CN112326501A - System and method for testing various performances of hydrogen storage material - Google Patents

System and method for testing various performances of hydrogen storage material Download PDF

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CN112326501A
CN112326501A CN202011284527.3A CN202011284527A CN112326501A CN 112326501 A CN112326501 A CN 112326501A CN 202011284527 A CN202011284527 A CN 202011284527A CN 112326501 A CN112326501 A CN 112326501A
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electric control
control valve
hydrogen
pressure
subsystem
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陈培源
徐义雄
刘峰
曾扬文
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Huizhou Huadatong Gas Manufacturing Co Ltd
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Huizhou Huadatong Gas Manufacturing Co Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N7/00—Analysing materials by measuring the pressure or volume of a gas or vapour
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N7/00—Analysing materials by measuring the pressure or volume of a gas or vapour
    • G01N7/02—Analysing materials by measuring the pressure or volume of a gas or vapour by absorption, adsorption, or combustion of components and measurement of the change in pressure or volume of the remainder

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Abstract

The invention relates to the technical field of hydrogen storage material performance testing, and discloses a hydrogen storage material multiple performance testing system, which comprises a main pipeline, a high-pressure gas source subsystem, a gas storage subsystem, a reaction subsystem, a temperature control subsystem, a thermal conductivity monitoring subsystem, an exhaust subsystem, a data acquisition and processing subsystem, a first pressure sensor and a second pressure sensor, wherein the high-pressure gas source subsystem is connected with the gas storage subsystem; the system can complete the following steps: the method comprises the following steps of calibrating the volume of a reaction chamber, measuring the leakage rate of the reaction chamber, testing the performance of the hydrogen storage material under different hydrogen purities, measuring the hydrogen purities before and after hydrogen storage/release, testing the cycle life of the hydrogen storage material under different initial hydrogen purities, and the like. The invention also discloses a testing method of the hydrogen material multiple performance testing system, which is controlled by a computer, is convenient to operate, has complete measurement parameters and higher accuracy, and thus better obtains the performance of the hydrogen storage material under different hydrogen charging purities.

Description

System and method for testing various performances of hydrogen storage material
Technical Field
The invention relates to the technical field of hydrogen storage material performance testing, in particular to a system and a method for testing various performances of a hydrogen storage material.
Background
The hydrogen is used as a clean energy source, has the characteristics of large reserve capacity, easiness in preparation, no pollution and the like, and has great potential as a new energy source for replacing the traditional energy source under the era background of constructing a resource-saving and environment-friendly society. The production, storage and transportation of hydrogen are all key issues when utilizing hydrogen energy.
The existing hydrogen storage technology can be divided into three types, one is a gaseous hydrogen storage technology, and hydrogen is compressed and stored in a high-pressure container; the second is a liquid hydrogen storage technology, which is to store the hydrogen gas in an insulated container after the hydrogen gas is liquefied at low temperature and high pressure; thirdly, solid-state hydrogen storage technology, hydrogen and solid-state hydrogen storage materials are combined in a physical or chemical mode. The three methods are widely applied in different fields. The continuous development of various hydrogen storage materials also promotes the continuous progress of the test method of the hydrogen storage materials.
Application No.: 201210462073.3, patent name: a new method for representing hydrogen absorption and desorption PCT curves of a hydrogen storage material and a testing device thereof disclose a testing device capable of representing hydrogen absorption and desorption PCT curves of the hydrogen storage material, the device is mainly used for testing the hydrogen absorption and desorption performance of the hydrogen storage material, but the device can only obtain the performance parameters of the hydrogen storage material under single hydrogen purity, and cannot explore the influence of different initial hydrogen purities on the performance of the hydrogen storage material. Application No.: 201811635247.5, patent name: an automatic tester for the cyclic life of hydrogen storage material is composed of a computer for automatically testing the cyclic life of hydrogen storage material, and a controller for controlling the operation of said computer.
The hydrogen storage and release performance of the hydrogen storage material, the cycle life of the hydrogen storage material and the change of hydrogen purity before and after the hydrogen storage technology is used are important parameters for testing whether the hydrogen storage material can be put into use. The pressure-component isotherm (PCT curve) is an important characteristic curve in consideration of the performance of the hydrogen storage material, and can obtain the adsorption amount of the hydrogen storage material at a certain temperature, the decomposition pressure value of the hydride, and the like. The hydrogen storage material has disproportionation reaction in the repeated use process, which causes the agglomeration of a small part of powder, and the process is irreversible, and the hydrogen storage capacity and the service life of the hydrogen storage material are greatly reduced. Thus, the cycle life of the material is also an important parameter. The reduction of the hydrogen purity leads the hydrogen to be incapable of meeting the design requirement and the production safety and meeting the use requirement of a user on the high-purity hydrogen, so the change of the hydrogen purity before and after hydrogen storage is tested, and the reason for influencing the hydrogen purity is found out, thereby finding out the improvement measure.
Therefore, it is essential to design a hydrogen storage material performance test system which can adapt to various conditions and simultaneously measure various parameters.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a hydrogen storage material multiple performance test system which is used for testing the performance of the hydrogen storage material under different initial hydrogen purities and detecting the hydrogen storage/release capacity, the cycle life and the hydrogen purity change before and after reaction of the hydrogen storage material. The invention also provides a method for testing the multiple properties of the hydrogen storage material, which has simple steps and is convenient to implement.
The purpose of the invention is realized by the following technical scheme: a hydrogen storage material multiple performance test system comprises a main pipeline, a high-pressure gas source subsystem, a gas storage subsystem, a reaction subsystem, a temperature control subsystem, a thermal conductivity monitoring subsystem, an exhaust subsystem, a data acquisition processing subsystem, a first pressure sensor and a second pressure sensor; the high-pressure gas source subsystem comprises a pure argon gas cylinder, a pure helium gas cylinder, a high-pressure hydrogen gas cylinder, a pure carbon dioxide steel cylinder, a first filter, a first stop valve, a second stop valve, a first electric control valve and a second electric control valve; the pure argon gas cylinder, the pure helium gas cylinder, the high-pressure hydrogen cylinder and the pure carbon dioxide steel cylinder are respectively provided with a first filter at the outlet end, the pure argon gas cylinder is connected with the main pipeline through a first stop valve, the pure helium gas cylinder is connected with the main pipeline through a second stop valve, the high-pressure hydrogen cylinder is connected with the main pipeline through a first electric control valve and the pure carbon dioxide steel cylinder is connected with the main pipeline through a second electric control valve, and the pure argon gas cylinder is positioned in front of a third electric control valve;
the gas storage subsystem comprises a first gas storage tank, a second filter, a fifth electric control valve and a sixth electric control valve; the open ends of the first air storage tank and the second air storage tank are provided with a second filter, wherein the open end of the first air storage tank is connected with the main pipeline through a fifth electric control valve, the open end of the second air storage tank is connected with the main pipeline through a sixth electric control valve, and the connection positions of the first air storage tank and the second air storage tank with the main pipeline are sequentially positioned behind the third electric control valve;
the reaction subsystem comprises a reaction chamber, a third filter, a fourth electric control valve and a third stop valve, wherein an air inlet of the reaction chamber is connected with the main pipeline and is positioned between the connection position of the first air storage tank and the main pipeline and the connection position of the second air storage tank and the main pipeline, and the third filter, the fourth electric control valve and the third stop valve are sequentially arranged between the air inlet of the reaction chamber and the main pipeline; the first pressure sensor is arranged on the main pipeline and is positioned between the first gas storage tank and the reaction chamber, the second pressure sensor is arranged between the fourth electric control valve and the third stop valve, and the temperature control subsystem is connected with the reaction chamber;
and the temperature control subsystem, the thermal conductivity monitoring subsystem, the exhaust subsystem, the first electric control valve, the second electric control valve, the third electric control valve, the fourth electric control valve, the fifth electric control valve, the sixth electric control valve, the seventh electric control valve, the first pressure sensor and the second pressure sensor are all connected with the data acquisition and processing subsystem.
Further, the reaction chamber comprises a sample chamber and a jacketed heat exchanger; the jacketed type heat exchanger is coated on the periphery of the sample chamber, the top end of the sample chamber is provided with an air inlet, the top end of one side of the jacketed type heat exchanger is provided with a high-temperature steam inlet, the bottom end of the jacketed type heat exchanger is provided with a cooling water inlet, the top end of the other side of the jacketed type heat exchanger is provided with a cooling water outlet, the bottom end of the jacketed type heat exchanger is provided with a condensed water outlet, and the high-temperature steam inlet and the cooling water inlet are connected.
Furthermore, the thermal conductivity monitoring subsystem comprises a thermal conductivity pipeline connected with the main pipeline, a fourth stop valve, a first heater and a thermal conductivity cell are sequentially installed on the thermal conductivity pipeline, and the first heater and the thermal conductivity cell are both connected with the data acquisition and processing subsystem.
Further, the exhaust subsystem comprises an evacuation portion and a vacuum portion which are connected with the main pipeline in parallel; the emptying part comprises a first branch and a second branch which are connected with the main pipeline, a first flow limiting valve is arranged on the first branch, and a fifth stop valve and a carbon dioxide steel cylinder are sequentially arranged on the second branch; the vacuum part comprises a vacuum pumping pipeline connected with the main pipeline, and an eighth electric control valve, a second flow limiting valve and a vacuum pump which are sequentially arranged on the vacuum pumping pipeline, wherein the eighth electric control valve is connected with the data acquisition and processing subsystem.
Further, the temperature control subsystem comprises a second heater and a cooler, and the second heater and the cooler are both connected with the reaction chamber and the data acquisition and processing subsystem.
Further, the data acquisition and processing subsystem comprises a computer and a hub; the first electric control valve, the second electric control valve, the third electric control valve, the fourth electric control valve, the fifth electric control valve, the sixth electric control valve, the seventh electric control valve, the thermal conductivity monitoring subsystem, the exhaust subsystem, the temperature control subsystem, the first pressure sensor and the second pressure sensor are all connected with a computer through a concentrator.
Further, a safety valve is installed on each of the first air storage tank and the second air storage tank in the air storage subsystem.
A test method of a system for testing various performances of a hydrogen storage material comprises the following steps:
s101, vacuumizing a test system: and putting a sample into the sample chamber, putting the sample into a jacketed heat exchanger, connecting a third filter and a fourth electric control valve, connecting a test system through a third stop valve, opening a seventh electric control valve, an eighth electric control valve and a second flow limiting valve, closing the first stop valve, the second stop valve, the fourth stop valve, the first electric control valve, the second electric control valve and the first flow limiting valve, and opening a vacuum pump for vacuumizing for about 15-20 min.
S201, volume calibration of a test system: closing all valves, opening the first stop valve, the third electric control valve and the fifth electric control valve, introducing pure argon into the system, and recording the pressure in the system at the moment by the first pressure sensor to obtain P1(ii) a Opening the third stop valve and the fourth electric control valve to enable argon in the circulating system to enter the sample chamber, recording the reading of the second pressure sensor at the moment, and obtaining P2。
The existing gas state equation PV ═ nZRT, where P is pressure, V is reaction chamber volume, n is the amount of argon species, R is the gas molar constant, Z is the compression factor:
from P2Vs＝(P1-P2)V1Z2/Z1The volume V of the reaction chamber can be determinedsIn which V is1The volume of the first hydrogen storage bottle is the compression factor Z under constant temperature1、Z2Is a function of pressure;
repeating step S201 several times to obtain multiple VsAnd calculating an average value to reduce errors;
s202: closing all the valves, opening the second stop valve, the third electric control valve and the fifth electric control valve, introducing pure helium into the system, and recording the pressure in the system at the moment by the first pressure sensor; the third stop valve and the fourth electrically controlled valve are opened to allow helium gas in the circulation system to enter the sample chamber, at which time the second pressure sensor reading is recorded.
Step S202 is repeated as above and V is obtained from PV ═ nZRTtAnd calculating the average value, V under normal conditionssAnd VtAre substantially equal on average.
S301, testing the leakage rate of the system: opening the first electric control valve, the third electric control valve and the fourth electric control valveThe control valve and the third stop valve are closed, the seventh electric control valve is closed, after 8-15 MPa hydrogen is introduced into the system, the first electric control valve and the third electric control valve are closed, the system operates at room temperature for 10-20 hours, the pressure changes of the sample chamber, the first gas storage tank and the second gas storage tank in the process are monitored, the pressure data of all measurement points are subjected to linear fitting, the leakage rate is obtained, and under the normal condition, the leakage rate of a container with good tightness is 10-8mol/s or less.
S401, after completing S101 to S301, the test system can perform the following parameter measurement:
determination of the purity of the initial hydrogen:
closing all valves; opening a high-pressure hydrogen cylinder, a pure carbon dioxide steel cylinder, a first electric control valve, a second electric control valve, a third electric control valve, a fifth electric control valve, controlling the first electric control valve and the second electric control valve by a computer to adjust the flow of hydrogen and carbon dioxide so as to change the purity of the hydrogen, enabling the hydrogen and the carbon dioxide to enter a system through a first filter, flowing into a first gas storage tank to wait for a period of time so as to uniformly mix the hydrogen and the carbon dioxide, then closing the third electric control valve, opening a seventh electric control valve and a fourth stop valve, heating the hydrocarbon mixed gas to a high temperature of 300-500 ℃ through a first heater, enabling the hydrocarbon mixed gas to enter a1。
Measurement of hydrogen storage/release Performance of the Hydrogen storage Material:
hydrogen absorption: closing the fourth electric control valve, the third stop valve, the sixth electric control valve and the seventh electric control valve, opening the high-pressure hydrogen cylinder, the first electric control valve and the fifth electric control valve, allowing hydrogen to enter the system through the first filter, flowing into the first gas storage tank for a period of time, monitoring pressure change through the first pressure sensor, opening the third stop valve and the fourth electric control valve, and maintaining the temperature of the sample chamber to be proper low temperature T through the cooler1At the moment, hydrogen flows into the reaction chamber, the pressure change condition along with time in the hydrogen absorption process is recorded by the second pressure sensor, the pressure is continuously increased, then a hydrogen absorption platform appears, the pressure is increased again, and the pressure of the hydrogen absorption platform is recorded.
Hydrogen discharge: and closing the fifth electric control valve, opening the sixth electric control valve, keeping the temperature of the sample chamber to be proper high temperature T2 by using the second heater, enabling the hydrogen in the sample chamber to flow into the second gas storage tank, opening the fifth stop valve, the seventh electric control valve and the first flow limiting valve when the pressure displayed by the first pressure sensor is similar to that displayed by the second pressure sensor, slowly discharging the hydrogen in the second gas storage tank into the air, and recording the data of the change of the system pressure along with time by using the second pressure sensor to obtain a PCT curve.
Performance test of hydrogen storage materials under different initial hydrogen purities:
hydrogen absorption: closing the fourth electric control valve, the third stop valve, the sixth electric control valve and the seventh electric control valve, opening the high-pressure hydrogen cylinder, the pure carbon dioxide steel cylinder, the first electric control valve, the second electric control valve and the fifth electric control valve, enabling the hydrogen and the carbon dioxide to enter a main pipeline through a first filter and be mixed, enabling the hydrogen and the carbon dioxide to flow into a first gas storage tank, waiting for a period of time, uniformly mixing, monitoring pressure change through a first pressure sensor, opening the third stop valve and the fourth electric control valve, and keeping the temperature of the reaction chamber to be proper low temperature T by using a cooler1At the moment, the hydrocarbon mixed gas flows into the reaction chamber, the change condition of the pressure along with the time in the hydrogen absorption process is recorded by the second pressure sensor, the pressure is continuously increased, a hydrogen absorption platform appears, and the pressure of the hydrogen absorption platform is recorded;
hydrogen discharge: closing the fifth electric control valve, opening the sixth electric control valve, and maintaining the temperature of the reaction chamber at the proper high temperature T by the second heater2And when the pressure displayed by the first pressure sensor is similar to that displayed by the second pressure sensor, the fifth stop valve, the seventh electric control valve and the first flow limiting valve are opened, the hydrocarbon mixed gas in the second gas storage tank is slowly discharged into the air, and the pressure of the system is recorded by the second pressure sensor along with the change of time, so that a pressure-component isotherm (PCT curve) under the hydrogen purity is obtained.
The test was carried out by adjusting the flow rates of hydrogen and carbon dioxide with a computer so that the purity of hydrogen was 95%, 90%, 75%, 50%, respectively.
Test to determine the cycle life of hydrogen storage materials at different initial hydrogen purities:
step 1: closing the third stop valve, the sixth electric control valve and the seventh electric control valve, opening the high-pressure hydrogen cylinder, the pure carbon dioxide steel cylinder, the first electric control valve, the second electric control valve, the third electric control valve and the fifth electric control valve, controlling the first electric control valve and the second electric control valve by a computer to adjust the flow of hydrogen and carbon dioxide so as to change the purity of the hydrogen, enabling the hydrogen and the carbon dioxide to enter the system through the first filter to be mixed, flowing into the first gas storage tank, enabling the hydrogen and the carbon dioxide to be uniformly mixed after waiting for a period of time, monitoring the pressure change through the first pressure sensor, closing the third electric control valve after the pressure reaches a certain value, and recording the system pressure P at the moment3Opening the third stop valve and the second electric control valve, flowing the hydrocarbon mixed gas into the reaction chamber, and maintaining the temperature of the reaction chamber at a low temperature T by using a cooler1At this point, the sample begins to absorb hydrogen, the pressure change is monitored by the second pressure sensor, and the pressure P at this point is recorded after stabilization4。
Step 2: closing the fifth electric control valve, opening the sixth electric control valve, and maintaining the temperature of the reaction chamber at a high temperature T by the second heater2Then the hydrocarbon gas mixture in the reaction chamber flows to the second gas storage tank, the system pressure is reduced, the pressure change is monitored by the second pressure sensor, and the pressure P at the moment is recorded5And opening the seventh electric control valve, the fifth stop valve and the first flow limiting valve, reducing the purity of hydrogen after the hydrocarbon mixed gas and the carbon dioxide are mixed, discharging the gas in the system into the air, then closing the fifth stop valve and the first flow limiting valve, opening the eighth electric control valve and the second flow limiting valve, and vacuumizing the system for 15-20 min.
And (3) setting cycle times in the computer, performing multiple cycles on the step 1 and the step 2, automatically stopping after the cycle times are reached, and recording data.
The change in purity of the hydrogen before and after the cycle was measured:
initial hydrogen purity testing step:
closing all valves; opening the high pressure hydrogen cylinder, the pure carbon dioxide steel cylinder, the first to the third electric control valves, the secondAnd the fifth electric control valve is used for controlling the first electric control valve and the second electric control valve by a computer to adjust the flow of the hydrogen and the carbon dioxide so as to change the purity of the hydrogen, the hydrogen and the carbon dioxide enter the system through the first filter to be mixed and flow into the first gas storage tank, the hydrogen and the carbon dioxide are uniformly mixed after waiting for a period of time, then the third electric control valve is closed, the seventh electric control valve and the fourth stop valve are opened, the hydrocarbon mixed gas is heated to the high temperature of 300-500 ℃ through the first heater and enters the heat conducting cell, and the heat conductivity lambda at the moment is recorded1。
And (3) testing the purity of the circulated hydrogen:
only opening the fourth electric control valve, the third stop valve, the seventh electric control valve and the fourth stop valve, enabling the hydrocarbon mixed gas to flow out of the sample chamber, heating the hydrocarbon mixed gas to the high temperature of 300-500 ℃ through the first heater, then enabling the hydrocarbon mixed gas to enter the thermal conductivity cell, and recording the thermal conductivity lambda at the moment2。
Compared with the prior art, the invention has the following advantages:
1. the test system can be suitable for the performance test of the hydrogen storage material under various conditions and simultaneously measures a plurality of parameters. The high-pressure gas source of the test system consists of four gases, and the performance parameters of the hydrogen storage material under different initial hydrogen purities can be obtained by changing the flow of hydrogen and carbon dioxide and changing the purity of the hydrogen entering the system. The test system combines the hydrogen absorption and desorption test subsystem and the thermal conductivity monitoring subsystem, can measure various performances of the hydrogen storage material through program setting, and has the advantages of convenient and safe use and comprehensive and sufficient monitoring parameters. The pressure sensor, the electric control valve and the temperature control subsystem of the test system are connected with the data acquisition and processing subsystem, so that the hydrogen charging and discharging temperature can be automatically controlled and the valve can be opened and closed in the circulating process, the operation can be carried out for a long time, the manual operation is reduced, and the test efficiency and the test accuracy are improved.
2. The testing process of the testing system is controlled by a computer, the operation is convenient, the measurement parameters are complete, the precision is high, and the performance of the hydrogen storage material under different hydrogen charging purities can be better obtained.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a schematic structural diagram of a system for testing various properties of a hydrogen storage material according to the present invention;
FIG. 2 shows a schematic structural view of a reaction chamber according to the present invention;
in the figure, 1 is a main pipeline; 101 is a third electric control valve; 102 is a seventh electrically controlled valve; 2 is a high-pressure gas source subsystem; 201 is a pure argon bottle; 202 is a pure helium cylinder; 203 is a high-pressure hydrogen cylinder; 204 is a pure carbon dioxide steel cylinder; 205 is a first filter; 206 is a first stop valve; 207 is a second stop valve; 208 is a first electrically controlled valve; 209 is a second electrically controlled valve; 3 is a gas storage subsystem; 301 is a first air storage tank; 302 is a second air reservoir; 303 is a second filter; 304 is a fifth electrically controlled valve; 305 is a sixth electrically controlled valve; 4 is a reaction subsystem; 401 is a reaction chamber; 402 is a third filter; 403 is a fourth electrically controlled valve; 404 is a third stop valve; 405 is a sample chamber; 406 is a jacketed heat exchanger; 407 is an air inlet; 408 is a high-temperature steam inlet; 409 is a cooling water inlet; 410 is a cooling water outlet; 411 is a condensed water outlet; 5 is a temperature control subsystem; 501 is a second heater; 502 is a cooler; 6 is a thermal conductivity monitoring subsystem; 601 is a heat conducting pipeline; 602 is a fourth stop valve; 603 is a first heater; 604 is a thermal conductivity cell; 7 is an exhaust subsystem; 701 is a first branch; 702 is a first flow limiting valve; 703 is a second branch; 704 is a fifth stop valve; 705 a carbon dioxide steel cylinder; 706 is a vacuum pumping pipeline; 707 an eighth electrically controlled valve; 708 is a second flow limiting valve; 709 is a vacuum pump; 8 is a first pressure sensor; 9 is a second pressure sensor; 10 is a computer; 11 is a concentrator; 12 is a safety valve; 13 is the sample to be tested.
Detailed Description
The invention is further illustrated by the following figures and examples.
The system for testing multiple performances of a hydrogen storage material shown in fig. 1 comprises a main pipeline 1, a high-pressure gas source subsystem 2, a gas storage subsystem 3, a reaction subsystem 4, a temperature control subsystem 5, a thermal conductivity monitoring subsystem 6, an exhaust subsystem 7, a data acquisition and processing subsystem, a first pressure sensor 8 and a second pressure sensor 9; the high-pressure gas source subsystem 2 comprises a pure argon gas cylinder 201, a pure helium gas cylinder 202, a high-pressure hydrogen gas cylinder 203, a pure carbon dioxide gas cylinder 204, a first filter 205, a first stop valve 206, a second stop valve 207, a first electric control valve 208 and a second electric control valve 209; the outlet ends of the pure argon gas cylinder 201, the pure helium gas cylinder 202, the high-pressure hydrogen cylinder 203 and the pure carbon dioxide steel cylinder 204 are respectively provided with a first filter 205, the pure argon gas cylinder 201 is connected with the main pipeline 1 through a first stop valve 206, the pure helium gas cylinder 202 is connected with the second stop valve 207, the high-pressure hydrogen cylinder 203 is connected with the first electric control valve 208 and the pure carbon dioxide steel cylinder 204 through a second electric control valve 209, and the pure argon gas cylinder 201, the pure helium gas cylinder 202 and the pure carbon dioxide steel cylinder 204 are positioned in front of a third electric control valve 101 on; the high-pressure gas source subsystem provides gas with stable flow rate for the test system. The pure argon gas cylinder 201, the pure helium gas cylinder 202, the high-pressure hydrogen cylinder 203 and the pure carbon dioxide steel cylinder 204 are all cylinders with the diameter of 140mm and the height of 580mm, and can bear 10-30 MPa, wherein the purity of hydrogen of a gas source is not lower than 99.999%, the purity of carbon dioxide is not lower than 99.999%, the purity of helium is not lower than 99.999%, and the purity of argon is not lower than 99.999%. A filter is arranged between the gas storage steel cylinder and the valve, so that no impurity is introduced into the detection system.
The gas storage subsystem 3 comprises a first gas tank 301, a second gas tank 302, a second filter 303, a fifth electrically controlled valve 304 and a sixth electrically controlled valve 305; a second filter 303 is installed at the open end of each of the first air tank 301 and the second air tank 302, wherein the open end of the first air tank 301 is connected with the main pipeline 1 through a fifth electric control valve 304, the open end of the second air tank 302 is connected with the main pipeline 1 through a sixth electric control valve 305, and the connection positions of the first air tank 301 and the second air tank 302 with the main pipeline 1 are sequentially located behind the third electric control valve 101; the gas storage subsystem 3 is used for temporarily storing the hydrocarbon mixed gas entering from the high-pressure gas source subsystem 2, so that the hydrogen and the carbon dioxide to be tested are uniformly mixed, the pressure is stable, and then the mixed gas is introduced into the reaction chamber 401 for absorption, and the accuracy of the test is ensured. The diameter of the two gas storage tanks is 108mm, the height of the two gas storage tanks is 150mm, and the two gas storage tanks can bear 10-30 MPa. Can monitor the pressure variation in the first gas holder through first pressure sensor, simultaneously, relief valve 12 is connected respectively to two gas holders, can open exhaust gas voluntarily when pressure is too high, prevents that pressure is too high to produce the incident. The fifth electric control valve 304 and the sixth electric control valve 305 are connected with the hub 11, semi-automatic operation can be realized through computer program control, and the hydrocarbon mixed gas entering the testing system from the high-pressure gas source subsystem 2 firstly enters the first gas storage tank 301 to be uniformly mixed, and then enters the reaction subsystem 4 after being stabilized.
The reaction subsystem 4 comprises a reaction chamber 401, a third filter 402, a fourth electric control valve 403 and a third stop valve 404, wherein an air inlet 407 of the reaction chamber 401 is connected with the main pipeline 1 and is positioned between the connection position of the first air storage tank 301 and the main pipeline 1 and the connection position of the second air storage tank 302 and the main pipeline 1, and the third filter 402, the fourth electric control valve 403 and the third stop valve 404 are sequentially arranged between the air inlet 407 of the reaction chamber 401 and the main pipeline 1; the first pressure sensor 8 is installed on the main pipeline 1 and located between the first gas storage tank 301 and the reaction chamber 401, the second pressure sensor 9 is installed between the fourth electric control valve 403 and the third stop valve 404, and the temperature control subsystem 5 is connected with the reaction chamber 401.
The main pipeline 1 is also provided with a seventh electric control valve 102, the seventh electric control valve 102 is positioned behind the connection part of the second air storage tank 302 and the main pipeline 1, the evacuation subsystem 7 and the thermal conductivity monitoring subsystem 6 are both connected with the main pipeline 1 and positioned behind the seventh electric control valve 102, and the temperature control subsystem 5, the thermal conductivity monitoring subsystem 6, the exhaust subsystem 7, the first electric control valve 208, the second electric control valve 209, the third electric control valve 101, the fourth electric control valve 403, the fifth electric control valve 304, the sixth electric control valve 305, the seventh electric control valve 102, the first pressure sensor 8 and the second pressure sensor 9 are all connected with the data acquisition and processing subsystem.
As shown in fig. 2, the reaction chamber 401 includes a sample chamber 405 and a jacketed heat exchanger 406; the above-mentionedThe jacketed heat exchanger 406 and the sample chamber 405 adopt an S-1L type double-layer glass reaction kettle, the top end of the sample chamber 405 is provided with an air inlet 407, the top end of one side of the jacketed heat exchanger 406 is provided with a high-temperature steam inlet 408, the bottom end of the jacketed heat exchanger 406 is provided with a cooling water inlet 409, the top end of the other side of the jacketed heat exchanger is provided with a cooling water outlet 410, the bottom end of the jacketed heat exchanger is provided with a condensed water outlet 411, and the high-temperature steam inlet 408 and the cooling water inlet 409 are connected with a. As shown in fig. 2, the hydrogen storage material (sample 13 to be tested) is placed in the sample chamber 405, the mixed gas of hydrogen and carbon dioxide enters the reaction subsystem 4 from the gas inlet 407, and when the reaction subsystem 4 is cooled, the cooling water flows from the cooling water inlet 409 to the cooling water outlet 410 from bottom to top; when the reaction subsystem 4 is heating, the high temperature steam flows from the high temperature steam inlet 408 to the condensed water outlet 411 from top to bottom. The reaction subsystem 4 is connected with the temperature control subsystem 5, the hydrogen storage/release operation is controlled by controlling the temperature, and in the hydrogen absorption process of the hydrogen storage material, the cooler 502 is opened to introduce cooling water to enable the interior of the jacketed heat exchanger 406 to be at a low temperature T1During the hydrogen discharging process of the hydrogen storage material, the second heater 501 is turned on to introduce high-temperature water vapor to make the inside of the jacketed heat exchanger 406 at a high temperature T2. The jacketed heat exchanger 406 serves as a heat retention.
The thermal conductivity monitoring subsystem 6 comprises a thermal conduit 601 connected with the main conduit 1, a fourth stop valve 602, a first heater 603 and a thermal conductivity cell 604 are sequentially installed on the thermal conduit 601, and the first heater 603 and the thermal conductivity cell 504 are both connected with the computer 10. The gas to be detected passing through the first heater 603 is heated to a high temperature of 300-500 ℃ and enters the thermal conductivity cell 604, and the detection principle is as follows: according to the concentration change of the gas to be detected, the temperature of the thermosensitive element is changed, so that the resistance is changed, and the Wheatstone bridge is out of balance to generate an electric signal.
The exhaust subsystem 7 comprises an evacuation part and a vacuum part which are connected with the main pipeline 1 in parallel; the emptying part comprises a first branch 701 and a second branch 703 which are both connected with the main pipeline 1, wherein the first branch 701 is provided with a first flow limiting valve 702, and the second branch 703 is sequentially provided with a fifth stop valve 704 and a carbon dioxide steel cylinder 705; the vacuum part comprises a vacuum pumping pipeline 706 connected with the main pipeline 1, and an eighth electric control valve 707, a second flow limiting valve 708 and a vacuum pump 709 which are sequentially arranged on the vacuum pumping pipeline 706, wherein the eighth electric control valve 707 is connected with a computer. The exhaust subsystem 7 is connected with the main pipeline 1 through a seventh electric control valve 102, the exhaust subsystem is composed of an emptying part and a vacuum part which are connected in parallel, the emptying part is provided with a carbon dioxide steel cylinder 705, carbon dioxide discharged by the carbon dioxide steel cylinder is mixed with hydrogen discharged by the test system and then discharged into the air to prevent explosion caused by overhigh hydrogen concentration. The vacuum part is provided with a vacuum pump 709, gas in the system is pumped out before testing, interference of other impurities (such as water vapor) is eliminated, and the fact that mixed gas with accurate proportion is tested is guaranteed; the eighth electrically controlled valve 707 in the vacuum line 706 is connected to the second flow limiting valve 708, so that the gas flow can be effectively controlled during vacuum pumping, and the sample in the reaction chamber can be prevented from being sucked back to cause loss.
The temperature control subsystem 5 includes a second heater 501 and a cooler 502, and the second heater 501 (existing electric steam generator) and the cooler 502 (existing cooling water circulation device) are connected to the reaction chamber 401 and the computer 10. The supply of hot steam or cold flow required for the test to the reaction chamber 401 is controlled by the computer 10.
The data acquisition processing subsystem comprises a computer 10 and a hub 11; the first to eighth electrically controlled valves, the first pressure sensor 8, the second pressure sensor 9, the first and second heaters, the cooler 502, and the thermal conductivity cell 604 are all connected to the computer 10 through the hub 11. Used for recording the parameters of hydrogen purity, system pressure, temperature, etc. in the hydrogen storage/release process. The method specifically comprises the following steps: the computer is connected with the thermal conductivity cell 604, the first pressure sensor and the second pressure sensor and is used for monitoring the change of the hydrogen purity and the change of the system pressure in the hydrogen storage/release process; the computer is connected with the second heater 501 and the cooler 502, and changes the hydrogen storage/release state of the material by changing the temperature; meanwhile, the computer is connected with the first to eighth electric control valves, and the opening and closing of the valves can be controlled according to the program setting.
A test method of a system for testing various performances of a hydrogen storage material comprises the following steps:
s101, vacuumizing a test system: and putting a sample to be tested 13 into the sample chamber, putting the sample chamber into a jacketed heat exchanger, connecting a third filter and a fourth electric control valve, connecting a test system through a third stop valve, opening a seventh electric control valve, an eighth electric control valve and a second flow limiting valve, closing the first stop valve, the second stop valve, the fourth stop valve, the first electric control valve, the second electric control valve and the first flow limiting valve, and opening a vacuum pump for vacuumizing for about 15-20 min.
S201, volume calibration of a test system: closing all valves, opening the first stop valve, the third electric control valve and the fifth electric control valve, introducing pure argon into the system, and recording the pressure in the system at the moment by the first pressure sensor to obtain P1(ii) a Opening the third stop valve and the fourth electric control valve to enable argon in the circulating system to enter the sample chamber, recording the reading of the second pressure sensor at the moment, and obtaining P2. And pure helium and pure argon are used during volume calibration, so that the condition that the subsequent test is influenced by the fact that hydrogen is sucked into the material in the reaction chamber in advance is prevented.
The existing gas state equation PV ═ nZRT, where P is pressure, V is reaction chamber volume, n is the amount of argon species, R is the gas molar constant, Z is the compression factor:
from P2Vs＝(P1-P2)V1Z2/Z1The volume V of the reaction chamber can be determinedsIn which V is1The volume of the first hydrogen storage bottle is the compression factor Z under constant temperature1、Z2Is a function of pressure;
repeating step S201 several times to obtain multiple VsAnd calculating an average value to reduce errors;
s202: closing all the valves, opening the second stop valve, the third electric control valve and the fifth electric control valve, introducing pure helium into the system, and recording the pressure in the system at the moment by the first pressure sensor; the third stop valve and the fourth electrically controlled valve are opened to allow helium gas in the circulation system to enter the sample chamber, at which time the second pressure sensor reading is recorded.
Step S202 is repeated as above and V is obtained from PV ═ nZRTtAnd findAverage value, normal, VsAnd VtAre substantially equal on average.
S301, testing the leakage rate of the system: opening the first electric control valve, the third electric control valve, the fourth electric control valve and the third stop valve, closing the seventh electric control valve, introducing 8-15 MPa hydrogen into the system, closing the first electric control valve and the third electric control valve, operating at room temperature for 10-20 h, monitoring the pressure change of the sample chamber, the first air storage tank and the second air storage tank in the process, performing linear fitting on the pressure data of all measurement points to obtain the leakage rate, and under the normal condition, the leakage rate of the container with good tightness is 10-8mol/s or less.
S401, after completing S101 to S301, the test system can perform the following parameter measurement:
determination of the purity of the initial hydrogen:
closing all valves; opening a high-pressure hydrogen cylinder, a pure carbon dioxide steel cylinder, a first electric control valve, a second electric control valve, a third electric control valve, a fifth electric control valve, controlling the first electric control valve and the second electric control valve by a computer to adjust the flow of hydrogen and carbon dioxide so as to change the purity of the hydrogen, enabling the hydrogen and the carbon dioxide to enter a system through a first filter, flowing into a first gas storage tank to wait for a period of time so as to uniformly mix the hydrogen and the carbon dioxide, then closing the third electric control valve, opening a seventh electric control valve and a fourth stop valve, heating the hydrocarbon mixed gas to a high temperature of 300-500 ℃ through a first heater, enabling the hydrocarbon mixed gas to enter a1。
Measurement of hydrogen storage/release Performance of the Hydrogen storage Material:
hydrogen absorption: closing the fourth electric control valve, the third stop valve, the sixth electric control valve and the seventh electric control valve, opening the high-pressure hydrogen cylinder, the first electric control valve and the fifth electric control valve, allowing hydrogen to enter the system through the first filter, flowing into the first gas storage tank for a period of time, monitoring pressure change through the first pressure sensor, opening the third stop valve and the fourth electric control valve, and maintaining the temperature of the sample chamber to be proper low temperature T through the cooler1When hydrogen gas flows into the reaction chamber, the second pressure sensor records the absorptionAnd (3) the pressure changes along with time in the hydrogen process, the pressure continuously increases, then a hydrogen absorption platform appears, the pressure rises again, and the pressure of the hydrogen absorption platform is recorded.
Hydrogen discharge: and closing the fifth electric control valve, opening the sixth electric control valve, keeping the temperature of the sample chamber to be proper high temperature T2 by using the second heater, enabling the hydrogen in the sample chamber to flow into the second gas storage tank, opening the fifth stop valve, the seventh electric control valve and the first flow limiting valve when the pressure displayed by the first pressure sensor is similar to that displayed by the second pressure sensor, slowly discharging the hydrogen in the second gas storage tank into the air, and recording the data of the change of the system pressure along with time by using the second pressure sensor to obtain a PCT curve.
Performance test of hydrogen storage materials under different initial hydrogen purities:
hydrogen absorption: closing the fourth electric control valve, the third stop valve, the sixth electric control valve and the seventh electric control valve, opening the high-pressure hydrogen cylinder, the pure carbon dioxide steel cylinder, the first electric control valve, the second electric control valve and the fifth electric control valve, enabling the hydrogen and the carbon dioxide to enter a main pipeline through a first filter and be mixed, enabling the hydrogen and the carbon dioxide to flow into a first gas storage tank, waiting for a period of time, uniformly mixing, monitoring pressure change through a first pressure sensor, opening the third stop valve and the fourth electric control valve, and keeping the temperature of the reaction chamber to be proper low temperature T by using a cooler1At the moment, the hydrocarbon mixed gas flows into the reaction chamber, the change condition of the pressure along with the time in the hydrogen absorption process is recorded by the second pressure sensor, the pressure is continuously increased, a hydrogen absorption platform appears, and the pressure of the hydrogen absorption platform is recorded;
hydrogen discharge: closing the fifth electric control valve, opening the sixth electric control valve, and maintaining the temperature of the reaction chamber at the proper high temperature T by the second heater2And when the pressure displayed by the first pressure sensor is similar to that displayed by the second pressure sensor, the fifth stop valve, the seventh electric control valve and the first flow limiting valve are opened, the hydrocarbon mixed gas in the second gas storage tank is slowly discharged into the air, and the second pressure sensor records the change of the system pressure along with time, so that the PCT curve of the hydrogen purity is obtained.
The test was carried out by adjusting the flow rates of hydrogen and carbon dioxide with a computer so that the purity of hydrogen was 95%, 90%, 75%, 50%, respectively.
Test to determine the cycle life of hydrogen storage materials at different initial hydrogen purities:
step 1: closing the third stop valve, the sixth electric control valve and the seventh electric control valve, opening the high-pressure hydrogen cylinder, the pure carbon dioxide steel cylinder, the first electric control valve, the second electric control valve, the third electric control valve and the fifth electric control valve, controlling the first electric control valve and the second electric control valve by a computer to adjust the flow of hydrogen and carbon dioxide so as to change the purity of the hydrogen, enabling the hydrogen and the carbon dioxide to enter the system through the first filter to be mixed, flowing into the first gas storage tank, enabling the hydrogen and the carbon dioxide to be uniformly mixed after waiting for a period of time, monitoring the pressure change through the first pressure sensor, closing the third electric control valve after the pressure reaches a certain value, and recording the system pressure P at the moment3Opening the third stop valve and the second electric control valve, flowing the hydrocarbon mixed gas into the reaction chamber, and maintaining the temperature of the reaction chamber at a low temperature T by using a cooler1At this point, the sample begins to absorb hydrogen, the pressure change is monitored by the second pressure sensor, and the pressure P at this point is recorded after stabilization4。
Step 2: closing the fifth electric control valve, opening the sixth electric control valve, and maintaining the temperature of the reaction chamber at a high temperature T by the second heater2Then the hydrocarbon gas mixture in the reaction chamber flows to the second gas storage tank, the system pressure is reduced, the pressure change is monitored by the second pressure sensor, and the pressure P at the moment is recorded5And opening the seventh electric control valve, the fifth stop valve and the first flow limiting valve, reducing the purity of hydrogen after the hydrocarbon mixed gas and the carbon dioxide are mixed, discharging the gas in the system into the air, then closing the fifth stop valve and the first flow limiting valve, opening the eighth electric control valve and the second flow limiting valve, and vacuumizing the system for 15-20 min.
And (3) setting cycle times in the computer, performing multiple cycles on the step 1 and the step 2, automatically stopping after the cycle times are reached, and recording data.
The change in purity of the hydrogen before and after the cycle was measured:
initial hydrogen purity testing step:
closing all valves; opening a high-pressure hydrogen cylinder, a pure carbon dioxide steel cylinder, a first electric control valve, a third electric control valve and a fifth electric control valve, controlling the first electric control valve and the second electric control valve by a computer to adjust the flow of hydrogen and carbon dioxide to change the purity of the hydrogen, enabling the hydrogen and the carbon dioxide to enter a system through a first filter to be mixed and flow into a first gas storage tank, enabling the hydrogen and the carbon dioxide to be uniformly mixed after waiting for a period of time, then closing the third electric control valve, opening a seventh electric control valve and a fourth stop valve, enabling the hydrocarbon mixed gas to be heated to a high temperature of 300-500 ℃ through a first heater and enter a thermal conductivity cell, and recording the thermal conductivity lambda1。
And (3) testing the purity of the circulated hydrogen:
only opening the fourth electric control valve, the third stop valve, the seventh electric control valve and the fourth stop valve, enabling the hydrocarbon mixed gas to flow out of the sample chamber, heating the hydrocarbon mixed gas to the high temperature of 300-500 ℃ through the first heater, then enabling the hydrocarbon mixed gas to enter the thermal conductivity cell, and recording the thermal conductivity lambda at the moment2。
In particular use, reference may be made to the following operations:
preparation before system testing:
a pure argon gas cylinder and a first filter are connected with a first stop valve, a pure helium gas cylinder and the first filter are connected with a second stop valve, a high-pressure hydrogen gas cylinder and the first filter are connected with a first electric control valve, a pure carbon dioxide steel cylinder is connected with the first filter and a second electric control valve, and the pure argon gas cylinder and the first filter are connected with a main pipeline through a third electric control valve to serve as a high-pressure gas source for providing stable flow rate gas for a system. The first gas storage tank and the second gas storage tank are respectively connected with the main pipeline through a fifth electric control valve and a sixth electric control valve and are used for temporarily storing gas to ensure the accuracy of the test. The sample chamber is arranged in the jacketed heat exchanger and is connected with the main pipeline through a fourth electric control valve and a third stop valve, the jacketed heat exchanger is simultaneously connected with a second heater and a cooler, and the temperature of the reaction subsystem is controlled to control the hydrogen storage/release operation through water vapor and cooling water which are respectively provided by the second heater and the cooler. The exhaust subsystem is connected with the main pipeline through a seventh electric control valve, the evacuation pipeline is connected with the carbon dioxide steel cylinder and communicated with the outside (convenient for evacuation to the air) through the first flow limiting valve, and the vacuum pumping pipeline is connected with the vacuum pump through the eighth electric control valve and the second flow limiting valve. The computer is connected with the thermal conductivity cell, the cooler, the first heater, the second heater, the first pressure sensor and the second pressure sensor through the connecting concentrator, and parameters such as hydrogen purity, system pressure, temperature and the like in the hydrogen storage/release process are recorded.
PCT curve test:
putting a sample to be tested into a sample chamber, putting the sample to be tested into a jacketed heat exchanger, connecting a third filter and a fourth electric control valve, connecting a test system through a third stop valve, connecting the jacketed heat exchanger with a cooler, cooling to 20 ℃, closing all valves, opening a high-pressure hydrogen cylinder, a pure carbon dioxide steel cylinder, first to third electric control valves and a fifth electric control valve, controlling the flow of hydrogen and carbon dioxide to enable the purity of hydrogen in the hydrocarbon mixed gas to reach 95%, then enabling the hydrocarbon mixed gas to flow to a first gas storage tank, closing the third electric control valve to open the third stop valve and the fourth electric control valve when the set pressure is reached, enabling the hydrocarbon mixed gas to flow into the sample chamber, monitoring the pressure change of a reaction chamber through a second pressure sensor, making a PCT curve through a computer, and recording the pressure of a hydrogen absorption and release platform; and when the hydrogen absorption of the sample is saturated, closing the cooler, opening the second heater, setting the heating temperature to be 100 ℃, closing the fifth electric control valve, opening the sixth electric control valve, allowing the hydrocarbon mixed gas in the sample chamber to flow to the second gas storage tank, monitoring the pressure change through the second pressure sensor, and obtaining the volume of the released hydrogen through a gas state equation.
And (3) testing the cycle life:
step 1: and putting a sample to be tested into the sample chamber, putting the sample into the jacketed heat exchanger, connecting a third filter and a fourth electric control valve, connecting a test system through a third stop valve, and respectively controlling the temperature of a cooler and the temperature of a second heater to be 20 ℃ and 100 ℃.
Step 2: after the system is vacuumized, all valves are closed, then a high-pressure hydrogen bottle and first to third electric control valves are opened, the hydrogen purity in the hydrocarbon mixed gas is enabled to reach 95% by controlling the flow of hydrogen and carbon dioxide, then the hydrocarbon mixed gas flows into a first gas storage tank, after the two gases are uniformly mixed and the pressure reading of a first pressure sensor is stable, a cooler is opened, the cooling temperature is set to be 20 ℃, a third stop valve and a fourth electric control valve are opened, the hydrocarbon mixed gas flows into a sample chamber, a sample absorbs hydrogen, and the pressure change in the sample chamber is monitored by a second pressure sensor.
And step 3: and when the pressure in the sample chamber reaches the pressure of the hydrogen absorption and discharge platform, opening the second heater, setting the heating temperature to be 100 ℃, closing the fifth electric control valve, opening the sixth electric control valve, allowing the hydrocarbon mixed gas in the sample chamber to flow to the second gas storage tank, after the pressure of the first pressure sensor and the pressure of the second pressure sensor are stabilized, opening the seventh electric control valve, the fifth stop valve and the first flow limiting valve, combining the hydrocarbon mixed gas with carbon dioxide discharged from a carbon dioxide steel cylinder, reducing the purity of hydrogen, discharging the hydrogen into the air, when the pressure of the system is reduced to about 0.2MPa, closing the fifth stop valve and the first flow limiting valve, opening the eighth electric control valve and the second flow limiting valve, and opening the vacuum pump to vacuumize the system for 20 min.
And (3) setting the circulation times through a data acquisition and processing subsystem, and monitoring the change of the hydrogen storage capacity in the circulation process by sequentially circulating the steps 2-3 (200, 500 and 1000 times).
Through the data acquisition and processing subsystem, the purity of the hydrogen is set to 90%, 75% and 50%, and the change of the hydrogen storage capacity in the circulation process under different initial hydrogen purities is measured so as to explore the influence of different hydrogen purities on the cycle life of the hydrogen storage material.
Hydrogen purity testing before and after cycling
Placing a sample to be tested into the sample chamber, placing the sample into a jacketed heat exchanger, connecting a third filter and a fourth electric control valve, connecting a test system through a third stop valve, wherein the temperatures of a cooler and a second heater are respectively 20 ℃ and 100 ℃, pumping the system to vacuum, closing all valves, then opening a high-pressure hydrogen bottle, the first electric control valve, the third electric control valve, the fourth electric control valve, the third stop valve and the fourth stop valve, closing all valves, opening a high-pressure hydrogen bottle, a first electric control valve,The hydrogen is heated to 400 ℃ by a second heater and enters a thermal conductivity cell, and the thermal conductivity lambda at the moment is recorded1. After the sample to be tested is circulated for 200, 500 and 1000 times, the third electric control valve, the fifth electric control valve and the sixth electric control valve are closed, the fourth electric control valve, the seventh electric control valve, the third stop valve and the fourth stop valve are opened, hydrogen flows out of the sample chamber, is heated to 400 ℃ by the first heater and enters the thermal conductivity cell, and the thermal conductivity lambda at the time is recorded2Comparison of λ1And λ2A change in (c).
Analysis of social and economic benefits
The invention adopts a volume method as a basis, can test various properties of the same sample, and can continuously measure the hydrogen storage/release performance of the hydrogen storage material, the cycle life and the hydrogen purity change before and after hydrogen storage under different initial hydrogen purities. The decomposition pressure of the sample at any temperature can be obtained through a PCT curve, and the PCT curve is an important index of the performance of the hydrogen storage material and is also a theoretical basis for researching a new hydrogen storage material. Conventionally, a scanning electron microscope analysis method is used to obtain hydrogen storage/release performance by knowing the surface tissue morphology and the surface components of a sample before and after hydrogen storage/release, and the method has high cost and cannot obtain a plurality of parameters; the gravimetric method obtains the hydrogen storage performance by measuring the mass change before and after hydrogen storage/release or making a weight loss curve, but the sample is easy to be polluted in the transferring process, and the method has limited application only in the aspect of alloy hydrogen storage.
The first and second pressure sensors, the first heater, the second heater and the cooler, and the first to eighth electric control valves are connected through a computer, and then parameters are set in a computer program, wherein the set parameters comprise the heating temperature of the reaction chamber, the cooling temperature, the heating temperature of the thermal conductivity system, the cycle number and the corresponding valve opening and closing. The cycle life detection can be automatically carried out under different hydrogen purities through a computer program, and the trouble of manual operation is greatly saved.
The above-mentioned embodiments are preferred embodiments of the present invention, and the present invention is not limited thereto, and any other modifications or equivalent substitutions that do not depart from the technical spirit of the present invention are included in the scope of the present invention.

Claims (10)

1. A hydrogen storage material multiple performance test system which is characterized in that: the system comprises a main pipeline, a high-pressure gas source subsystem, a gas storage subsystem, a reaction subsystem, a temperature control subsystem, a thermal conductivity monitoring subsystem, an exhaust subsystem, a data acquisition and processing subsystem, a first pressure sensor and a second pressure sensor; the high-pressure gas source subsystem comprises a pure argon gas cylinder, a pure helium gas cylinder, a high-pressure hydrogen gas cylinder, a pure carbon dioxide steel cylinder, a first filter, a first stop valve, a second stop valve, a first electric control valve and a second electric control valve; the pure argon gas cylinder, the pure helium gas cylinder, the high-pressure hydrogen cylinder and the pure carbon dioxide steel cylinder are respectively provided with a first filter at the outlet end, the pure argon gas cylinder is connected with the main pipeline through a first stop valve, the pure helium gas cylinder is connected with the main pipeline through a second stop valve, the high-pressure hydrogen cylinder is connected with the main pipeline through a first electric control valve and the pure carbon dioxide steel cylinder is connected with the main pipeline through a second electric control valve, and the pure argon gas cylinder is positioned in front of a third electric control valve;
the gas storage subsystem comprises a first gas storage tank, a second filter, a fifth electric control valve and a sixth electric control valve; the open ends of the first air storage tank and the second air storage tank are provided with a second filter, wherein the open end of the first air storage tank is connected with the main pipeline through a fifth electric control valve, the open end of the second air storage tank is connected with the main pipeline through a sixth electric control valve, and the connection positions of the first air storage tank and the second air storage tank with the main pipeline are sequentially positioned behind the third electric control valve;
the reaction subsystem comprises a reaction chamber, a third filter, a fourth electric control valve and a third stop valve, wherein an air inlet of the reaction chamber is connected with the main pipeline and is positioned between the connection position of the first air storage tank and the main pipeline and the connection position of the second air storage tank and the main pipeline, and the third filter, the fourth electric control valve and the third stop valve are sequentially arranged between the air inlet of the reaction chamber and the main pipeline; the first pressure sensor is arranged on the main pipeline and is positioned between the first gas storage tank and the reaction chamber, the second pressure sensor is arranged between the fourth electric control valve and the third stop valve, and the temperature control subsystem is connected with the reaction chamber;
and the temperature control subsystem, the thermal conductivity monitoring subsystem, the exhaust subsystem, the first electric control valve, the second electric control valve, the third electric control valve, the fourth electric control valve, the fifth electric control valve, the sixth electric control valve, the seventh electric control valve, the first pressure sensor and the second pressure sensor are all connected with the data acquisition and processing subsystem.
2. The system for testing multiple properties of a hydrogen storage material according to claim 1, wherein: the reaction chamber comprises a sample chamber and a jacketed heat exchanger; the jacketed type heat exchanger is coated on the periphery of the sample chamber, the top end of the sample chamber is provided with an air inlet, the top end of one side of the jacketed type heat exchanger is provided with a high-temperature steam inlet, the bottom end of the jacketed type heat exchanger is provided with a cooling water inlet, the top end of the other side of the jacketed type heat exchanger is provided with a cooling water outlet, the bottom end of the jacketed type heat exchanger is provided with a condensed water outlet, and the high-temperature steam inlet and the cooling water inlet are connected.
3. The system for testing multiple properties of a hydrogen storage material according to claim 1, wherein: the thermal conductivity monitoring subsystem comprises a thermal conductivity pipeline connected with the main pipeline, a fourth stop valve, a first heater and a thermal conductivity cell are sequentially installed on the thermal conductivity pipeline, and the first heater and the thermal conductivity cell are connected with the data acquisition and processing subsystem.
4. The system for testing multiple properties of a hydrogen storage material according to claim 1, wherein: the exhaust subsystem comprises an evacuation part and a vacuum part which are connected with the main pipeline in parallel; the emptying part comprises a first branch and a second branch which are connected with the main pipeline, a first flow limiting valve is arranged on the first branch, and a fifth stop valve and a carbon dioxide steel cylinder are sequentially arranged on the second branch; the vacuum part comprises a vacuum pumping pipeline connected with the main pipeline, and an eighth electric control valve, a second flow limiting valve and a vacuum pump which are sequentially arranged on the vacuum pumping pipeline, wherein the eighth electric control valve is connected with the data acquisition and processing subsystem.
5. The system for testing multiple properties of a hydrogen storage material according to claim 1, wherein: the temperature control subsystem comprises a second heater and a cooler, and the second heater and the cooler are both connected with the reaction chamber and the data acquisition and processing subsystem.
6. The system for testing multiple properties of a hydrogen storage material according to claim 1, wherein: the data acquisition processing subsystem comprises a computer and a hub; the first electric control valve, the second electric control valve, the third electric control valve, the fourth electric control valve, the fifth electric control valve, the sixth electric control valve, the seventh electric control valve, the thermal conductivity monitoring subsystem, the exhaust subsystem, the temperature control subsystem, the first pressure sensor and the second pressure sensor are all connected with a computer through a concentrator.
7. A test method based on the hydrogen storage material multiple performance test system of any one of claims 1-6, characterized by comprising the following steps:
s101, vacuumizing a test system;
s201, calibrating the volume of the test system;
s301, testing the leakage rate of the system;
s401, after completing S101 to S301, the test system can perform the following parameter measurement:
determining the purity of the initial hydrogen;
measuring the hydrogen storage/release performance of the hydrogen storage material;
testing the performance of the hydrogen storage material under different initial hydrogen purities;
testing the cycle life of the hydrogen storage material at different initial hydrogen purities;
the change in purity of the hydrogen before and after the cycle was measured.
8. The method for testing multiple properties of a hydrogen storage material according to claim 7, wherein: the performance test steps of the hydrogen storage material under different initial hydrogen purities are as follows:
hydrogen absorption: closing the fourth electric control valve, the third stop valve, the sixth electric control valve and the seventh electric control valve, opening the high-pressure hydrogen cylinder, the pure carbon dioxide steel cylinder, the first electric control valve, the second electric control valve and the fifth electric control valve, enabling the hydrogen and the carbon dioxide to enter the main pipeline through the first filter and be mixed, enabling the hydrogen and the carbon dioxide to flow into the first gas storage tank, waiting for a period of time, uniformly mixing, monitoring pressure change through the first pressure sensor, opening the third stop valve and the fourth electric control valve, and keeping the temperature of the sample chamber to be proper low temperature T by using the cooler1At the moment, a hydrogen-carbon dioxide mixture (hereinafter referred to as 'hydrocarbon mixed gas') flows into the sample chamber, the change condition of the pressure along with the time in the hydrogen absorption process is recorded by the second pressure sensor, the pressure is continuously increased, a hydrogen absorption platform appears, and the pressure of the hydrogen absorption platform is recorded;
hydrogen discharge: closing the fifth electric control valve, opening the sixth electric control valve, and maintaining the sample chamber at the desired elevated temperature T with the second heater2And when the pressure displayed by the first pressure sensor is similar to that displayed by the second pressure sensor, the fifth stop valve, the seventh electric control valve and the first flow limiting valve are opened, the hydrocarbon mixed gas in the second gas storage tank is slowly discharged to the air, and the pressure of the system is recorded by the second pressure sensor along with the change of time, so that the pressure-component isotherm under the hydrogen purity is obtained.
The test was carried out by adjusting the flow rates of hydrogen and carbon dioxide with a computer so that the purity of hydrogen was 95%, 90%, 75%, 50%, respectively.
9. The method for testing multiple properties of a hydrogen storage material according to claim 7, wherein: the method comprises the following steps of:
step 1: closing the third stop valve, the sixth electric control valve and the seventh electric control valve, opening the high-pressure hydrogen cylinder, the pure carbon dioxide steel cylinder, the first electric control valve, the second electric control valve, the third electric control valve and the fifth electric control valve, controlling the first electric control valve and the second electric control valve by a computer to adjust the flow of hydrogen and carbon dioxide so as to change the purity of the hydrogen, enabling the hydrogen and the carbon dioxide to enter the system through the first filter to be mixed, flowing into the first gas storage tank, enabling the hydrogen and the carbon dioxide to be uniformly mixed after waiting for a period of time, monitoring the pressure change through the first pressure sensor, closing the third electric control valve after the pressure reaches a certain value, and recording the system pressure P at the moment3Opening the third stop valve and the second electric control valve, allowing the hydrocarbon mixture to flow into the sample chamber, and maintaining the temperature of the sample chamber at low temperature T by using a cooler1At this point, the sample begins to absorb hydrogen, the pressure change is monitored by the second pressure sensor, and the pressure P at this point is recorded after stabilization4。
Step 2: closing the fifth electric control valve, opening the sixth electric control valve, and maintaining the sample chamber at the high temperature T with the second heater2Then the hydrocarbon gas mixture in the sample chamber flows to the second gas storage tank, the system pressure is reduced, the pressure change is monitored by the second pressure sensor, and the pressure P at the moment is recorded5And opening the seventh electric control valve, the fifth stop valve and the first flow limiting valve, reducing the purity of hydrogen after the hydrocarbon mixed gas and the carbon dioxide are mixed, discharging the gas in the system into the air, then closing the fifth stop valve and the first flow limiting valve, opening the eighth electric control valve and the second flow limiting valve, and vacuumizing the system for 15-20 min.
And (3) setting cycle times in the computer, performing multiple cycles on the step 1 and the step 2, automatically stopping after the cycle times are reached, and recording data.
10. The method for testing multiple properties of a hydrogen storage material according to claim 7, wherein: the hydrogen purity change test steps before and after the determination cycle are as follows:
initial hydrogen purity testing step:
closing all valves; opening a high-pressure hydrogen cylinder, a pure carbon dioxide steel cylinder, a first electric control valve, a third electric control valve and a fifth electric control valve, controlling the first electric control valve and the second electric control valve by a computer to adjust the flow of hydrogen and carbon dioxide to change the purity of the hydrogen, enabling the hydrogen and the carbon dioxide to enter a system through a first filter to be mixed and flow into a first gas storage tank, enabling the hydrogen and the carbon dioxide to be uniformly mixed after waiting for a period of time, then closing the third electric control valve, opening a seventh electric control valve and a fourth stop valve, enabling the hydrocarbon mixed gas to be heated to a high temperature of 300-500 ℃ through a first heater and enter a thermal conductivity cell, and recording the thermal conductivity lambda1。
And (3) testing the purity of the circulated hydrogen:
only opening the fourth electric control valve, the third stop valve, the seventh electric control valve and the fourth stop valve, enabling the hydrocarbon mixed gas to flow out of the sample chamber, heating the hydrocarbon mixed gas to the high temperature of 300-500 ℃ through the first heater, then enabling the hydrocarbon mixed gas to enter the thermal conductivity cell, and recording the thermal conductivity lambda at the moment2。
CN202011284527.3A 2020-11-17 2020-11-17 System and method for testing various performances of hydrogen storage material Pending CN112326501A (en)

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CN113418825A (en) * 2021-06-24 2021-09-21 中国核动力研究设计院 Carbon dioxide eliminating agent eliminating performance test system and test method
CN113586949A (en) * 2021-08-04 2021-11-02 上海氢枫能源技术有限公司 Method and system for monitoring service life of hydrogen storage cylinder group
CN113933208A (en) * 2021-10-13 2022-01-14 扬州大学 Hydrogen absorption and desorption cycle life testing device and testing method for hydrogen storage material
CN114113194A (en) * 2021-11-16 2022-03-01 浙江大学 Thermal signal testing device and system based on phase change latent heat of solid hydrogen storage and supply material and thermal signal testing and analyzing method
CN114749111A (en) * 2022-04-21 2022-07-15 云南电网有限责任公司电力科学研究院 Reactor for testing hydrogen absorption and desorption performance of organic liquid hydrogen storage material
CN114778378A (en) * 2022-03-31 2022-07-22 哈尔滨工业大学 Hydrogen storage testing device and method based on Sieverts method
CN115032114A (en) * 2022-05-17 2022-09-09 江苏氢枫能源装备有限公司 Hydrogen storage material performance testing device and testing method thereof
WO2022247108A1 (en) * 2021-05-27 2022-12-01 华南理工大学 Intrinsically safe high-purity and high-pressure hydrogen environment material compatibility testing system and method
WO2023206975A1 (en) * 2022-04-28 2023-11-02 惠州市华达通气体制造股份有限公司 Reaction vessel, and device and method for testing hydrogen storage/desorption material
CN118031105A (en) * 2024-04-10 2024-05-14 常州常成热力设备有限公司 Intelligent filling device for hydrogen storage tank

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WO2022247108A1 (en) * 2021-05-27 2022-12-01 华南理工大学 Intrinsically safe high-purity and high-pressure hydrogen environment material compatibility testing system and method
CN113418825A (en) * 2021-06-24 2021-09-21 中国核动力研究设计院 Carbon dioxide eliminating agent eliminating performance test system and test method
CN113586949A (en) * 2021-08-04 2021-11-02 上海氢枫能源技术有限公司 Method and system for monitoring service life of hydrogen storage cylinder group
CN113586949B (en) * 2021-08-04 2023-02-28 上海氢枫能源技术有限公司 Method and system for monitoring service life of hydrogen storage cylinder group
CN113933208A (en) * 2021-10-13 2022-01-14 扬州大学 Hydrogen absorption and desorption cycle life testing device and testing method for hydrogen storage material
CN114113194A (en) * 2021-11-16 2022-03-01 浙江大学 Thermal signal testing device and system based on phase change latent heat of solid hydrogen storage and supply material and thermal signal testing and analyzing method
CN114778378A (en) * 2022-03-31 2022-07-22 哈尔滨工业大学 Hydrogen storage testing device and method based on Sieverts method
CN114749111A (en) * 2022-04-21 2022-07-15 云南电网有限责任公司电力科学研究院 Reactor for testing hydrogen absorption and desorption performance of organic liquid hydrogen storage material
CN114749111B (en) * 2022-04-21 2024-03-19 云南电网有限责任公司电力科学研究院 Reactor for testing hydrogen absorption and desorption performance of organic liquid hydrogen storage material
WO2023206975A1 (en) * 2022-04-28 2023-11-02 惠州市华达通气体制造股份有限公司 Reaction vessel, and device and method for testing hydrogen storage/desorption material
CN115032114A (en) * 2022-05-17 2022-09-09 江苏氢枫能源装备有限公司 Hydrogen storage material performance testing device and testing method thereof
CN118031105A (en) * 2024-04-10 2024-05-14 常州常成热力设备有限公司 Intelligent filling device for hydrogen storage tank
CN118031105B (en) * 2024-04-10 2024-06-07 常州常成热力设备有限公司 Intelligent filling device for hydrogen storage tank

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