Full-automatic test system based on solid hydrogen storage material hydrolysis performance evaluation

Abstract

The utility model belongs to the technical field of solid hydrogen storage materials, and relates to a full-automatic test system based on solid hydrogen storage material hydrolysis performance evaluation, which comprises a liquid supply system, a gas measurement system, a reaction system, a temperature control system and an electrical control system, the gas measuring system is connected with a gas outlet of the reaction system, and the temperature control system is connected with the reaction system to control the temperature of the reaction system; the liquid supply system, the gas measurement system, the temperature control system and the reaction system are all connected with the electrical control system. The reaction monitoring of different liquid types can be realized, two reaction forms of liquid water and water vapor can be realized, and reaction research under different temperatures and different pressures can be automatically controlled; the functions of full-automatic testing, high-precision measurement, sampling and detection of hydrogen at any time and the like are achieved, more comprehensive and reliable data support is provided for development of hydrolysis hydrogen production equipment in the future, and application of hydrolysis hydrogen production in various scenes is greatly promoted.

Description

Technical Field

[0001] The utility model belongs to the technical field of solid hydrogen storage materials, and particularly relates to a full-automatic test system for evaluating the hydrolysis performance of solid hydrogen storage materials. Background Technique

[0002] Hydrogen is a gas that is difficult to store. The most common hydrogen storage method is to obtain compressed and stored hydrogen in a high-pressure storage tank. However, there are certain problems with high-pressure hydrogen storage in terms of energy storage density, safety, and stability. To solve the problems existing in the current high-pressure gaseous hydrogen storage system, domestic and foreign researchers have actively developed hydrogen storage systems based on solid hydrogen storage materials. Among many hydrogen storage materials, typical representatives are metal hydrides and composite material hydrogen storage. Among them, most hydrogen storage materials can release hydrogen through both pyrolysis and hydrolysis.

[0003] The materials that release hydrogen through hydrolysis belong to irreversible hydrogen storage materials. They release hydrogen through hydrolysis reactions and are suitable for on-site hydrogen use forms that are produced and used immediately. Hydrolysis hydrogen production has the following advantages: 1) Both the mass hydrogen storage density and the volume hydrogen storage density are relatively high. For example, the theoretical mass hydrogen storage density of systems such as NaBH4, LiBH4, Mg(BH4)2, and MgH2 can reach up to about 30%, and at the same time, the volume hydrogen storage density of these materials is also much higher than that of commercial high-pressure hydrogen storage; 2) Hydrolysis hydrogen production is a spontaneous exothermic reaction that occurs at normal temperature and pressure, and the hydrogen production device is relatively simple; 3) The hydrolysis hydrogen production materials are easy to store, relatively safe, and convenient for storage and transportation; 4) The reaction by-products are basically non-toxic and harmless, meeting the requirements of green chemistry.

[0004] Although the hydrolysis hydrogen production technology of solid hydrogen storage materials has many advantages, it still faces some challenges, such as cost, hydrolysis reaction rate, material life cycle, and long-term stability. Therefore, it is necessary to evaluate the hydrolysis performance of solid hydrogen storage materials.

[0005] The evaluation indexes of the hydrolysis performance of solid hydrogen storage materials mainly include the following: 1) Hydrogen production rate at different temperatures and pressures; 2) Hydrogen production amount at different temperatures and pressures; 3) Hydrogen production purity at different temperatures and pressures; 4) The required proportion of the reaction solution corresponding to the hydrogen production amount at different temperatures and pressures; 5) Heat release during the entire thermodynamic process of hydrogen production; 6) The characteristics of the products after the hydrogen production reaction.

[0006] Currently, universities and research institutions at home and abroad have shown great enthusiasm for the hydrolysis performance and mechanism research of solid-state hydrogen storage materials. However, the main tools used for testing and evaluation are simple glassware, which have problems such as poor test accuracy, few test conditions that can be set, and low test efficiency. Chinese patent document CN102590374A discloses a test system for hydrogen production by hydrolysis of complex metal hydride vapor. This patent can evaluate the hydrogen release rate and yield of different complex metal hydride materials during hydrolysis in water vapor containing different promoters and catalysts, so as to screen out low-cost hydrogen storage materials and steam hydrolysis agent formulations that can meet the requirements. However, this test system is only an improvement on the simple test device of the original glassware and can only conduct simple tests on the characteristics of hydrolysis reactions, and there are many limitations in terms of test conditions, test accuracy, test efficiency, etc. Summary of the Utility Model

[0007] In order to solve the problems of single test conditions, low test accuracy and low test efficiency existing in the evaluation system of the hydrolysis performance of solid-state hydrogen storage materials in the prior art, a full-automatic test system based on the evaluation of the hydrolysis performance of solid-state hydrogen storage materials is provided.

[0008] In order to achieve the above object, the present utility model adopts the following technical solutions:

[0009] A full-automatic test system based on the evaluation of the hydrolysis performance of solid-state hydrogen storage materials, comprising a liquid supply system, a gas measurement system, a reaction system, a temperature control system and an electrical control system,

[0010] The liquid supply system is connected to the liquid inlet of the reaction system, the gas measurement system is connected to the gas outlet of the reaction system, and the temperature control system is connected to the reaction system to realize temperature control of the reaction system; the liquid supply system, the gas measurement system, the temperature control system and the reaction system are all connected to the electrical control system;

[0011] The liquid supply system includes a liquid storage tank, a metering pump, a first three-way solenoid valve, a steam generator, and a second three-way solenoid valve connected in sequence through pipelines; there is a pipeline connected between the first three-way solenoid valve and the second three-way solenoid valve;

[0012] The gas measurement system includes a hydrogen pipeline connected to the reaction system, and a reaction system solenoid valve, a dryer, a pressurizing device, a temperature sensor, a vacuum pump, a pressure sensor, a gas storage device, an adjustable back pressure valve and a flow meter are sequentially arranged on the hydrogen pipeline.

[0013] Preferably, the temperature control system is connected to the circulating medium pipeline of the reaction system.

[0014] Preferably, the liquid storage tank is used to store different types of reaction liquids and is connected to a metering pump. The metering pump is used to supply liquid to the reaction system and automatically measure the liquid supply volume. The metering pump is equipped with a built-in measurement and calculation unit, which can simultaneously achieve the functions of on-line display and remote control. The function of the steam generator is to vaporize a non-corrosive liquid (such as pure water, etc.) at a specified temperature.

[0015] Preferably, a nitrogen purging device is also connected to the pipeline between the metering pump and the first three-way solenoid valve; a waste liquid discharge port is provided on the pipeline connecting the liquid supply system to the inlet pipe of the reaction system, and the opening and closing of the waste liquid discharge port are controlled by a bypass hand valve.

[0016] Preferably, a check valve is also provided on the pipeline connecting the liquid supply system to the reaction system, and its function is to prevent the gas in the reaction process from flowing back under a certain pressure.

[0017] Preferably, the nitrogen purging device is used to purge the liquid supply system pipeline before and after testing to maintain the daily use of the test system. The nitrogen purging device includes a nitrogen cylinder, a nitrogen pressure reducing valve, and a nitrogen cylinder solenoid valve; the control software controls the start and stop of nitrogen purging by controlling the nitrogen cylinder solenoid valve.

[0018] Through the coordinated control of the first three-way solenoid valve and the second three-way solenoid valve, the isolated supply of non-corrosive liquid and corrosive liquid is realized. At the same time, the steam generator is used to control the reaction characteristics of non-corrosive liquid (such as pure water, etc.) with solid hydrogen storage materials in the gaseous state; by opening and closing the bypass hand valve, the liquid supply pipeline can be filled with the corresponding liquid or vapor before the reaction to achieve a more accurate automatic calculation of the required liquid volume for the reaction. Among them, the pipeline connecting the liquid storage tank to the reaction system is uniformly called the liquid supply pipeline.

[0019] Preferably, the pressurizing device includes a hydrogen cylinder, a hydrogen cylinder solenoid valve, and a hydrogen cylinder pressure reducing valve. The control software controls the start and stop of the pressurizing device by controlling the hydrogen cylinder solenoid valve.

[0020] Preferably, the gas storage device includes a gas storage tank and a gas storage tank solenoid valve. The gas storage device is used to calibrate the volume of the gas measurement system. The gas storage tank is connected to the hydrogen pipeline through the gas storage tank solenoid valve. The gas storage tank solenoid valve is used to control the opening and closing of the gas storage tank. A gas storage tank pressure sensor is provided on the outlet pipeline of the gas storage tank, and the gas storage tank pressure sensor is used to detect the change of the internal gas pressure of the gas storage tank.

[0021] Preferably, the gas measurement system also includes a gas chromatograph analyzer. The gas chromatograph analyzer is connected to the gas sampling interface on the hydrogen pipeline through a needle valve and is used to on-line monitor the composition of the gas components after the reaction.

[0022] The dryer is a metering dryer used to dry the gas after the reaction, so as to accurately measure the actual hydrogen production of the hydrolysis reaction. At the same time, the metering dryer is used to measure the amount of water carried out with the product hydrogen during the reaction process to correct the metering evaluation of the actual required reaction water in the reaction process. The vacuum pump is used to vacuum the gas measurement system before and after the reaction. The vacuum pump is connected to the hydrogen pipeline through a vacuum pump solenoid valve, and the control software controls the opening and closing of the vacuum pump by controlling the vacuum pump solenoid valve.

[0023] Preferably, the full-automatic test system further includes a system framework for fixing and protecting each system and a hydrogen recovery interface for discharging hydrogen. More preferably, a ventilation system is further provided inside the system framework to quickly maintain the temperature stability inside the gas measurement system.

[0024] In order to study the kinetics of the hydrolysis reaction of solid hydrogen storage materials at different reaction temperatures, a temperature control system is used to achieve the reaction characteristics at different set temperatures.

[0025] The liquid supply system of the present utility model can be used to provide the reaction system with the required liquid regularly and quantitatively according to the reaction requirements, and can monitor relevant parameters such as the flow rate, temperature, and pressure of the liquid in real time, and is required to be able to generate and supply high-temperature steam.

[0026] The gas test system is mainly used to monitor key parameters such as the pressure, temperature, and flow rate of the gas generated by the reaction in real time. An adjustable backpressure valve is provided inside to measure the reaction performance of the hydrogen storage material at different pressures. A gas sampling interface is reserved inside for the detection of gas components. The temperature control system is used to control the temperature of the reaction system to evaluate and study the performance of the hydrolysis reaction at different specified temperatures. Considering that the hydrolysis reaction of solid hydrogen storage materials is an exothermic reaction, the heat dissipation requirements of the reaction system itself need to be considered synchronously in the whole temperature control process, so as to effectively control the temperature of the reaction system.

[0027] Preferably, the electrical control system mainly consists of a host computer control unit, a DC power supply, power distribution, and an extended I / O interface module. Its main function is to provide an auxiliary low-voltage DC power supply for the electrical components of the system test bench; reserve a certain number of digital, analog input, communication, etc. interfaces for users to facilitate the expansion of system functions. The host computer control unit realizes data acquisition, system control, system status monitoring, man-machine dialogue, etc., and has functions such as processing, displaying, storing, analyzing, and exporting data during the test and system operation process. The host computer control unit mainly consists of a main controller, an industrial computer, a display, a communication module, a system control software, etc.

[0028] Specifically, the electrical control components and measurement units of all systems interact with the electrical control system to realize the automatic measurement and control of the overall test system.

[0029] The reaction system is the place for the hydrolysis reaction of solid hydrogen storage materials, mainly including a pressure-resistant reaction kettle, a circulating medium pipeline, a quick-connect module, a temperature monitoring device, and a pressure monitoring device. The pressure-resistant reaction kettle is provided with a jacket, which is connected to the circulating medium pipeline and used to fill the cooling medium or heating medium. A temperature sensor is arranged on the circulating medium pipeline and connected to the temperature control system to control the reaction system to work at a certain temperature; the quick-connect module is used for the quick and reliable connection of the reaction system to the liquid supply system and the gas measurement system respectively; the temperature and pressure monitoring devices are connected to the electrical control system to monitor the temperature and pressure states of the reaction system in real time. The reaction chamber of the pressure-resistant reaction kettle is the sample chamber, and the volume of the pressure-resistant reaction kettle is the volume of the sample chamber.

[0030] The evaluation method for the hydrolysis performance of solid hydrogen storage materials using the above system includes the following steps:

[0031] (1) Calibrate the volume V of the gas measurement system sys and the "dead volume" V of the sample chamber of the reaction system dead , and the "dead volume" V of the sample chamber dead is the volume of the sample chamber minus the sample volume;

[0032] (2) Preparation of the liquid supply system

[0033] First, confirm that the quick connection between the liquid supply system and the reaction system is disconnected. Open the bypass manual valve to connect the liquid supply pipeline to the waste liquid discharge port. Open the nitrogen purge program of the control software to purge the liquid supply pipeline. After purging, store the raw material liquid required for the reaction in the liquid storage tank, start the metering pump to work. When the raw material liquid flows out from the waste liquid discharge port of the bypass manual valve, turn off the metering pump, close the bypass manual valve, and perform the liquid supply zero setting on the control software;

[0034] (3) Set the working temperature and pressure of the reaction system

[0035] Set the working temperature of the reaction system through the temperature control system, and set the basic pressure before the reaction through the adjustable back-pressure valve and the pressurizing device to achieve the hydrolysis reaction at a certain temperature and a certain pressure;

[0036] (4) Start the hydrolysis reaction

[0037] Confirm that the quick connection between the liquid supply system and the reaction system is reliably connected, and the quick connection between the gas measurement system and the reaction system is reliably connected; connect the quick connection of the hydrogen recovery port to the gas tail discharge or gas utilization device at the back end, and perform the zero setting on the gas flowmeter; open the solenoid valve entering the gas measurement system, start the metering pump according to the test condition requirements, and supply liquid at the set rate. The electrical control system reads the gas flowmeter, the temperature of the gas measurement system, and the pressure of the gas measurement system in real time;

[0038] (5) Automatically generate test results for the hydrolysis test through control software

[0039] Monitor the real-time hydrogen flow rate and cumulative hydrogen flow rate during the reaction process through a flow meter. The control software measures the stable temperature TN sys and stable pressure PN sys of the gas measurement system through a temperature sensor and a pressure sensor, the volume V sys of the gas measurement system, and the "dead volume" V dead of the sample chamber to correct the real-time hydrogen flow rate and cumulative hydrogen flow rate, thereby improving the accuracy of the overall test results.

[0040] Preferably, the volume V sys of the gas measurement system described in step (1) and the "dead volume" V dead of the sample chamber of the reaction system are obtained using the volume calibration method.

[0041] More preferably, the specific steps of the volume calibration method described in step (1) are as follows:

[0042] 1) Test the airtightness of the system to be calibrated with hydrogen to ensure that the hydrogen leakage rate of the pipeline system ≤ 1.7×10 -4 Pa·m 3 / s;

[0043] 2) Evacuate the system to be calibrated and then close all valves;

[0044] 3) Fill the system to be calibrated with hydrogen at a certain pressure. After the pressure and temperature of the system are stable, record the temperature T0 sys and pressure P0 sys of the system to be calibrated;

[0045] 4) Let hydrogen flow into the gas storage device until the pressure and temperature of the system to be calibrated are stable, and record the temperature T1 sys and pressure P1 sys of the system to be calibrated at this time;

[0046] 5) For the two measurements, the influence of temperature is negligible, T1 sys = T0 sys . According to the gas mass conservation equation:

[0047] P0 sys V sys = P1 sys (V sys + V bd )

[0048] 6) Evacuate the system again and record the hydrogen pressure P1 bd in the hydrogen storage device;

[0049] 7) Let the hydrogen in the gas storage device flow into the system to be calibrated. Wait for the pressure and temperature of the system to stabilize, and record the temperature T2 of the system to be calibrated. sys and the pressure P2 sys ;

[0050] 8) For two measurements, ignoring the influence of temperature, according to the gas mass conservation equation:

[0051] P1 bd V bd = P2 sys (V sys + V bd )

[0052] 9) Through the above binary equation system, obtain the volume V of the gas measurement system sys and the volume V of the gas storage device bd .

[0053] Preferably, in step (3), for high-temperature working conditions, turn on the temperature control switch of the heating tape on the connecting pipeline between the liquid supply system and the reaction system, and it is in the working state to ensure the overall temperature control accuracy.

[0054] Preferably, through the above test system and method, realize the performance index test of the hydrolysis performance of solid-state hydrogen storage, including one or more of the following: a) hydrogen production rate at different temperatures and pressures; b) hydrogen production amount at different temperatures and pressures; c) hydrogen production purity at different temperatures and pressures; d) reaction liquid requirements corresponding to the hydrogen production amount at different temperatures and pressures; e) heat release amount during hydrogen production; f) characteristics of the product after the hydrogen production reaction. Among them, the characteristics of the product include physical and chemical: physical characteristics mainly include whether the reaction product is in the form of a solid precipitate or emulsion, the viscosity of the product, the volume change of the product, etc.; chemical characteristics need to analyze its composition through material detection.

[0055] Preferably, the control software is obtained by using LABVIEW visual programming according to the overall requirements of the test system. The signals of the metering pump, dryer, temperature sensor, pressure sensor, adjustable backpressure valve, flowmeter, gas storage tank pressure sensor, and temperature control system are connected to the electrical control system, and through the control software, the test system can automatically generate test results under different working conditions.

[0056] Advantages of the present utility model:

[0057] In the actual process of engineering use, especially when coupled with equipment with different hydrogen demand (such as fuel cell systems, hydrogen pumps, etc.), it is necessary to meet the hydrogen production performance research under different temperatures and pressures. However, the existing hydrolysis performance tests have problems such as being cumbersome, inefficient, and involving a large amount of work. One or more technical solutions provided by the specific embodiments of the present utility model have at least the following technical effects and advantages:

[0058] 1) Realize the monitoring of reactions with different liquid types, including different reaction media such as pure water, acids, alkalis, and seawater;

[0059] 2) Realize two reaction forms of liquid water and water vapor, and through the temperature control system, automatically control the reaction research at different temperatures;

[0060] 3) Set the basic pressure of the reaction by the back pressure valve and the initial hydrogen filling of the system to realize the analysis of the reaction characteristics under different pressures;

[0061] 4) Through the changes in system pressure and temperature, accurately monitor the change of hydrogen production rate over time in real time, and realize the accurate measurement of the hydrogen production amount of micro reactions;

[0062] 5) The system realizes functions such as fully automatic testing, high-precision measurement, and hydrogen sampling and detection at any time, provides more comprehensive and reliable data support for the development of future hydrolysis hydrogen production equipment, and will greatly promote the application of hydrolysis hydrogen production in various scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] Figure 1 is a schematic diagram of the fully automatic test system for evaluating the hydrolysis performance of the solid hydrogen storage material described in the present utility model.

[0064] Figure 2 is the instantaneous hydrogen production rate and cumulative hydrogen production amount of the hydrolysis reaction in Example 1 of the present utility model.

[0065] Reference Numerals:

[0066] Liquid storage tank 1, metering pump 2, first three-way solenoid valve 3, steam generator 4, second three-way solenoid valve 5, check valve 6, gas sampling interface 7, needle valve 8, reaction system solenoid valve 9, dryer 10, temperature sensor 11, pressure sensor 12, gas storage tank solenoid valve 13, adjustable back pressure valve 14, flow meter 15, hydrogen recovery interface 16, ventilation system 17, gas storage tank pressure sensor 18, gas storage tank 19, vacuum pump solenoid valve 20, vacuum pump 21, hydrogen cylinder solenoid valve 22, hydrogen cylinder pressure reducing valve 23, reaction system 24, temperature control system 25, bypass manual valve 26, nitrogen pressure reducing valve 27, nitrogen cylinder solenoid valve 28. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0067] The following will further explain the present utility model in combination with specific embodiments.

[0068] like Figure 1 As shown, the utility model provides a fully automatic testing system based on the hydrolysis performance evaluation of solid hydrogen storage materials, including a liquid supply system, a gas measurement system, a reaction system, a temperature control system 25 and an electrical control system;

[0069] The liquid supply system is connected to the liquid inlet of the reaction system 24, the gas measurement system is connected to the gas outlet of the reaction system 24, and the temperature control system 25 is connected to the circulating medium (such as water, heat transfer oil, etc.) pipeline of the reaction system 24 to achieve temperature control of the reaction system 24; the liquid supply system, the gas measurement system, the temperature control system 25, and the reaction system 24 are all connected to the electrical control system;

[0070] The liquid supply system comprises a liquid storage tank 1, a metering pump 2, a first three-way solenoid valve 3, a steam generator 4, and a second three-way solenoid valve 5 which are connected in sequence through pipelines; a pipeline is connected between the first three-way solenoid valve 3 and the second three-way solenoid valve 5; a nitrogen purge device is also connected to the pipeline between the metering pump 2 and the first three-way solenoid valve 3; a waste liquid discharge port is provided on the pipeline connecting the liquid supply system and the liquid inlet pipe of the reaction system 24, and the opening and closing of the waste liquid discharge port is controlled by a bypass manual valve 26;

[0071] The gas measurement system includes a hydrogen pipeline connected to the reaction system 24, on which the reaction system 24 solenoid valve 9, a gas chromatograph, a dryer 10, a pressurizing device, a temperature sensor 11, a vacuum pump 21, a pressure sensor 12, a gas storage device, an adjustable back pressure valve 14 and a flow meter 15 are sequentially arranged; the gas chromatograph is connected to the gas sampling interface 7 through a needle valve 8 for online monitoring of the composition of the gas components after the reaction; the air inlet and the air outlet of the dryer 10 are respectively connected to the pipelines on both sides.

[0072] Specifically, the liquid storage tank 1 is used to store different types of reaction liquids and is connected to the metering pump 2. The metering pump 2 is used to realize the liquid supply of the reaction system 24 and the automatic metering of the liquid supply amount. The metering pump 2 has a built-in measurement and calculation unit, which can simultaneously realize online display and remote control functions; the function of the steam generator 4 is to vaporize non-corrosive liquids (such as pure water, etc.).

[0073] Specifically, a check valve 6 is provided on the pipeline connecting the liquid supply system and the reaction system 24, and its function is to prevent the gas from flowing back during the reaction process under a certain pressure.

[0074] Specifically, the nitrogen purge device is used to purge the liquid supply system pipeline before and after the test to maintain the daily use of the test system. The nitrogen purge device includes a nitrogen bottle, a nitrogen pressure reducing valve 27 and a nitrogen bottle solenoid valve 28; the control software controls the start and stop of the nitrogen purge by controlling the nitrogen bottle solenoid valve 28.

[0075] Through the coordinated control of the first three-way solenoid valve 3 and the second three-way solenoid valve 5, the isolated supply of non-corrosive liquid and corrosive liquid is realized. At the same time, the steam generator 4 is used to control the reaction characteristics of the non-corrosive liquid (such as pure water, etc.) with the solid hydrogen storage material in the gaseous state; by opening and closing the bypass hand valve 26, it is possible to control the filling of the liquid supply pipeline with the corresponding liquid or vapor before the reaction, so as to realize the automatic calculation of the more accurate liquid volume required for the reaction. Among them, the pipeline connecting the liquid storage tank to the reaction system 24 is uniformly called the liquid supply pipeline.

[0076] Specifically, the pressurizing device includes a hydrogen cylinder, a hydrogen cylinder solenoid valve 22, and a hydrogen cylinder pressure reducing valve 23. The control software controls the start and stop of the pressurizing device by controlling the hydrogen cylinder solenoid valve 22.

[0077] Specifically, the gas storage device includes a gas storage tank 19 and a gas storage tank solenoid valve 13. The gas storage device is used to calibrate the volume of the gas measurement system. The gas storage tank 19 is connected to the hydrogen pipeline through the gas storage tank solenoid valve 13. The gas storage tank solenoid valve 13 is used to control the opening and closing of the gas storage tank. A gas storage tank pressure sensor 18 is provided on the outlet pipeline of the gas storage tank 19. The gas storage tank pressure sensor 18 is used to detect the change of the internal gas pressure of the gas storage tank 19.

[0078] Specifically, the dryer 10 is a metering dryer used to dry the gas after the reaction, so as to accurately measure the actual hydrogen production of the hydrolysis reaction; at the same time, the metering dryer is used to measure the amount of water carried out with the product hydrogen during the reaction process, so as to correct the metering evaluation of the actual required reaction water during the reaction process. The vacuum pump 21 is used to perform vacuum treatment on the gas measurement system before and after the reaction. The vacuum pump 21 is connected to the hydrogen pipeline through the vacuum pump solenoid valve 20. The control software controls the opening and closing of the vacuum pump by controlling the vacuum pump solenoid valve 20.

[0079] Specifically, the full-automatic test system further includes a system framework for fixing and protecting each system and a hydrogen recovery interface 16 for discharging hydrogen. Further, a ventilation system 17 is also provided inside the system framework, which is used to quickly maintain the temperature stability inside the gas measurement system.

[0080] In order to study the kinetics of the hydrolysis reaction of the solid hydrogen storage material at different reaction temperatures, the temperature control system 25 is used to realize the reaction characteristics at different set temperatures.

[0081] The liquid supply system of the present utility model can supply the liquid required for the reaction to the reaction system 24 regularly and quantitatively according to the reaction requirements, real-time monitor relevant parameters such as the flow rate, temperature, and pressure of the liquid, and is required to be able to generate and supply high-temperature steam.

[0082] The gas test system is mainly used to monitor in real time the key parameters such as the pressure, temperature, and flow rate of the gas generated by the reaction; an adjustable backpressure valve is provided inside to measure the reaction performance of the hydrogen storage material under different pressures; a gas sampling interface 7 is reserved inside for the detection of gas components. The temperature control system 25 is used to control the temperature of the reaction system 24 to evaluate and study the performance of the hydrolysis reaction at different specified temperatures. Considering that the hydrolysis reaction of the solid-state hydrogen storage material is an exothermic reaction, the heat dissipation requirement of the reaction system 24 itself needs to be considered synchronously during the entire temperature control process, so as to effectively control the temperature of the reaction system 24.

[0083] Specifically, the electrical control system mainly consists of a host computer control unit, a DC power supply, power distribution, and an extended I / O interface module. Its main function is to provide an auxiliary low-voltage DC power supply for the electrical components of the system test bench; a certain number of digital, analog input, communication, etc. interfaces are reserved for users to facilitate the expansion of system functions by users. The host computer control unit realizes data acquisition, system control, system status monitoring, man-machine dialogue, etc., and has functions such as processing, displaying, storing, analyzing, and exporting the data during the test and system operation process. The host computer control unit mainly consists of a main controller, an industrial computer, a display, a communication module, system control software, etc.

[0084] Specifically, the electrical control components and measurement units of all systems interact with the electrical control system to realize the automated measurement and control of the overall test system.

[0085] A method for evaluating the hydrolysis performance of a solid-state hydrogen storage material using the above system includes the following steps:

[0086] 1) Calibrate the volume V of the gas measurement system sys and the "dead volume" V of the sample chamber of the reaction system 24 dead , where the "dead volume" V of the sample chamber dead is the sample chamber volume minus the sample volume;

[0087] 2) Preparation of the liquid supply system

[0088] First, confirm that the quick connection between the liquid supply system and the reaction system 24 is disconnected. Open the bypass hand valve 26 to connect the liquid supply pipeline to the waste liquid discharge port. Open the nitrogen purge program of the control software to purge the liquid supply pipeline. After purging, store the raw material liquid required for the reaction in the liquid storage tank 1, start the metering pump 2 to work. When the raw material liquid flows out from the waste liquid discharge port of the bypass hand valve 26, turn off the metering pump 2, close the bypass hand valve 26, and perform the liquid supply zeroing setting on the control software;

[0089] 3) Set the working temperature and pressure of the reaction system 24

[0090] Set the operating temperature of the reaction system 24 through the temperature control system 25, and set the base pressure before the reaction through the adjustable back pressure valve 14 and the pressurizing device to achieve the hydrolysis reaction at a certain temperature and a certain pressure;

[0091] 4) Start the hydrolysis reaction

[0092] Confirm the reliable quick connection of the liquid supply system to the reaction system 24 and the reliable quick connection of the gas measurement system to the reaction system 24; quickly connect the hydrogen recovery interface 16 to the gas tail exhaust or gas utilization device at the rear end, and perform a zero setting on the gas flow meter 15; open the solenoid valve 9 of the reaction system 24 that enters the gas measurement system, start the metering pump 2 according to the test condition requirements, and supply liquid at the set rate. The electrical control system reads the gas flow meter 15, the temperature of the gas measurement system, and the pressure of the gas measurement system in real time;

[0093] 5) Generate the automatic test results of the hydrolysis test through the control software

[0094] Monitor the real-time hydrogen flow rate and cumulative hydrogen flow rate during the reaction process through the flow meter 15. The control software measures the stable temperature TN sys and stable pressure PN sys of the gas measurement system, the volume V sys of the gas measurement system, and the "dead volume" V dead of the sample chamber to correct the real-time hydrogen flow rate and cumulative hydrogen flow rate, thereby improving the accuracy of the overall test results.

[0095] The specific method of the correction is as follows: The cumulative gas flow rate is defined as the difference in the mass fraction of the gas before and after the reaction in the cumulative gas flow rate value of the hydrogen flow meter and the volume V sys of the gas measurement system and the "dead volume" V dead of the sample chamber. The real-time gas flow rate is located as the difference in the mass fraction of the gas before and after the reaction in the real-time gas flow rate value of the hydrogen flow meter and the volume V sys of the gas measurement system and the "dead volume" V dead of the sample chamber. That is, the volume V sys of the gas measurement system and the "dead volume" V dead of the sample chamber are used to correct the real-time hydrogen flow rate and cumulative hydrogen flow rate, thereby improving the accuracy of the overall test results.

[0096] The calibration steps of the volume V sys of the gas measurement system are as follows:

[0097] 1) Select hydrogen as the calibration gas, complete the airtightness test of the gas test system, and ensure that the hydrogen leakage rate of the pipeline system to be calibrated ≤ 1.7×10 -4Pa·m 3 / s (at a temperature of 0 °C and an absolute pressure of 101.325 kPa);

[0098] 2) Evacuate the gas measurement system to be calibrated. Open solenoid valve 20 and the solenoid valve of the gas storage tank 13, start the vacuum pump 21, and evacuate for 25 - 35 minutes. After evacuation, close all valves;

[0099] 3) Open the solenoid valve of the hydrogen cylinder 22 to fill the gas measurement system with hydrogen at a certain pressure, then close the solenoid valve of the hydrogen cylinder 22, and wait for 4 - 6 minutes to ensure the pressure and temperature of the system are stable. Measure the temperature T0 sys and pressure P0 sys ;

[0100] 4) Open the solenoid valve of the gas storage tank 13 to allow the hydrogen in the pipeline to flow into the hydrogen storage calibration device 19, and wait for 4 - 6 minutes until the values of the pressure sensor 18 of the gas storage tank and the pressure sensor 12 are stable. Ensure the pressure and temperature of the system are stable, and measure the temperature T1 sys and pressure P1 sys ;

[0101] 5) According to the gas mass conservation equation in the closed cavity before and after opening the solenoid valve of the gas storage tank 13, T1 sys is the same as T0 sys , and the influence of temperature can be ignored in the equation:

[0102] P0 sys V sys = P1 sys (V sys +V bd )

[0103] 6) Close the solenoid valve of the gas storage tank 13, evacuate the system again. Open solenoid valve 20, start the vacuum pump 21, and evacuate for 25 - 35 minutes. After evacuation, close all valves; Record the hydrogen pressure P1 in the hydrogen storage calibration tank 19 through the pressure sensor 18 of the gas storage tank bd ;

[0104] 7) Open the solenoid valve of the gas storage tank 13 to allow the hydrogen in the hydrogen storage calibration tank 19 to flow into the pipeline system, and wait for 4 - 6 minutes until the values of the pressure sensor 18 of the gas storage tank and the pressure sensor 12 are stable. Ensure the pressure and temperature of the system are basically stable, and measure the temperature T2 sys and pressure P2 sys ;

[0105] 8) According to the gas mass conservation equation in the closed cavity before and after the opening of the gas storage tank solenoid valve 13, considering the same temperature change, the influence of temperature can be ignored in the equation:

[0106] P1 bd V bd = P2 sys (V sys +V bd )

[0107] 9) Through the above binary equation system, the volume V sys of the gas measurement system and the volume V bd of the calibrated hydrogen storage device are obtained.

[0108] Select hydrogen as the calibration gas. Since the test gas is hydrogen, using hydrogen as the calibration gas can reduce the test deviation caused by gas inconsistency;

[0109] The specific calibration steps for the "dead volume" V dead of the sample chamber of the reaction system 24 are as follows:

[0110] 1) First, prepare the reaction system 24 filled with solid hydrogen storage powder, keep the quick connection of the liquid supply system disconnected, and connect the quick connection of the gas measurement system.

[0111] 2) Select hydrogen as the calibration gas, complete the airtightness test of the gas test system, and ensure that the hydrogen leakage rate of the calibrated pipeline system and the reaction system 24 to be calibrated is ≤ 1.7×10 -4 Pa·m 3 / s (when the temperature is 0 °C and the absolute pressure is 101.325 kPa);

[0112] 3) Simultaneously evacuate the calibrated gas measurement system and the reaction system 24 to be calibrated. Open the solenoid valve 9, the gas storage tank solenoid valve 13, and the solenoid valve 20 of the reaction system 24, start the vacuum pump 18, and evacuate for 25 - 35 minutes. After evacuation, close all valves;

[0113] 4) Open the hydrogen cylinder solenoid valve 22 and the gas storage tank solenoid valve 13, fill the gas measurement system with hydrogen at a certain pressure, then close the hydrogen cylinder solenoid valve 22, wait for 4 - 6 minutes to ensure the pressure and temperature of the system are stable, and measure the temperature T3 sys and pressure P3 sys of the pipeline system through the temperature sensor 11 and the pressure sensor 12;

[0114] 5) Open the solenoid valve 9 of the reaction system 24 to allow hydrogen in the pipeline to flow into the reaction system 24. Wait for 4 - 6 minutes until the pressure in the reaction system 24 and the value of the pressure sensor 12 become stable, ensuring the stability of the system pressure and temperature. Measure the temperature T4 of the pipeline system through the temperature sensor 11 and the pressure sensor 12 sys and the pressure P4 sys ;

[0115] 6) According to the gas mass conservation equation in the closed cavity before and after opening the solenoid valve 9 of the reaction system 24, T4 sys is the same as T3 sys , and the influence of temperature can be ignored in the equation:

[0116] P3 sys (V sys +V bd ) = P4 sys (V sys +V bd +V dead )

[0117] 7) Since the volume V sys of the gas measurement system and the volume V bd of the calibrated hydrogen storage device are known, the "dead volume" V dead of the reaction system 24 is obtained through the above system of linear equations.

[0118] The following embodiments are carried out using the above test system and test method to further explain the technical solution of the present invention.

[0119] Embodiment 1

[0120] The following takes the hydrolysis reaction of a magnesium-based composite material with Mg(BH4)2 as the substrate at - 35°C as an example to introduce the entire system, test method, and automatically generated test results.

[0121] (1) Complete the calibration of the volume V sys of the gas measurement system as required, and then load 1 g of the Mg(BH4)2 composite material into the sample chamber of the reaction system 24. Complete the calibration work of the "dead volume" V dead according to the specific calibration method of the "dead volume" V dead of the reaction system 24; simultaneously add ethylene glycol solution below - 25°C to the liquid storage tank 1, control the first three-way solenoid valve 3 and the second three-way solenoid valve 5 to allow the low-temperature ethylene glycol solution to pass through the bypass pipe, open the bypass valve 26 and connect it to the waste liquid port; start the metering pump 2, and when the liquid flows out of the bypass valve 26, close the bypass valve 26 and stop the metering pump 2. At this time, in the control system, set the metering pump to zero.

[0122] (2) Add 1 g of powdered magnesium-based composite material to the sample chamber of the reaction system 24. According to the requirements of the test conditions, set the base pressure to 0.5 MPa and the reaction temperature to -35 °C: 1) Set the base pressure to 0.5 MPa. Simultaneously evacuate the calibrated gas measurement system and the reaction system 24. Open the solenoid valve 9 of the reaction system 24 and the solenoid valve 20 of the vacuum pump, start the vacuum pump 18, and evacuate for 25 - 35 min. After the evacuation is completed, close all valves. Open the solenoid valve 22 of the hydrogen cylinder and the solenoid valve 9 of the reaction system 24, and fill the gas measurement system and the reaction system 24 with hydrogen at a pressure of 0.5 MPa. At the same time, set the pressure of the adjustable backpressure valve 14 to 0.5 MPa, then close the solenoid valve 22 of the hydrogen cylinder, and wait for 4 - 6 min to ensure the stability of the system pressure and temperature, and perform a zero setting on the flowmeter 15. 2) Set the reaction temperature to -35 °C, start the temperature control system 25, and control the temperature of the reaction system 24 at -35 °C.

[0123] (3) Set the liquid supply flow rate of the liquid supply system in the control system to 3 ml / min. Confirm that the pressures, temperatures, and flow rates monitored by each system are in normal operation. Connect the quick connection of the liquid supply system to the reaction system 24, and start the low-temperature hydrolysis reaction test. At this time, simultaneously record the instantaneous flow rate and cumulative flow rate of the metering pump 2, the working pressure and temperature of the reaction system 24, the pressure and temperature of the gas measurement system, and the instantaneous flow rate and cumulative flow rate of the flowmeter 15.

[0124] Finally, the hydrolysis kinetic test results of the instantaneous hydrogen production rate and cumulative hydrogen production of the magnesium-based composite material at -35 °C are automatically generated by the upper computer system (the abscissa is time, and the ordinates are the instantaneous flow rate and cumulative flow rate), as Figure 2 shown. It can be concluded that the high point of the instantaneous hydrogen production rate of the magnesium-based composite material at -35 °C is in the initial reaction stage, and the highest hydrogen production rate is close to 5 L / min. At about 80 s, the reaction is basically completed. The effective reaction liquid demand is 4.5 ml, and the final cumulative hydrogen production is 2.72 L. From this, the maximum hydrogen production rate of this reaction is calculated to be 82%. In the future, from the perspective of hydrogen production rate, there is room for further improvement in the hydrolysis performance of the magnesium-based composite material.

Claims

1. An automatic test system for evaluating the hydrolysis performance of solid-state hydrogen storage materials, characterized in that, It includes a liquid supply system, a gas measurement system, a reaction system (24), a temperature control system (25) and an electrical control system. The liquid supply system is connected to the liquid inlet of the reaction system (24), the gas measurement system is connected to the gas outlet of the reaction system (24), and the temperature control system (25) is connected to the reaction system (24) to achieve temperature control of the reaction system (24); the liquid supply system, the gas measurement system, the temperature control system (25), and the reaction system (24) are all connected to the electrical control system. The liquid supply system includes a liquid storage tank (1), a metering pump (2), a first three-way solenoid valve (3), a steam generator (4), and a second three-way solenoid valve (5) connected in sequence through pipelines; there is a pipeline connected between the first three-way solenoid valve (3) and the second three-way solenoid valve (5). The gas measurement system includes a hydrogen pipeline connected to the reaction system (24), and a reaction system solenoid valve (9), a dryer (10), a pressurizing device, a temperature sensor (11), a vacuum pump (21), a pressure sensor (12), a gas storage device, an adjustable backpressure valve (14), and a flowmeter (15) are sequentially arranged on the hydrogen pipeline.

2. The fully automatic test system for evaluating the hydrolysis performance of solid-state hydrogen storage materials according to claim 1, characterized in that, A check valve (6) is also provided on the pipeline where the liquid supply system is connected to the reaction system (24).

3. The fully automatic test system for evaluating the hydrolysis performance of solid-state hydrogen storage materials according to claim 1, wherein, A nitrogen purge device is also connected to the pipeline between the metering pump (2) and the first three-way solenoid valve (3); a waste liquid discharge port is provided on the pipeline where the liquid supply system is connected to the liquid inlet pipe of the reaction system (24), and the opening and closing of the waste liquid discharge port are controlled by a bypass hand valve (26).

4. The fully automatic test system for evaluating the hydrolysis performance of solid-state hydrogen storage materials according to claim 1, wherein The gas measurement system also includes a gas chromatograph analyzer, and the gas chromatograph analyzer is connected to a gas sampling interface (7) on the hydrogen pipeline through a needle valve (8) for on-line monitoring of the composition of the gas components after the reaction.

5. The fully automatic test system for evaluating the hydrolysis performance of solid-state hydrogen storage materials according to claim 3, characterized in that, The nitrogen purge device includes a nitrogen cylinder, a nitrogen pressure reducing valve (27) and a nitrogen cylinder solenoid valve (28).

6. The fully automatic test system for evaluating the hydrolysis performance of solid-state hydrogen storage materials according to claim 1, wherein, The pressurizing device includes a hydrogen cylinder, a hydrogen cylinder solenoid valve (22) and a hydrogen cylinder pressure reducing valve (23).

7. The full-automatic test system for evaluating the hydrolysis performance of solid-state hydrogen storage materials according to claim 1, characterized in that The gas storage device includes a gas storage tank (19) and a gas storage tank solenoid valve (13), the gas storage tank (19) is connected to the hydrogen pipeline through the gas storage tank solenoid valve (13), and a gas storage tank pressure sensor (18) is provided on the outlet pipeline of the gas storage tank (19).

8. The fully automatic test system for evaluating the hydrolysis performance of solid-state hydrogen storage materials according to claim 1, wherein, The full-automatic test system also includes a system frame for fixing and protecting each system and a hydrogen recovery interface (16) for discharging hydrogen, and a ventilation system (17) is also provided inside the system frame.

9. The fully automatic test system for evaluating the hydrolysis performance of solid-state hydrogen storage materials according to claim 1, characterized in that, The electrical control system includes a host computer control unit, a DC power supply, power distribution, and an extended I / O interface module, and the host computer control unit includes a main controller, an industrial computer, a display, a communication module, and control software.

10. The fully automatic test system for evaluating the hydrolysis performance of solid-state hydrogen storage materials according to claim 9, characterized in that, The control software is obtained by using LABVIEW visual programming according to the overall requirements of the test system.

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