CN116793893A - Novel hydrogen content testing device and testing method for high-pressure hydrogen-contacting material - Google Patents
Novel hydrogen content testing device and testing method for high-pressure hydrogen-contacting material Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 350
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 350
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 320
- 238000012360 testing method Methods 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000012544 monitoring process Methods 0.000 claims abstract description 71
- 239000007789 gas Substances 0.000 claims abstract description 56
- 238000004458 analytical method Methods 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 239000003921 oil Substances 0.000 claims description 283
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 103
- 230000005540 biological transmission Effects 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 26
- 150000002431 hydrogen Chemical class 0.000 claims description 24
- 239000011261 inert gas Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 238000007599 discharging Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 12
- 238000004364 calculation method Methods 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 230000007613 environmental effect Effects 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 239000000346 nonvolatile oil Substances 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010998 test method Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 17
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 229
- 238000003466 welding Methods 0.000 description 10
- 238000012546 transfer Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000010354 integration Effects 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 235000019483 Peanut oil Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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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
- G01N7/14—Analysing materials by measuring the pressure or volume of a gas or vapour by allowing the material to emit a gas or vapour, e.g. water vapour, and measuring a pressure or volume difference
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- General Health & Medical Sciences (AREA)
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- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
- Investigating Or Analyzing Materials Using Thermal Means (AREA)
Abstract
The invention discloses a novel hydrogen content testing device and a testing method for a high-pressure hydrogen-contacting material. The device comprises a control system, a heat exchange system, an oil source system, an environment box system, a hydrogen content analysis system and an air source system. The control system comprises an industrial personal computer; the heat exchange system, the air source system and the oil source system are all connected with the environment box system and are connected with the industrial personal computer in a wired way; the environment box system comprises an upper cylinder and a lower cylinder; the hydrogen content analysis system includes a hydrogen exposure module, a hydrogen delivery module, and a hydrogen monitoring module. The invention realizes high-precision on-line analysis of the hydrogen content change characteristic of the high-pressure hydrogen-bearing material by utilizing the monitoring data of the gas/liquid pressure sensor, meets the hydrogen content in-situ test requirement of the material after single-time and cyclic multi-station high-pressure hydrogen exposure, provides the hydrogen content in-situ test environment for the hydrogen energy equipment with wide-temperature high-pressure function, and develops the research on the influence rule of temperature on the hydrogen content change characteristic of the high-pressure hydrogen environment material.
Description
Technical Field
The invention belongs to the field of hydrogen compatibility testing of materials for hydrogen energy equipment, and particularly relates to a novel hydrogen content testing device and a testing method for a high-pressure hydrogen material.
Background
As the pressure on global climate change and natural disaster exacerbation continues to increase, hydrogen energy has gained significant attention in countries around the world. The hydrogen energy equipment material is exposed to high-pressure hydrogen environment for a long time, and solute hydrogen molecules can enter the material to degrade the mechanical properties of the material, and even cause hydrogen leakage and explosion accidents. Under the action of high-pressure hydrogen, the content of dissolved hydrogen in the material has a great influence on the self performance of the material and the safety of a high-pressure hydrogen system. Therefore, it is important to develop a hydrogen content testing device for high-pressure hydrogen-bearing materials.
At present, the hydrogen content testing device of materials under high-pressure hydrogen is mainly divided into three types, and the testing environments are single hydrogen exposure at normal temperature. The first is a conventional thermal desorption analysis gas chromatography test device. The device adopts heating and inert gas to sweep the sample, so that hydrogen escapes from the hydrogen-filled sample, and the hydrogen is conveyed into a gas chromatograph by carrier gas for hydrogen content measurement. However, the device is expensive and the measured hydrogen content data of the material is distorted. The second is a simple electronic balance weight testing device. The device is used for placing a hydrogen-filled sample on an electronic microbalance, allowing hydrogen to slowly escape from the sample, and indirectly calculating the corresponding hydrogen content according to the mass change of the sample measured by the balance. But the device has lower measurement accuracy, so the application range is smaller. And the third is a novel measuring cylinder type hydrogen volume testing device. The device installs the hydrogen sample that fills in the customization container, makes the sample release hydrogen slowly in the container, leads to the water liquid level of the graduated flask part of container to reduce, utilizes electrode slice and the capacitance appearance that wraps up in the graduated flask outside to analyze the hydrogen content that the sample released. However, the device adopts an ex-situ test means, so that the total hydrogen release amount of the sample is extrapolated by a theoretical formula, and a certain system error is caused. In addition, the normal temperature water in the measuring cylinder can volatilize slowly in a test time of up to several days, and deviation in test results is liable to be caused.
In summary, the testing accuracy of the existing high-pressure hydrogen environment material hydrogen content testing device needs to be further improved, and the testing function of the testing device cannot meet the requirements of multifunctional testing working conditions such as hydrogen cyclic exposure, high temperature, low temperature, in-situ and the like. Therefore, how to realize high-precision in-situ test of the hydrogen content change characteristic of the high-pressure hydrogen-contacting material, and to ascertain the rule of influence of special working conditions such as hydrogen circulation charge and discharge, wide-temperature high-pressure environment and the like on the hydrogen content of the material for the hydrogen energy equipment is an important problem to be solved.
Disclosure of Invention
In order to at least solve one of the technical problems in the prior art, the invention provides a novel hydrogen content testing device and a testing method for a high-pressure hydrogen material, which can realize online in-situ testing and accurate and reliable analysis of the hydrogen content change characteristics of the material for hydrogen energy equipment.
In order to achieve the aim of the invention, the novel hydrogen content testing device for the high-pressure hydrogen-contacting material comprises a control system, a heat exchange system, an oil source system, an environment box system, a hydrogen content analysis system and an air source system;
the control system comprises an industrial personal computer;
the heat exchange system, the air source system and the oil source system are all connected with the environment box system and are connected with the industrial personal computer in a wired way;
The environment box system comprises an upper cylinder and a lower cylinder;
the hydrogen content analysis system comprises a hydrogen exposure module, a hydrogen transmission module and a hydrogen monitoring module, wherein the hydrogen exposure module is arranged in an upper cylinder, the hydrogen exposure module comprises an upper temperature sensor for monitoring the test temperature of the hydrogen exposure module and a sample table for placing a sample, the hydrogen monitoring module is arranged in a lower cylinder, the hydrogen exposure module and the hydrogen monitoring module are connected through the hydrogen transmission module so as to transmit hydrogen released by the sample to the hydrogen monitoring module, the hydrogen monitoring module comprises a lower temperature sensor for monitoring the test temperature of the hydrogen monitoring module, a gas pressure sensor for monitoring the pressure of the hydrogen, a liquid pressure sensor for monitoring the pressure of an oil body, a first oil groove and a second oil groove, the first oil groove is positioned in the second oil groove and is communicated with an oil body storage space inside the two oil grooves, and each sensor is in signal connection with the industrial personal computer.
The hydrogen exposure module enables hydrogen released by the sample to flow into the hydrogen monitoring module through the hydrogen transmission module, so that the integration of the test functions of hydrogen exposure, hydrogen transmission and hydrogen monitoring is realized; the gas pressure sensor and the liquid pressure sensor are arranged in the hydrogen monitoring module, so that the pressure data of the gas and the oil in the hydrogen monitoring module can be collected in real time, and the change characteristic of the hydrogen content in the first oil groove is analyzed on line by utilizing a hydrogen content calculation formula.
The oil body storage space in the first oil groove and the second oil groove is in a communicating state, and the gas pressure above the oil surface inside the second oil groove is always close to the atmospheric pressure, so that the communicating vessel principle is reasonably applied and the hydrogen content is accurately calculated.
Internal cross-sectional area S of first oil groove 47 1 Equal to the internal cross-sectional area of the second sump 50 minus S 1 Residual area S after 2 I.e. area S 1 Equal to area S 2 Therefore, the change of the oil level in the first oil groove is kept consistent with the change of the oil level in the second oil groove, namely, the oil level in the first oil groove can be reversely pushed out only according to the oil pressure data obtained by the liquid pressure sensor at the right lower end of the second oil groove.
Further, the sample is cylindrical and is placed on a sample table; the sample table is two cuboids and is fixed on the outer wall of the lower cylinder body through a welding process, so that hydrogen released by a sample can conveniently enter the hydrogen monitoring module through the hydrogen transmission module.
Further, the heat exchange system comprises a refrigerating and heating machine, a water inlet valve, an upper water inlet pipe, an upper heat exchange elbow pipe, an upper water outlet pipe, a lower water inlet pipe, a lower heat exchange elbow pipe, a lower water outlet pipe and a water outlet valve,
the refrigerating and heating machine is connected with the industrial personal computer in a wired way;
The upper water inlet pipe, the upper heat exchange bent pipe and the upper water outlet pipe are sequentially connected and penetrate through the upper cylinder, the lower water inlet pipe, the lower heat exchange bent pipe and the lower water outlet pipe are sequentially connected and penetrate through the lower cylinder, the upper water inlet pipe and the lower water inlet pipe are both connected with the water outlet end of the refrigerating and heating machine, and the upper water outlet pipe and the lower water outlet pipe are both connected with the water return end of the refrigerating and heating machine;
the water inlet valve and the water outlet valve are respectively arranged at the water outlet end and the water return end of the refrigerating and heating machine and are connected with the industrial personal computer through signals.
The water inlet pipe and the water outlet pipe are all in split flow, the split flow of the water inlet pipe and the water outlet pipe and the real-time monitoring of the upper temperature sensor and the lower temperature sensor can ensure the unification of the test temperature of the hydrogen content analysis system, and the high temperature/low temperature test condition required by the test is realized.
Further, the oil source system comprises an oil tank, an oil filling valve, an oil filling pipe, an oil discharging valve and an oil discharging pipe; the oil tank is connected with the environment tank system through the oil filling pipe and the oil discharging pipe to form a circulation loop of an oil body, the oil filling valve and the oil discharging valve are respectively arranged on the oil filling pipe and the oil discharging pipe, the oil tank is connected with the industrial personal computer in a wired mode, and the oil filling valve and the oil discharging valve are connected with the industrial personal computer in a signal mode. The oil body flows into the first oil groove and the second oil groove through the oil filling pipe, and can flow back to the oil tank from the first oil groove and the second oil groove through the oil discharging pipe, so that the recycling of the oil body is realized.
Furthermore, the oil tank is filled with the oil body which is not easy to volatilize, and the oil body comprises common oils such as peanut oil, soybean oil and the like, so that the test error caused by volatilization of liquid in the hydrogen content test process can be reduced.
Further, the environmental box system further comprises a support base, the support base is located at the bottom of the lower cylinder, and the second oil groove is fixed on the support base. The supporting base is used for supporting and fixing the whole environment box system and the hydrogen content analysis system.
Further, the environment box system further comprises a heat preservation jacket, and the heat preservation jacket is arranged on the outer cylinder walls of the upper cylinder body and the lower cylinder body in a surrounding mode. The heat preservation jacket is used for guaranteeing the stability of the internal environment temperature of the environment box system.
Further, the environmental tank system further includes a static seal member located at a contact surface of the upper cylinder and the lower cylinder for preventing leakage of high-pressure hydrogen gas from the hydrogen exposure module.
Further, the air source system comprises a pressurizing module and a depressurizing module;
the pressurizing module comprises an air inlet and outlet pressure sensor, an air inlet and outlet valve, an air inlet and outlet pipe, an air outlet valve, a pressurizer, an air source main valve, an inert gas source valve, an inert gas bottle, a hydrogen source valve and a hydrogen bottle, wherein the air inlet and outlet pressure sensor is used for measuring the internal pressure value of the hydrogen exposing module;
The vacuum pump is connected with the hydrogen content analysis system through the lower exhaust pipe, the lower exhaust pipe is connected with the air inlet and outlet pipe, the lower exhaust valve is arranged on the lower exhaust pipe, the vacuum degree sensor, the vacuum pipeline valve and the air outlet valve are all arranged on the air inlet and outlet pipe, the vacuum pump is connected with the industrial computer in a wired mode, and each valve and the vacuum degree sensor are all connected with the industrial computer in a signal mode.
Preferably, the right end of the first oil groove is sequentially connected with the lower extraction valve and the lower extraction pipe. The vacuum pump is convenient for vacuumize the gas above the oil surface in the first oil groove, so that the internal oil level of the first oil groove and the internal oil level of the second oil groove reach a set height difference when the air extraction operation is finished.
The hydrogen exposure module is connected with the air source system through the air inlet and outlet pipe, and the cycle times of pressurization, pressure maintaining and pressure relief of the high-pressure hydrogen in the hydrogen exposure module are independently selected according to the test requirements, so that multiple test working conditions such as single time and cycle exposure of the hydrogen in the hydrogen exposure module can be realized.
Further, the hydrogen transmission module comprises an upper transmission air pipe, a transmission air valve and a lower transmission air pipe which are sequentially connected, the upper transmission air pipe is communicated with the hydrogen exposure module, the lower transmission air pipe is communicated with the hydrogen monitoring module, and the transmission air valve is used for controlling hydrogen to enter the hydrogen monitoring module from the hydrogen exposure module.
Preferably, the upper end of the upper transmission air pipe is fixedly connected with the inner wall of the lower cylinder body through a welding process, and the lower end of the upper transmission air pipe is sequentially connected with the transmission air valve and the lower transmission air pipe.
Further, the hydrogen monitoring module further comprises a lower side plate, a connecting part and a positioning part, the upper temperature sensor is fixedly connected with the upper side plate through a welding process, the lower temperature sensor is fixedly connected with the lower side plate through a welding process, the first oil groove and the second oil groove are fixedly connected through the connecting part, and the positioning part is fixedly connected with the supporting base through a welding process and used for fixing the position of the second oil groove.
In the device, the industrial personal computer can not only control the operation of the refrigerating and heating machine, the oil tank, the booster and the vacuum pump in a wired manner, but also control the opening and closing of all valves in a wireless manner, and can collect wireless signals sent by all sensors in an online manner.
The invention also provides an in-situ test method for the hydrogen content of the material for the hydrogen energy equipment, which adopts the device, and comprises the following steps:
step A: installing, namely separating the upper cylinder body from the lower cylinder body, enabling a sample table at the upper end of the lower cylinder body to be completely exposed, and finally placing a sample on the sample table;
and (B) step (B): filling, namely closing the upper cylinder body and the lower cylinder body, vacuumizing the hydrogen exposure module until a vacuum degree value shown by a vacuum degree sensor reaches a value required by heat preservation of a heat preservation jacket; filling hydrogen into the upper cylinder through the gas source system to enable the hydrogen to be filled in the hydrogen exposure module, and then alternately circulating vacuumizing and hydrogen filling operation for a plurality of times, and finally enabling the hydrogen exposure module to be filled with low-pressure high-purity hydrogen;
Step C: the temperature of the upper cylinder body and the temperature of the lower cylinder body are regulated by starting the heat exchange system until the temperature value shown by the upper temperature sensor and the temperature value shown by the lower temperature sensor are equal and reach the set test temperature, and in the subsequent series of steps from pressurizing to pressure releasing, the heat exchange system is kept on so as to ensure that the test temperature of the hydrogen content analysis system is kept unchanged;
step D: pressurizing, namely slowly pressurizing high-purity hydrogen of the hydrogen exposure module through an air source system until a pressure value shown by the inlet and outlet pressure sensor reaches a set test pressure and the value is stable;
step E: maintaining pressure, namely enabling hydrogen of the hydrogen exposure module to be in a closed pressure maintaining state, enabling the sample to be exposed for preset time in a high-pressure hydrogen environment, and enabling subsequent oiling and air extraction steps to be carried out synchronously with the pressure maintaining process;
step F: oiling, namely enabling gas in the hydrogen monitoring module to be directly communicated with the atmosphere and keeping the preset time, enabling the pressure of the gas in the hydrogen monitoring module to be equal to the atmospheric pressure, and injecting oil bodies into the first oil groove and the second oil groove through an oil source system until the pressure of the oil bodies in the hydrogen monitoring module reaches a set value;
step G: pumping air, starting a vacuum pump and a vacuum pipeline valve, and vacuumizing air above the oil surface in the first oil tank until a vacuum degree value shown by a vacuum degree sensor and an oil pressure value in the monitoring hydrogen monitoring module reach set values;
Step H: after the pressure maintaining, oiling and exhausting steps are completed, the hydrogen exposure module is rapidly depressurized until the pressure value shown by the pressure sensor is equal to the atmospheric pressure; vacuumizing the hydrogen exposure module until the vacuum degree value shown by the vacuum degree sensor is equal to the atmospheric pressure;
step I: the temperature is returned, and the temperature is regulated through the heat exchange system, so that the temperature value shown by the upper temperature sensor is equal to the temperature value shown by the lower temperature sensor and both reach the set test temperature;
step J: the method comprises the steps of testing, enabling hydrogen released by a sample to enter a first oil groove through a hydrogen transmission module, so that the height of an oil level in the first oil groove is reduced, displaying a hydrogen pressure value and an oil pressure value of a hydrogen monitoring module on a screen of the oil pressure of an industrial personal computer through a server of the industrial personal computer, and drawing a relation curve of the hydrogen content released by the sample and testing time in real time through a hydrogen content calculation formula;
step K: after the hydrogen content test is completed, releasing hydrogen in the hydrogen content analysis system and the gas source system, and after the hydrogen content analysis system and the gas source system are kept for a preset time, purging the hydrogen content analysis system and the gas source system by using low-pressure inert gas to remove residual hydrogen;
step L: discharging oil, namely enabling oil bodies to flow back to an oil source system of the oil tank from the first oil tank and the second oil tank;
Step M: unloading the sample, separating the upper cylinder from the lower cylinder, and taking out the sample.
Further, the hydrogen content calculation formula is that
Wherein M is the molar mass of hydrogen, M is the initial mass of the sample, and Deltan is the number of hydrogen moles increased above the oil surface in the first oil tank in a time of 0 to t.
Compared with the prior art, the invention has the following beneficial effects that:
1. according to the invention, the gas pressure sensor and the liquid pressure sensor are respectively arranged in the first oil groove and the second oil groove, the gas pressure data and the oil pressure data in the hydrogen monitoring module are collected in real time, and the hydrogen content change characteristics of the high-pressure hydrogen material are analyzed in situ on line by utilizing a hydrogen content calculation formula.
2. The invention realizes the integration of the test functions of hydrogen exposure, hydrogen transmission and hydrogen monitoring, and avoids the systematic errors caused by ex-situ test and theoretical formula extrapolation; the method has the advantages that the conventional water body is replaced by the non-volatile oil body, the interference of the volatilization of the water body on the test result is eliminated, and the hydrogen content test precision of the material for the hydrogen energy equipment is greatly improved.
3. According to the invention, the hydrogen exposure module is communicated with the air source system by utilizing the air inlet and outlet pipe, so that the cycle times of pressurization, pressure maintaining and pressure relief of the high-pressure hydrogen in the hydrogen exposure module are independently selected according to the test requirements, and multiple test working conditions such as single time and cycle exposure of the hydrogen in the hydrogen exposure module are realized.
4. The diversion of the water inlet/outlet pipe and the monitoring of the upper/lower temperature sensors can ensure the unification of the test temperature of the hydrogen content analysis system, so that the water inlet temperature of the refrigerating and heating machine is automatically regulated according to the test requirement, thereby realizing wide-temperature test conditions and researching the influence of the temperature on the hydrogen content change characteristics of the high-pressure hydrogen environment material.
Drawings
Fig. 1 is a schematic diagram of a hydrogen content testing device for a novel high-pressure hydrogen-contacting material according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view of a hydrogen content analysis system in accordance with an embodiment of the present invention.
FIG. 3 is a top view of a hydrogen monitoring module according to an embodiment of the invention.
FIG. 4 is a diagram illustrating parameters of a hydrogen monitoring module prior to oil addition in an embodiment of the present invention.
FIG. 5 is a diagram illustrating parameters of a hydrogen monitoring module after oil addition in an embodiment of the present invention.
FIG. 6 is a diagram illustrating parameters of the hydrogen monitoring module after the temperature is returned in an embodiment of the present invention.
FIG. 7 is a diagram illustrating parameters of a hydrogen monitoring module at time t in a hydrogen content test according to an embodiment of the present invention.
In the figure, a 1-industrial personal computer, a 2-wired wire, a 3-refrigerating and heating machine, a 4-water inlet valve, a 5-upper water inlet pipe, a 6-upper heat exchange bent pipe, a 7-upper water outlet pipe, a 8-lower water inlet pipe, a 9-lower heat exchange bent pipe, a 10-lower water outlet pipe, a 11-water outlet valve, a 12-oil tank, a 13-oil filling valve, a 14-oil filling pipe, a 15-oil drain valve, a 16-oil drain pipe, a 17-air inlet and outlet pressure sensor, a 18-air inlet and outlet valve, a 19-air inlet and outlet pipe, a 20-air outlet valve, a 21-booster, a 22-air source main valve, a 23-inert gas source valve, a 24-inert gas bottle, a 25-hydrogen source valve, a 26-hydrogen bottle, a 27-lower extraction pipe, a 28-lower extraction valve, a 29-vacuum pump, a 30-vacuum degree sensor, a 31-vacuum pipeline valve, a 32-air drain valve, a 33-heat preservation jacket, a 34-upper cylinder, a 35-lower cylinder, a 36-static sealing component, a 37-supporting base, a 38-upper side plate, a 39-upper temperature sensor, a 40-sample, a 41-sample delivery table, a 41-air pipe, a 42-delivery table, a 42-lower gas valve, a 43-delivery table, a 43-lower oil groove, a 43-45-delivery valve, a 44-45-pressure sensor, a 45-liquid sensor, a 45-delivery sensor, a 45-pressure sensor, a 45-delivery part, a 45-pressure sensor, and a 48-pressure sensor.
Detailed Description
In order to facilitate understanding of the present invention to those skilled in the art, specific embodiments of the present invention will be described below with reference to the accompanying drawings, but the practice and protection of the present invention are not limited thereto. Various modifications and variations of the present invention will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
The invention provides a novel hydrogen content testing device for a high-pressure hydrogen-contacting material, which is used for realizing online in-situ testing and accurate and reliable analysis of hydrogen content change characteristics of a material for hydrogen energy equipment, and referring to fig. 1 to 7, the device comprises a control system, a heat exchange system, an oil source system, an environment box system, a hydrogen content analysis system and an air source system.
As shown in fig. 1 and 2, the control system comprises an industrial personal computer 1, a wired electric wire 2 and a wireless signal; the industrial personal computer 1 is connected with the refrigerating and heating machine 3, the oil tank 12, the booster 21 and the vacuum pump 29 through the wired electric wires 2, and is connected with the air inlet and outlet pressure sensor 17, the vacuum degree sensor 30, the upper temperature sensor 39, the lower temperature sensor 46, the gas pressure sensor 48, the liquid pressure sensor 51 and all valves through wireless signals.
The heat exchange system comprises a refrigerating and heating machine 3, a water inlet valve 4, an upper water inlet pipe 5, an upper heat exchange elbow 6, an upper water outlet pipe 7, a lower water inlet pipe 8, a lower heat exchange elbow 9, a lower water outlet pipe 10 and a water outlet valve 11; the refrigerating and heating machine 3 is connected with an environment box system through an upper water inlet pipe 5, an upper water outlet pipe 7, a lower water inlet pipe 8 and a lower water outlet pipe 10. Specifically, an upper water inlet pipe 5, an upper heat exchange bent pipe 6 and an upper water outlet pipe 7 are sequentially connected, a lower water inlet pipe 8, a lower heat exchange bent pipe 9 and a lower water outlet pipe 10 are sequentially connected, the upper water inlet pipe 5 and the lower water inlet pipe 8 are both connected with the water outlet end of the refrigerating and heating machine 3, the upper water outlet pipe 7 and the lower water outlet pipe 10 are both connected with the water return end of the refrigerating and heating machine 3, and the upper water inlet pipe 5 and the upper water outlet pipe 6 are both connected with an upper cylinder 34 through a heat insulation jacket 33; the lower water inlet pipe 8 and the lower water outlet pipe 10 pass through a heat insulation jacket and a lower cylinder 35. The water inlet valve 4 and the water outlet valve 11 are respectively arranged at the water outlet end and the water return end of the refrigeration and heating machine 3 and are connected with the industrial personal computer 1 in a signal way.
The oil source system comprises an oil tank 12, an oil filling valve 13, an oil filling pipe 14, an oil discharging valve 15 and an oil discharging pipe 16; the oil tank 12 is connected with an environment tank system through an oil filling pipe 14 and an oil discharging pipe 16 to form a circulation loop of an oil body, and an oil filling valve 13 and an oil discharging valve 15 are respectively arranged on the oil filling pipe 14 and the oil discharging pipe 16; the filler tube 14 passes through the support base 37 to allow the oil body to flow from the oil tank 12 into the first oil groove 47 and the second oil groove 50; the oil drain pipe 16 penetrates through the supporting base 37, so that the oil body flows back to the oil tank 12 from the first oil groove 47 and the second oil groove 50, and the recycling of the oil body is realized.
The environment box system comprises a heat preservation jacket 33, an upper cylinder 34, a lower cylinder 35, a static sealing part 36 and a support base 37; the upper cylinder 34 is covered and fixed on the top of the lower cylinder 35, the heat-insulating jacket 33 is sleeved on the outer walls of the upper cylinder 34 and the lower cylinder 35, and the heat-insulating jacket 33 is used for ensuring the stability of the internal environment temperature of the environment box system; the hydrogen content analysis system is arranged in the cavity inside the two cylinders; the support base 37 is used for supporting and fixing the whole environmental tank system and the hydrogen content analysis system.
The hydrogen content analysis system comprises a hydrogen exposure module, a hydrogen transmission module and a hydrogen monitoring module; the hydrogen exposure module includes an upper side plate 38, an upper temperature sensor 39, a sample 40, and a sample stage 41; the hydrogen transmission module comprises an upper transmission air pipe 42, a transmission air valve 43 and a lower transmission air pipe 44; the hydrogen monitoring module comprises a lower side plate 45, a lower temperature sensor 46, a first oil groove 47, a gas pressure sensor 48, a small cylindrical connecting part 49, a second oil groove 50, a liquid pressure sensor 51 and a triangular prism-shaped positioning part 52; the upper temperature sensor 39 is fixedly connected with the upper side plate 38 through a welding process and is used for monitoring the test temperature of the hydrogen exposure module in real time; the sample 40 is cylindrical and placed on a sample table 41; the sample table 41 is two rectangular solids, and is fixed on the outer wall of the lower cylinder 35 through a welding process, and a gap is reserved between the two rectangular solids, so that hydrogen released by the sample 40 can conveniently enter the hydrogen monitoring module through the hydrogen transmission module; the upper end of the upper transmission air pipe 42 is fixedly connected with the inner wall of the lower cylinder 35 through a welding process, the lower end of the upper transmission air pipe is sequentially connected with a transmission air valve 43 and a lower transmission air pipe 44, and the transmission air valve 43 is used for controlling hydrogen to enter the hydrogen monitoring module from the hydrogen exposure module; the lower temperature sensor 46 is fixedly connected with the lower side plate 45 through a welding process and is used for monitoring the test temperature of the hydrogen monitoring module in real time; the upper left end of the first oil groove 47 is provided with a gas pressure sensor 48, and the gas pressure sensor 48 is used for monitoring the pressure of hydrogen entering the hydrogen monitoring module in real time; the small cylindrical connecting part 49 connects and fixes the first oil groove 47 and the second oil groove 50; the lower right end of the second oil groove 50 is provided with a liquid pressure sensor 51, and the liquid pressure sensor 51 is used for monitoring the oil pressure in the hydrogen monitoring module in real time; the triangular prism positioning member 52 is fixedly connected to the outer wall of the support base 37 through a welding process, and is used for fixing the position of the second oil groove 50.
In some embodiments of the present invention, the first oil groove 47 is a cylindrical oil groove and the second oil groove 50 is a square oil groove, it being understood that in other embodiments, other shapes are possible.
As shown in fig. 1, the gas source system includes a pressurization module and a depressurization module. The pressurizing module comprises an inlet and outlet air pressure sensor 17, an inlet and outlet air valve 18, an inlet and outlet air pipe 19, an air outlet valve 20, a pressurizing device 21, an air source main valve 22, an inert gas source valve 23, an inert gas bottle 24, a hydrogen source valve 25 and a hydrogen bottle 26 which are used for measuring the internal pressure value of the hydrogen exposing module; the pressure reducing module includes a lower exhaust pipe 27, a lower exhaust valve 28, a vacuum pump 29, a vacuum sensor 30 for testing the vacuum level inside the hydrogen exposure module, a vacuum line valve 31, and a purge valve 32. The right end of the first oil groove 47 is sequentially connected with the lower extraction valve 28 and the lower extraction pipe 27, so that the vacuum pump 29 can conveniently vacuumize the gas above the oil surface in the first oil groove 47, the internal oil levels of the first oil groove 47 and the second oil groove 50 reach a set height difference when the air extraction operation is finished, the lower extraction pipe 27 is communicated with the air outlet of the supercharger 21 and the air inlet and outlet pipe 19, the hydrogen cylinder 26 and the inert gas cylinder 24 are respectively connected with the air inlet of the supercharger 21 through pipelines, the air inlet and outlet valve 18 is arranged on the air inlet and outlet pipe 19, the air outlet valve 20 is arranged at the air outlet end of the supercharger 21, the air source main valve 22 is arranged at the air inlet end of the supercharger 21, and the inert gas source valve 23 and the hydrogen source valve 25 are respectively arranged at the air outlet ends of the inert gas cylinder 24 and the hydrogen cylinder 26. The vacuum pump 29 is connected with the air inlet and outlet pipe 19, and the vacuum sensor 30, the vacuum pipeline valve 31 and the vent valve 32 are all arranged on the air inlet and outlet pipe 19, and the vacuum sensor 30 is used for testing the vacuum degree in the hydrogen exposure module.
In some embodiments of the present invention, the inert gas is argon, it being understood that other inert gases may be used in other embodiments.
The industrial personal computer 1 can not only control the operation of the refrigerating and heating machine 3, the oil tank 12, the booster 21 and the vacuum pump 29 in a wired manner, but also control the opening and closing of all valves in a wireless manner, collect wireless signals sent by all sensors in an online manner, convert the wireless signals into various values by using a self-contained server, display the values on a screen of the industrial personal computer, and draw a relation curve of the content of hydrogen escaping from the sample 40 and the test time in real time based on a hydrogen content calculation formula.
As shown in fig. 1 and 2, the water inlet pipe adopts a split-flow arrangement and is divided into an upper water inlet pipe 5 and a lower water inlet pipe 8, so that a heat exchange water source from the refrigerating and heating machine 3 flows into an upper heat exchange bent pipe 6 and a lower heat exchange bent pipe 9 respectively; the water outlet pipe 6 is divided into an upper water outlet pipe 7 and a lower water outlet pipe 10 by adopting a split-flow arrangement, so that a heat exchange water source flows back to the refrigerating and heating machine 3 from the upper heat exchange bent pipe 6 and the lower heat exchange bent pipe 9 respectively; the split arrangement of the water inlet pipe and the water outlet pipe and the real-time monitoring of the upper temperature sensor 39 and the lower temperature sensor 46 can ensure the unification of the test temperature of the hydrogen content analysis system and realize the high temperature/low temperature test condition required by the test.
In some embodiments of the present invention, the liquid used in the oil source system is a non-volatile oil, including but not limited to peanut oil, soybean oil, and other common oils, which can reduce testing errors caused by volatilization of the liquid during the hydrogen content testing process.
In some embodiments of the present invention, the static seal member 36 is positioned at the interface of the upper cylinder 34 and the lower cylinder 35 to prevent leakage of high pressure hydrogen gas from the hydrogen exposure module.
The hydrogen exposure module is connected with the air source system through the air inlet and outlet pipe 19, and the number of times of pressurization-pressure maintaining-pressure relief of the high-pressure hydrogen in the hydrogen exposure module is independently selected according to the test requirement, so that multiple test working conditions such as single time and cycle exposure of the hydrogen in the hydrogen exposure module are realized.
The hydrogen exposure module enables hydrogen released by the sample 40 to flow into the hydrogen monitoring module through the hydrogen transmission module, so that the integration of the test functions of hydrogen exposure, hydrogen transmission and hydrogen monitoring is realized; the gas pressure sensor 48 is arranged at the left upper end of the first oil groove 47 and the liquid pressure sensor 51 is arranged at the right lower end of the second oil groove 50 of the hydrogen monitoring module, so that the gas pressure data and the oil pressure data in the hydrogen monitoring module can be collected in real time, and the hydrogen content change characteristic in the longitudinal oil groove can be analyzed on line by utilizing a hydrogen content calculation formula.
The oil body storage spaces in the first oil groove 47 and the second oil groove 50 are in a communicating state, and the gas pressure above the oil surface in the second oil groove 50 is always close to the atmospheric pressure, so that the communicating vessel principle is reasonably applied and the hydrogen content is accurately calculated.
As shown in fig. 3, the internal cross-sectional area of the first oil groove 47 is defined as S 1 (vertical cross-hatching portion of FIG. 3), subtracting S from the internal cross-sectional area of the second sump 50 1 The remaining area after that is defined as S 2 (transverse section line portion of FIG. 3), S 1 +S 2 Is the internal cross-sectional area of the second oil sump 50. Wherein the area S 1 Equal to area S 2 Thereby ensuring that the change in the internal oil level of the first oil tank 47 and the change in the internal oil level of the second oil tank 50 are kept identical, that is, the internal oil level of the first oil tank 47 can be reversely deduced only from the oil pressure data obtained by the liquid pressure sensor 51 at the right lower end of the second oil tank 50.
The specific application steps of the invention are as follows:
s1: and (5) installation. Firstly, ensuring that all valves are in a closed state through an industrial personal computer 1; next, the insulating jacket 33 is removed; the upper cylinder 34 is then removed to separate the upper and lower cylinders 35, leaving the sample stage 41 at the upper end of the lower cylinder 35 completely exposed; finally, the sample 40 is placed on the sample stage 41.
S2: filling. First, the upper cylinder body and the lower cylinder body 35 are closed; secondly, installing a heat preservation jacket 33 on the outer sides of the upper cylinder and the lower cylinder; the air inlet and outlet valve 18, the vacuum pump 29 and the vacuum pipeline valve 31 are opened again, and the hydrogen exposure module is vacuumized until the vacuum degree value VT shown by the vacuum degree sensor 30 1 The vacuum pump 29 and the vacuum pipeline valve 31 are closed when the value required by heat preservation of the heat preservation jacket 33 is reached; then opening the air outlet valve 20, the air source main valve 22 and the hydrogen source valve 23 to enable the hydrogen to be filled in the hydrogen exposure module, and closing the air outlet valve 20, the air source main valve 22 and the hydrogen source valve 23; then the operations of vacuumizing and hydrogen filling are alternately circulated for 10 times; and finally filling the hydrogen exposure module with low-pressure high-purity hydrogen.
S3: and (5) temperature adjustment. The refrigerating and heating machine 3, the water inlet valve 4 and the water outlet valve 11 are started, a heat exchange water source is introduced into the upper heat exchange elbow 6 through the upper water inlet pipe 5, and is introduced into the lower heat exchange elbow 9 through the lower water inlet pipe 8 until reaching a temperature value T shown by the upper temperature sensor 39 1 And a temperature value T indicated by a lower temperature sensor 46 2 Equal and all reach the set test temperature; in a subsequent series of steps from pressurization to depressurizationIn step (c), the refrigerating and heating machine 3, the water inlet valve 4 and the water inlet valve 11 are kept open so as to ensure that the test temperature of the hydrogen content analysis system is kept unchanged.
S4: pressurizing. Opening the air outlet valve 20, the booster 21, the air source main valve 22 and the hydrogen source valve 25 to slowly boost the high-purity hydrogen of the hydrogen exposure module until the pressure value F shown by the inlet and outlet pressure sensor 17 1 The set test pressure is reached and the value is stable.
S5: and (5) maintaining pressure. Closing the air inlet and outlet valve 18, the air outlet valve 20, the booster 21, the air source main valve 22 and the hydrogen source valve 25 to enable the hydrogen of the hydrogen exposure module to be in a closed pressure maintaining state, and exposing the sample for 24 hours in a high-pressure hydrogen environment; the subsequent refueling and pumping steps were synchronized with the dwell pressure for 24 hours.
S6: and (5) oiling. Opening the lower extraction valve 28 and the vent valve 32 so that the gas in the hydrogen monitoring module is directly communicated with the atmosphere outside the vent valve and maintained for 1 hour, and so that the gas pressure in the hydrogen monitoring module is equal to the atmospheric pressure; the oil tank 12 and the oil filling valve 13 are opened to allow the oil body to be filled into the first oil groove 47 and the second oil groove 50 through the oil filling pipe 14 until the pressure value P indicated by the liquid pressure sensor 51 L0 The set value is reached and the tank 12, the filler valve 13 and the purge valve 32 are closed.
S7: and (5) exhausting. The vacuum pump 29 and the vacuum pipeline valve 31 are started to vacuumize the gas in the lower exhaust pipe 27 and above the oil surface in the first oil groove 47 until the vacuum degree value VT shown by the vacuum degree sensor 30 2 And a pressure value P indicated by the liquid pressure sensor 51 L1 The set point is reached and the lower extraction valve 28, vacuum pump and vacuum line valve are closed.
S8: and (5) pressure relief. After the pressure maintaining, oiling and pumping steps are completed, the air inlet and outlet valve 18 and the air outlet valve 32 are opened to rapidly release the pressure of the hydrogen exposure module until the pressure value F shown by the pressure sensor 17 2 When the pressure is equal to the atmospheric pressure, the evacuation valve 32 is closed, the vacuum pump 29 and the vacuum line valve 31 are opened, and the hydrogen exposure module is evacuated until the vacuum level VT shown by the vacuum level sensor 20 3 Equal to VT 2 The air inlet and outlet valve, the vacuum pump and the vacuum pipeline valve are closed.
S9: and (5) temperature returning. Regulating refrigeration and addingThe heat engine 3, through the upper heat exchanging elbow 6 and the lower heat exchanging elbow 9, causes the temperature value T shown by the upper temperature sensor 39 3 And a temperature value T indicated by a lower temperature sensor 46 4 Equal and all reach the set test temperature.
S10: and (5) testing. Opening the transfer valve 43 to allow the hydrogen gas released from the sample 40 to enter the first oil tank 47 through the upper transfer gas pipe 42 and the lower transfer gas pipe 44, thereby causing the oil level in the first oil tank 47 to be lowered; the pressure value P shown by the gas pressure sensor 48 and the liquid pressure sensor 51 is obtained by using the server of the industrial personal computer 1 G2 And P L2 Displaying the relationship curve between the content of hydrogen released from the sample and the test time on the screen of the industrial personal computer by utilizing a hydrogen content calculation formula; the detailed derivation of the formula for calculating the hydrogen content is listed later.
S11: and (5) purging. After the hydrogen content test is completed, opening the air inlet and outlet valve 18, the lower extraction valve 28 and the vent valve 32 to release the hydrogen in the hydrogen content analysis system and the gas source system pipeline; after 1 hour of maintenance, the air outlet valve 20, the air source main valve 22 and the inert gas source valve 23 are opened, the low-pressure argon is used for purging the hydrogen content analysis system and the air source module pipeline, residual hydrogen is removed, and the refrigerating and heating machine 3, the water inlet valve 4, the water outlet valve 11, the air inlet and outlet valve, the air source main valve and the inert gas source valve are closed.
S12: and (5) oil discharge. The tank 12 and the drain valve 15 were opened, and the oil body was returned to the tank from the first oil tank 47 and the second oil tank 50 through the drain pipe 16, and after 1 hour, the tank, the drain valve, the lower suction valve 28, the drain valve 32, and the transfer valve 43 were closed.
S13: and (5) sample unloading. The insulating jacket 33 is removed first, then the upper cylinder 34 is removed, the upper cylinder 34 and the lower cylinder 35 are separated, and finally the sample 40 is taken out.
The calculation formula of the hydrogen content is specifically as follows:
as shown in fig. 3, the first oil groove 47 has an inner cross-sectional area S 1 Equal to the internal cross-sectional area of the second sump 50 minus S 1 The remaining area after that, i.e. area S 1 Equal to area S 2 So that the amount of change in the internal oil level of the first oil groove 47 is equal to the amount of change in the internal oil level of the second oil groove 50.
Before refueling (as shown in fig. 4), the first oil tank 47 and the second oil tank 50 are both free of oil. The internal volume of the lower transfer air tube 44 is known as V 1 [m 3 ]The volume of the short pipe between the first oil tank 47 and the lower extraction valve 28 is V 2 [m 3 ]The vertical distance from the top end of the first oil groove 47 to the bottom end of the second oil groove 50 is H 1 [m]，
After refueling (as shown in fig. 5), the gas pressure above the oil level in the first oil tank 47 and the gas pressure above the oil level in the second oil tank 50 are both at the atmospheric pressure P 0 [Pa]Obtained according to the principle of communicating vessels, when the pressure P measured by the liquid pressure sensor 51 L0 [Pa]When the set value is reached, the liquid level heights of the inner and outer oil should be kept consistent at the moment, and are H 2 [m]。
After the air suction, since the gas above the oil surface in the first oil tank 47 is sucked away, the gas pressure thereof is reduced, and therefore the oil level in the first oil tank 47 rises, the oil level in the second oil tank 50 falls, and the increase in the oil level in the first oil tank 47 is equal to the decrease in the oil level in the second oil tank 50, as shown in fig. 6.
Since the pressure relief and the warming operation have substantially no effect on the level of the oil within the pumped first and second oil tanks 47, 50, the features of the warmed hydrogen monitoring module can still be seen in fig. 6. Assume that the pressure measured by the gas pressure sensor 48 after the temperature is returned is P G1 [Pa]The pressure measured by the liquid pressure sensor 51 is P L1 [Pa]The pressure of the gas above the oil surface in the longitudinal oil groove is P 1 [Pa]The height of the oil surface in the first oil groove 47 is H 3 [m]From the ideal gas state equation pv=nrt, we get:
P 1 (V 1 +V 2 +V 3 )＝n 1 RT (1)
P 1 ＝P G1 (2)
wherein V is 3 To the volume [ m ] of the gas above the oil surface in the first oil tank 47 after the temperature is returned 3 ]，n 1 For Fang Qiti mol number [ mol ] of the oil surface in the first oil tank after the temperature is returned]R is a gas constant of 8.314[ J/mol.K ]]T is the test temperature [ K ] of the whole hydrogen content analysis system after temperature return]ρ is the density of the oil body [ kg/m ] 3 ]G is gravity acceleration [ m/s ] 2 ]。
Simultaneous (1) (2) (3) (4) results in:
during the hydrogen content test (as shown in fig. 7), since hydrogen gas slowly enters the first oil tank 47 above the oil surface through the lower transfer gas pipe 44, the gas pressure thereof increases, and thus the first oil tank inner oil level decreases and the second oil tank 50 inner oil level increases. Assuming that time 0 represents both the end time of the warm-up and the instant when the transfer valve 46 is opened (because hydrogen gas does not enter the first oil tank during the period from the time of warm-up to the time of opening the purge valve), time t represents the time s elapsed from the time 0]The pressure measured by the gas pressure sensor 48 at time t is P G2 [Pa]The pressure measured by the liquid pressure sensor 51 is P L2 [Pa]The gas pressure above the oil surface in the first oil groove is P 2 [Pa]The height of the oil surface in the first oil groove is H 4 [m]From the ideal gas state equation pv=nrt, we get:
P 2 (V 1 +V 2 +V 4 )＝n 4 RT (6)
P 2 ＝P G2 (7)
wherein V is 4 Is the volume [ m ] of gas above the oil level in the first oil tank 47 at time t during the hydrogen content test 3 ]，n 2 Fang Qiti mol/mol of the oil surface in the first oil tank at t time in the hydrogen content test process]。
Simultaneous (4) (6) (7) (8) results in:
therefore, the number of moles Δn [ mol ] of hydrogen gas increased above the oil surface in the first oil tank 47 from the temperature return to the time t in the hydrogen content test process, that is, from 0 to t, is calculated as follows:
therefore, the released hydrogen content C (t) [ wt.ppm ] in the sample 40 from the temperature return to the time t during the hydrogen content test, i.e., in the period of 0 to t is:
wherein M is the molar mass [ g/mol ] of hydrogen, the value is 2.016, and M is the initial mass [ g ] of the sample.
The final high-pressure hydrogen material hydrogen content C (t) [ wt ppm ] can be obtained by combining (10) and (11) as follows:
the above examples are only illustrative embodiments of the present invention, and the present invention is not limited to the above-described preferred embodiments, but is not limited to the above-described embodiments, and any equivalent modifications and variations can be made by those skilled in the art without departing from the scope of the present invention, as defined by the following claims. For example, the present invention is not limited to use only with hydrogen as a test medium, but is also applicable to a test medium such as a hydrogen sulfide gas, a mixed gas of natural gas and hydrogen, or the like. Any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the technical solution of the present invention still falls within the scope of the technical solution of the present invention.
Claims (10)
1. The novel hydrogen content testing device for the high-pressure hydrogen-bearing material is characterized by comprising a control system, a heat exchange system, an oil source system, an environment box system, a hydrogen content analysis system and an air source system;
the control system comprises an industrial personal computer (1);
the heat exchange system, the air source system and the oil source system are all connected with the environment box system and are connected with the industrial personal computer (1) in a wired way;
the environment box system comprises an upper cylinder (34) and a lower cylinder (35);
the hydrogen content analysis system comprises a hydrogen exposure module, a hydrogen transmission module and a hydrogen monitoring module, wherein the hydrogen exposure module is arranged in an upper cylinder body (34), the hydrogen exposure module comprises an upper temperature sensor (39) for monitoring the test temperature of the hydrogen exposure module and a sample table (41) for placing a sample (40), the hydrogen monitoring module is arranged in a lower cylinder body (35), the hydrogen exposure module and the hydrogen monitoring module are connected through the hydrogen transmission module so as to transmit hydrogen released by the sample (40) to the hydrogen monitoring module, the hydrogen monitoring module comprises a lower temperature sensor (46) for monitoring the test temperature of the hydrogen monitoring module, a gas pressure sensor (48) for monitoring the pressure of the hydrogen, a liquid pressure sensor (51) for monitoring the pressure of the oil body, a first oil groove (47) and a second oil groove (50), the first oil groove (47) is positioned in the second oil groove (50) and the oil body storage spaces inside the two oil grooves are communicated, and each sensor is in signal connection with the industrial personal computer (1).
2. The hydrogen content testing device of the novel high-pressure hydrogen-bearing material according to claim 1, wherein the heat exchange system comprises a refrigerating and heating machine (3), a water inlet valve (4), an upper water inlet pipe (5), an upper heat exchange elbow pipe (6), an upper water outlet pipe (7), a lower water inlet pipe (8), a lower heat exchange elbow pipe (9), a lower water outlet pipe (10) and a water outlet valve (11),
the refrigerating and heating machine (3) is connected with the industrial personal computer (1) in a wired way;
the upper water inlet pipe (5), the upper heat exchange bent pipe (6) and the upper water outlet pipe (7) are sequentially connected, pass through the upper cylinder (34), the lower water inlet pipe (8), the lower heat exchange bent pipe (9) and the lower water outlet pipe (10) are sequentially connected, pass through the lower cylinder (35), the upper water inlet pipe (5) and the lower water inlet pipe (8) are both connected with the water outlet end of the refrigerating and heating machine (3), and the upper water outlet pipe (7) and the lower water outlet pipe (10) are both connected with the water return end of the refrigerating and heating machine (3);
the water inlet valve (4) and the water outlet valve (11) are respectively arranged at the water outlet end and the water return end of the refrigerating and heating machine (3) and are in signal connection with the industrial personal computer (1).
3. The hydrogen content testing device of a novel high-pressure hydrogen-bearing material according to claim 1, wherein the oil source system comprises an oil tank (12), an oil filling valve (13), an oil filling pipe (14), an oil discharging valve (15) and an oil discharging pipe (16); the oil tank (12) is connected with an environment tank system through the oil filling pipe (14) and the oil discharging pipe (16) to form a circulation loop of an oil body, the oil filling valve (13) and the oil discharging valve (15) are respectively arranged on the oil filling pipe (14) and the oil discharging pipe (16), the oil tank (12) is connected with the industrial personal computer (1) in a wired mode, and the oil filling valve (13) and the oil discharging valve (15) are connected with the industrial personal computer (1) in a signal mode.
4. A novel high-pressure hydrogen-bearing material hydrogen content testing device according to claim 3, wherein the oil tank (12) contains a nonvolatile oil body.
5. The hydrogen content testing device for a novel high-pressure hydrogen-bearing material according to claim 1, wherein the environmental box system further comprises a support base (37), the support base (37) is located at the bottom of the lower cylinder (35), and the second oil groove (50) is fixed on the support base (37).
6. The hydrogen content testing device for a novel high-pressure hydrogen-bearing material according to claim 1, wherein the environmental chamber system further comprises a heat-insulating jacket (33), and the heat-insulating jacket (33) is arranged on the outer cylinder walls of the upper cylinder (34) and the lower cylinder (35) in a surrounding manner.
7. The hydrogen content testing device for a novel high-pressure hydrogen-bearing material according to claim 1, wherein the gas source system comprises a pressurizing module and a depressurizing module;
the pressurizing module comprises an air inlet and outlet pressure sensor (17), an air inlet and outlet valve (18), an air inlet and outlet pipe (19), an air outlet valve (20), a pressurizer (21), an air source main valve (22), an inert gas source valve (23), an inert gas bottle (24), a hydrogen source valve (25) and a hydrogen bottle (26), wherein the hydrogen bottle (26) and the inert gas bottle (24) are respectively connected with an air inlet of the pressurizer (21) through pipelines, an air outlet of the pressurizer (21) is connected with a hydrogen content analysis system through the air inlet and outlet pipe (19), the air inlet and outlet valve (18) is arranged on the air inlet and outlet pipe (19), the air outlet valve (20) is arranged at the air outlet end of the pressurizer (21), the air source main valve (22) is arranged at the air inlet end of the pressurizer (21), and the inert gas source valve (23) and the hydrogen source valve (25) are respectively arranged at the air outlet ends of the inert gas bottle (24) and the hydrogen bottle (26);
The vacuum module comprises a lower exhaust pipe (27), a lower exhaust valve (28), a vacuum pump (29), a vacuum degree sensor (30), a vacuum pipeline valve (31) and a vent valve (32), wherein the vacuum degree sensor (30), the vacuum pipeline valve (31) and the vent valve (32) are used for testing the vacuum degree inside the hydrogen exposure module, the vacuum pump (29) is connected with a hydrogen content analysis system through the lower exhaust pipe (27), the lower exhaust pipe (27) is connected with an air inlet and outlet pipe (19), the lower exhaust valve (28) is arranged on the lower exhaust pipe (27), the vacuum degree sensor (30), the vacuum pipeline valve (31) and the vent valve (32) are all arranged on the air inlet and outlet pipe (19), the vacuum pump (29) is in wired connection with the industrial personal computer (1), and each valve and the vacuum degree sensor (30) are in signal connection with the industrial personal computer (1).
8. The device for testing the hydrogen content of the novel high-pressure hydrogen-contacting material according to any one of claims 1 to 7, wherein the hydrogen transmission module comprises an upper transmission air pipe (42), a transmission air valve (43) and a lower transmission air pipe (44) which are sequentially connected, the upper transmission air pipe (42) is communicated with the hydrogen exposure module, and the lower transmission air pipe (44) is communicated with the hydrogen monitoring module.
9. A method for in situ testing of hydrogen content of a material for hydrogen energy equipment, characterized in that the apparatus according to any one of claims 1 to 8 is used, said method comprising the steps of:
step A: mounting, namely separating the upper cylinder (34) from the lower cylinder (35) to enable a sample table (41) positioned at the upper end of the lower cylinder (35) to be completely exposed, and finally placing a sample (40) on the sample table (41);
And (B) step (B): filling, namely closing an upper cylinder (34) and a lower cylinder (35), and vacuumizing the hydrogen exposure module until a vacuum degree value shown by a vacuum degree sensor reaches a value required by heat preservation of a heat preservation jacket; filling hydrogen into the upper cylinder (34) through an air source system to enable the hydrogen to be filled in the hydrogen exposure module, then alternately circulating vacuumizing and hydrogen filling operation for a plurality of times, and finally enabling the hydrogen exposure module to be filled with low-pressure high-purity hydrogen;
step C: the temperature is regulated, a heat exchange system is started to regulate the temperature in the upper cylinder (34) and the temperature in the lower cylinder (35) until the temperature value shown by the upper temperature sensor and the temperature value shown by the lower temperature sensor are equal and reach the set test temperature, and in the subsequent series of steps from pressurizing to pressure releasing, the heat exchange system is kept on to ensure that the test temperature of the hydrogen content analysis system is kept unchanged;
step D: pressurizing, namely slowly pressurizing high-purity hydrogen of the hydrogen exposure module through an air source system until a pressure value shown by the inlet and outlet pressure sensor reaches a set test pressure and the value is stable;
step E: maintaining pressure, namely enabling hydrogen of the hydrogen exposure module to be in a closed pressure maintaining state, enabling the sample to be exposed for preset time in a high-pressure hydrogen environment, and enabling subsequent oiling and air extraction steps to be carried out synchronously with the pressure maintaining process;
Step F: oiling, namely directly communicating the gas in the hydrogen monitoring module with the atmosphere and keeping the gas pressure in the hydrogen monitoring module equal to the atmospheric pressure for a preset time, and injecting the oil body into the first oil groove (47) and the second oil groove (50) through an oil source system until the oil body pressure in the hydrogen monitoring module reaches a set value;
step G: pumping air, starting a vacuum pump and a vacuum pipeline valve, and vacuumizing air above the oil surface in the first oil groove (47) until a vacuum degree value shown by a vacuum degree sensor and an oil pressure value in the monitoring hydrogen monitoring module reach set values;
step H: after the pressure maintaining, oiling and exhausting steps are completed, the hydrogen exposure module is rapidly depressurized until the pressure value shown by the pressure sensor is equal to the atmospheric pressure; vacuumizing the hydrogen exposure module until the vacuum degree value shown by the vacuum degree sensor is equal to the atmospheric pressure;
step I: the temperature is returned, and the temperature is regulated by a heat exchange system, so that the temperature value shown by an upper temperature sensor (39) is equal to the temperature value shown by a lower temperature sensor (46) and both reach the set test temperature;
step J: the method comprises the steps of testing, enabling hydrogen released by a sample (40) to enter a first oil groove (47) through a hydrogen transmission module, so that the height of an oil level in the first oil groove (47) is reduced, displaying a hydrogen pressure value and an oil pressure value of a hydrogen monitoring module on a screen of the oil pressure of an industrial control machine by utilizing an industrial control machine (1), and drawing a relation curve of the hydrogen content released by the sample (40) and testing time in real time by utilizing a hydrogen content calculation formula;
Step K: after the hydrogen content test is completed, releasing hydrogen in the hydrogen content analysis system and the gas source system, and after the hydrogen content analysis system and the gas source system are kept for a preset time, purging the hydrogen content analysis system and the gas source system by using low-pressure inert gas to remove residual hydrogen;
step L: discharging oil, namely enabling oil bodies to flow back to an oil tank oil source system from a first oil tank (47) and a second oil tank (50);
step M: and unloading the sample, separating the upper cylinder (34) from the lower cylinder (35), and taking out the sample (40).
10. The in-situ test method for hydrogen content of hydrogen energy equipment material according to claim 9, wherein the hydrogen content calculation formula is as follows
Where M is the molar mass of hydrogen, M is the initial mass of the sample, and Deltan is the number of hydrogen moles increased above the oil level in the first oil tank (47) in a time period of 0 to t.
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