the third filter device (5) and the ninth throttle valve (14) is connected to the main pipeline, and the connection between the main pipeline and the connecting pipeline (34) is a structure with a larger diameter at the upper end and a smaller diameter at the lower end. The second sealing nut (35) is threadedly connected to the upper end of the connecting pipeline (34) at the upper end of the third filter device (5) and the ninth throttle valve (14), and an aluminum gasket (36) is provided inside the second sealing nut (35) between the connecting pipeline (34) at the upper end of the third filter device (5) and the ninth throttle valve (14) and the main pipeline, and a spring gasket (38) is also provided between the upper end of the second sealing nut (35) and the main pipeline.
2. The hydrogen storage testing device based on the Sieverts method according to claim 1, characterized in that: The adjustable temperature range in the reaction system is from room temperature to 500°C, and the temperature deviation is ≤0.1°C; the total volume of the connecting pipeline (34) and the reaction chamber (17) is 25 mL, the reaction chamber (17) is made of 304 stainless steel and is in the shape of a round tube with a closed lower end, the volume of the reaction chamber (17) is 15 mL, the total volume of the main pipeline including the high-pressure container (19) is 500 mL, the volume of the high-pressure container (19) is 300 mL, the total volume of the branch pipeline including the low-pressure container (20) is 1000 mL, and the volume of the low-pressure container (20) is 900 mL.
3. The hydrogen storage testing device based on Sieverts method according to claim 1, characterized in that: The data acquisition system comprises a computer (28), a display instrument (29) and a data acquisition device (30); the thermocouple (23), the high-pressure sensor (21), the low-pressure sensor (22) and the temperature sensor (24) are all signal-connected to the data acquisition device (30); the data acquisition device (30) is electrically connected to the display instrument (29); and the display instrument (29) is electrically connected to the computer (28).
4. A hydrogen storage test method, using the hydrogen storage test device based on the Sieverts method as claimed in claim 1, characterized in that: a) Loading of hydrogen storage material sample: the first throttle valve (6), the second throttle valve (7), the third throttle valve (8), the fourth throttle valve (9), the fifth throttle valve (10), the sixth throttle valve (11), the seventh throttle valve (12), the eighth throttle valve (13) and the ninth throttle valve (14) are in a closed state, firstly, the hydrogen storage material sample is loaded into the reaction chamber (17), the first disassembly interface (15) is assembled and the seal is tightened, and the second disassembly interface (16) is assembled and the seal is tightened; b) Leak detection of the gas pipeline system: first open the first throttle valve (6), the fourth throttle valve (9) and the ninth throttle valve (14), then open the vacuum pump (25) and the seventh throttle valve (12) in turn to evacuate the gas pipeline system; then close the seventh throttle valve (12) and the vacuum pump (25) in turn, then open the argon gas source (2) and the third throttle valve (8) in turn, fill the gas pipeline with argon gas to 1 MPa, and use an argon gas detector to check whether the first disassembly interface (15) and the second disassembly interface (16) are leaking; if there is a leak, close the third throttle valve (8) and the argon gas source (2) in turn. After the sixth throttle valve (11) is opened to exhaust to the standard atmospheric pressure, the sixth throttle valve (11) is closed, the second disassembly interface (16) and the first disassembly interface (15) are unscrewed in sequence, and steps a) and b) are repeated until there is no air leakage, and the air leakage operation is performed; if there is no air leakage, the sixth throttle valve (11) is opened to exhaust to the standard atmospheric pressure, the sixth throttle valve (11) is closed, and the vacuum pump (25) and the seventh throttle valve (12) are opened in sequence to evacuate the gas pipeline system; finally, the seventh throttle valve (12) and the vacuum pump (25) are closed in sequence to prepare for the performance test of the hydrogen storage material sample; c) Isothermal hydrogen absorption performance test: the first throttle valve (6), the second throttle valve (7), the third throttle valve (8), the fourth throttle valve (9), the fifth throttle valve (10), the sixth throttle valve (11), the seventh throttle valve (12), the eighth throttle valve (13) and the ninth throttle valve (14) are in a closed state. First, the temperature of the heating furnace (18) is set to heat and keep warm. Then, the hydrogen source (1) and the second throttle valve (7) are opened in sequence to fill the main pipeline system with hydrogen to a required hydrogen pressure. At this time, the hydrogen pressure is higher than the reaction hydrogen pressure. Then, the fourth throttle valve (9) and the ninth throttle valve (14) are opened in sequence to measure the isothermal hydrogen absorption curve. The data acquisition system records the data. d) Isothermal dehydrogenation performance test: After the hydrogen storage material sample has completed hydrogen absorption, an isothermal dehydrogenation performance test is performed. The first throttle valve (6), the second throttle valve (7), the third throttle valve (8), the fourth throttle valve (9), the fifth throttle valve (10), the sixth throttle valve (11), the seventh throttle valve (12), the eighth throttle valve (13) and the ninth throttle valve (14) are in a closed state. First, the fourth throttle valve (9) and the ninth throttle valve (14) are opened, and the hydrogen source (1) and the second throttle valve (7) are opened in sequence at the same time to increase the hydrogen pressure of the reaction system to a value required for the hydrogen storage material sample to remain stable. The second throttle valve (7) and the hydrogen source (1) are closed in sequence, and the temperature of the heating furnace (18) is set to heat and keep warm. Then, the ninth throttle valve (14) is closed, and the sixth throttle valve (11) is opened for exhaust. After the exhaust is completed, the vacuum pump ( 25) and the seventh throttle valve (12) to evacuate the main pipeline; then, the seventh throttle valve (12) and the vacuum pump (25) are closed in sequence, and the first throttle valve (6) and the ninth throttle valve (14) are opened in sequence to start measuring the isothermal dehydrogenation curve, and the data acquisition system records the data; since the hydrogen pressure required for dehydrogenation of the hydrogen storage material sample is relatively low, usually only 0-0.1 MPa, the dehydrogenation of the hydrogen storage material sample causes the hydrogen pressure of the reaction system to increase significantly, resulting in changes in the dehydrogenation environment, making it difficult to accurately measure the dehydrogenation curve; at this time, the first throttle valve (6) needs to be closed, and the main pipeline is temporarily used to measure the dehydrogenation curve; at the same time, the vacuum pump (25) and the eighth throttle valve (13) are opened in sequence, and after adjusting the hydrogen pressure of the branch pipeline, the eighth throttle valve (13) and the vacuum pump (25) are closed in sequence, and the first throttle valve (6) is opened, and the isothermal dehydrogenation curve is continued to be measured using the entire pipeline; e) Unloading of hydrogen storage material samples: After completing the isothermal hydrogen absorption / desorption performance test, the samples need to be taken out for further analysis; For the isothermal hydrogen absorption sample in step c), after the hydrogen absorption test is completed, the hydrogen pressure of the reaction system is increased to a value required for the hydrogen storage material to remain stable, and then the reaction chamber is cooled to room temperature, and the sixth throttle valve (11) is opened to exhaust; after the exhaust is completed, the sixth throttle valve (11) is closed, and the vacuum pump (25) and the eighth throttle valve (13) are opened in sequence to perform a vacuum treatment; then the argon source (2) and the third throttle valve (8) are opened in sequence, and after argon is filled into the main pipeline to 0.1 MPa, the third throttle valve (8) and the argon source (2) are closed in sequence, and the ninth throttle valve (14) and the fourth throttle valve (9) are closed at the same time, and the second disassembly interface (16) and the first disassembly interface (15) are unscrewed in sequence; For the isothermal dehydrogenation sample in step d), after the dehydrogenation test is completed, the vacuum pump (25) and the eighth throttle valve (13) are opened in sequence to perform a vacuum treatment. After the vacuum treatment is completed, the eighth throttle valve (13) and the vacuum pump (25) are first closed in sequence to cool the reaction chamber to room temperature; then, the argon source (2) and the third throttle valve (8) are opened in sequence, and after argon is filled into the main pipeline to 0.1 MPa, the third throttle valve (8) and the argon source (2) are closed in sequence, and the ninth throttle valve (14) and the fourth throttle valve (9) are closed at the same time, and the second disassembly interface (16) and the first disassembly interface (15) are sequentially unscrewed.
5. The hydrogen storage testing method according to claim 4, characterized in that: In the step c) and the step d), the heat preservation time after heating in the heating furnace (18) is greater than or equal to 2 hours.
6. The hydrogen storage testing method according to claim 4, characterized in that: In a reaction system with a constant volume, the amount of hydrogen absorbed and desorbed by the sample is calculated using the ideal gas equation: PV=ZnRT , and then the isothermal hydrogen absorption and desorption curve is obtained; among which, P is the pressure of hydrogen in the reaction system, V is the volume of the reaction system and pipeline used in the corresponding test, Z is the compression factor of hydrogen, n is the amount of substance participating in the reaction of hydrogen, R is the gas constant, T is the thermodynamic temperature of the environment surrounding the reaction system.