CN111751246A - Gas supply method and device for detecting hydrogen content in solid metal - Google Patents

Gas supply method and device for detecting hydrogen content in solid metal Download PDF

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Publication number
CN111751246A
CN111751246A CN202010672081.5A CN202010672081A CN111751246A CN 111751246 A CN111751246 A CN 111751246A CN 202010672081 A CN202010672081 A CN 202010672081A CN 111751246 A CN111751246 A CN 111751246A
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China
Prior art keywords
gas
hydrogen
electromagnetic valve
calibration
module
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CN202010672081.5A
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Inventor
陈建勋
戚政武
张大伟
张万宝
陈英红
杨宁祥
张少琼
叶忠巧
李晓峰
李继承
谢小娟
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Alashan League Special Equipment Inspection Institute
Guangdong Inspection and Research Institute of Special Equipment Zhuhai Inspection Institute
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Alashan League Special Equipment Inspection Institute
Guangdong Inspection and Research Institute of Special Equipment Zhuhai Inspection Institute
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Priority to CN202010672081.5A priority Critical patent/CN111751246A/en
Publication of CN111751246A publication Critical patent/CN111751246A/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N7/00Analysing materials by measuring the pressure or volume of a gas or vapour
    • G01N7/14Analysing 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
    • G01N7/16Analysing 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 by heating the material
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/20Metals
    • G01N33/202Constituents thereof
    • G01N33/2022Non-metallic constituents
    • G01N33/2025Gaseous constituents

Abstract

The invention relates to a gas supply method and a device for detecting the content of hydrogen in solid metal, wherein the gas supply device is connected with a hydrogen evolution chamber for evolving hydrogen in the solid metal, and the gas supply device mainly comprises: the device comprises a gas source module, a gas electromagnetic valve module, a gas purification module, a vacuumizing module and a control module. The hydrogen content detection device can provide carrier gas for detecting the hydrogen content of a sample, can also provide hydrogen-containing calibration gas for calibrating a high-temperature hydrogen sensor, and has the advantages of matching a gas supply process with a test process, high automation degree and high detection efficiency; and the calibration requirements of different hydrogen concentrations are met, and the gas flow control accuracy is improved.

Description

Gas supply method and device for detecting hydrogen content in solid metal
Technical Field
The invention relates to the technical field of detection of substance content in a sample, relates to detection of hydrogen content in a solid metal sample, such as detection of diffused hydrogen content or total hydrogen content in a steel block, an aluminum block and a metal welding joint, and particularly relates to a gas supply method and a gas supply device for detecting the hydrogen content in the solid metal.
Background
The hydrogen sensor prepared by taking the functional ceramic as a core element is a high-temperature sensor which develops rapidly in recent years, and the sensor is gradually applied to detecting the hydrogen content in high-temperature media such as liquid metal, molten salt and the like. The high temperature at which hydrogen gas is evolved from each material varies depending on the type of material. For detecting the content of hydrogen in the solid metal, if a high-temperature hydrogen sensor is adopted, the hydrogen precipitated at high temperature (generally 300-500 ℃ or higher) can be directly detected without cooling and secondary collection of the hydrogen. Compared with the traditional thermal conductivity cell, a gas chromatograph and an infrared element detection module, the high-temperature hydrogen sensor can realize high-temperature in-situ test of hydrogen content detection in solid metal without secondary hydrogen collection, and the hydrogen measuring device using the method is smaller and more portable, has higher hydrogen measuring efficiency and lower relative cost. When the high-temperature hydrogen sensor is used for detecting the hydrogen content in the solid metal, a set of gas supply device is used for providing carrier gas for the hydrogen separation chamber, and the carrier gas is used for gas replacement purging of the hydrogen separation chamber or providing the carrier gas in the hydrogen separation process; in the calibration process of the hydrogen measuring device, the gas supply device is required to provide calibration gas with known hydrogen content for the hydrogen measuring device, and the hydrogen measuring device is calibrated. The gas supply device is used as an important module of the device for detecting the content of hydrogen in the solid metal, and plays an important role in detecting the content of hydrogen and calibrating the hydrogen measuring device. However, the existing gas supply device has a single gas supply mode and low automation degree, so that the detection efficiency is low, data has large errors, and the detection result is seriously influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a gas supply method and a gas supply device for detecting the hydrogen content in solid metal, which can provide carrier gas for detecting the hydrogen content of a solid metal sample and also provide hydrogen-containing calibration gas for calibrating a high-temperature hydrogen sensor in a detection device, the gas supply process is matched with the test process, the automation degree is high, and the detection efficiency is high; high-hydrogen concentration calibration gas or low-hydrogen concentration calibration gas is provided, the calibration requirements of different hydrogen concentrations are met, the calibration of the high-temperature hydrogen sensor is realized, the influence of the factors of the sensor on the detection accuracy of the metal hydrogen content is avoided, and the detection precision of data is improved; meanwhile, by selecting the large-flow gas flow controller and the small-flow gas flow controller, the requirements of different gas flows entering the hydrogen separation chamber can be met, the gas flow control accuracy is improved, and the calibration process and the accuracy of the detection data of the solid metal hydrogen content are further improved.
In order to solve at least one of the above technical problems, the technical solution adopted by the present invention is:
in one aspect, the present invention provides a gas supply device for detecting hydrogen content in solid metal, wherein the gas supply device is used for connecting with a hydrogen evolution chamber for hydrogen evolution of solid metal, and the gas supply device comprises:
the gas source module comprises a hydrogen-containing calibration gas source and a carrier gas source;
a gas solenoid valve module, the gas solenoid valve module comprising: the hydrogen-containing calibration gas source comprises a carrier gas electromagnetic valve, a hydrogen-containing calibration gas electromagnetic valve, a first gas electromagnetic valve, a second gas electromagnetic valve and a gas outlet electromagnetic valve, wherein the carrier gas electromagnetic valve is connected with the carrier gas source, and the hydrogen-containing calibration gas electromagnetic valve is connected with the hydrogen-containing calibration gas source;
the inlet of the gas purification module is respectively connected with the carrier gas electromagnetic valve and the hydrogen-containing calibration gas electromagnetic valve, the outlet of the gas purification module is connected with the inlet of the first gas electromagnetic valve through a first gas flow controller, the outlet of the first gas electromagnetic valve is connected with the gas inlet of the sample preamplification area of the hydrogen analysis chamber, the outlet of the gas purification module is connected with the inlet of a second gas flow controller through the second gas electromagnetic valve, and the outlet of the second gas flow controller is connected with the gas inlet of the heating area of the hydrogen analysis chamber;
the vacuumizing module is connected with a gas outlet of a heating area of the hydrogen separation chamber through the gas outlet electromagnetic valve;
and the control module is used for the integral operation of the gas supply device.
Further, the method also comprises the following steps: and the carrier gas electromagnetic valve is connected with the carrier gas source through the pressure reducing valve module, and the hydrogen-containing calibration gas electromagnetic valve is connected with the hydrogen-containing calibration gas source through the pressure reducing valve module.
Further, the method also comprises the following steps: a pressure display module, the pressure display module comprising: the gas source pressure gauge and the hydrogen evolution chamber pressure gauge are arranged at the inlet of the gas purification module, and the hydrogen evolution chamber pressure gauge is arranged at the gas inlet of the heating area of the hydrogen evolution chamber.
Further, the gas purification module includes: the device comprises a water vapor removal unit and a carbon dioxide removal unit, wherein an inlet of the water vapor removal unit is respectively connected with the carrier gas electromagnetic valve and the hydrogen-containing calibration gas electromagnetic valve, an inlet of the carbon dioxide removal unit is connected with an outlet of the water vapor removal unit, and an outlet of the carbon dioxide removal unit is respectively connected with the first gas flow controller and the second gas electromagnetic valve.
Further, a high-temperature hydrogen sensor for detecting the concentration of hydrogen precipitated from the solid metal is arranged in the heating area.
Further, the hydrogen-containing calibration gas source comprises: the volume fraction of the high hydrogen concentration calibration gas source is 10 percent, and the volume fraction of the low hydrogen concentration calibration gas source is 0.1 percent.
Further, the carrier gas stored by the carrier gas source comprises: the hydrogen-containing calibration gas source stores hydrogen-containing calibration gas which is hydrogen-inert gas mixed gas, preferably hydrogen-argon mixed gas.
Further, the control module is a PLC, an industrial control computer or a personal computer.
In another aspect, the present invention provides a gas supply method for detecting hydrogen content in solid metal by using the gas supply apparatus, including the following steps:
s1: closing the hydrogen-containing calibration gas electromagnetic valve through the control module, opening the carrier gas electromagnetic valve, and adjusting the pressure reducing valve module to enable the pressure to be slightly greater than one atmosphere;
s2: putting a solid metal sample into a sample pre-discharge area of a hydrogen evolution chamber, closing a first gas electromagnetic valve and a second gas electromagnetic valve, simultaneously opening a gas outlet electromagnetic valve, setting a first gas flow controller to reach a certain gas flow rate, controlling a vacuumizing module to vacuumize the hydrogen evolution chamber, and closing the gas outlet electromagnetic valve and the vacuumizing module to enable the hydrogen evolution chamber to be in a vacuum state;
s3: opening a first gas electromagnetic valve to enable carrier gas in a carrier gas source to flow into a hydrogen evolution chamber through the first gas electromagnetic valve, and opening a gas outlet electromagnetic valve to enable the carrier gas to continuously purge and flow out a solid metal sample and the hydrogen evolution chamber when the pressure in the hydrogen evolution chamber is more than one atmosphere, so as to replace the hydrogen evolution chamber with a carrier gas atmosphere;
s4: moving the solid metal sample into a heating area of the hydrogen evolution chamber, opening a second gas electromagnetic valve, closing a first gas electromagnetic valve, adjusting a second gas flow controller to enable carrier gas to flow in the hydrogen evolution chamber, and enabling the carrier gas to gradually isolate the evolved hydrogen into the hydrogen chamber through an air outlet electromagnetic valve belt in the process of heating the solid metal sample to evolve the hydrogen;
s5: and after all hydrogen in the solid metal sample is separated out, closing the second gas electromagnetic valve, then opening the first gas electromagnetic valve, and continuously purging and cooling the inside of the hydrogen separation chamber by carrier gas.
In another aspect, the present invention provides a gas supply method for calibrating a high temperature hydrogen sensor by using the gas supply apparatus, comprising the following steps:
s1: the hydrogen-containing calibration gas electromagnetic valve is opened through the control module, the carrier gas electromagnetic valve is closed, and the pressure reducing valve module is adjusted to enable the pressure to be slightly larger than one atmosphere;
s2: closing the first gas electromagnetic valve and the second gas electromagnetic valve, simultaneously opening the gas outlet electromagnetic valve, setting the first gas flow controller to reach a certain gas flow rate, controlling the vacuumizing module to vacuumize the hydrogen evolution chamber, and closing the gas outlet electromagnetic valve and the vacuumizing module to enable the hydrogen evolution chamber to be in a vacuum state;
s3: opening a first gas electromagnetic valve to enable the hydrogen-containing calibration gas in the hydrogen-containing calibration gas source to flow into the hydrogen evolution chamber through the first gas electromagnetic valve, and opening a gas outlet electromagnetic valve to enable the hydrogen-containing calibration gas to continuously purge and flow out of the hydrogen evolution chamber when the pressure in the hydrogen evolution chamber is greater than one atmosphere, so that the hydrogen evolution chamber is replaced by the hydrogen-containing calibration gas atmosphere;
s4: and opening the second gas electromagnetic valve, closing the first gas electromagnetic valve, adjusting the second gas flow controller to enable the hydrogen-containing calibration gas to flow in the hydrogen evolution chamber, detecting the hydrogen concentration in the hydrogen evolution chamber by the high-temperature hydrogen sensor when the internal temperature of the hydrogen evolution chamber reaches the test temperature of the high-temperature hydrogen sensor, and comparing the detection result with the actual hydrogen concentration of the hydrogen-containing calibration gas to realize the calibration of the high-temperature hydrogen sensor.
Compared with the prior art, the invention has the beneficial effects that:
(1) the high-temperature hydrogen sensor which can be directly used at high temperature is used as a hydrogen measuring element, so that the separation and detection of hydrogen in solid metal are synchronously carried out, and the detection of hydrogen content is carried out after the separated hydrogen is not required to be collected;
(2) the structure form that the cylinder body is provided with the cylinder body branch is adopted, the sample pre-release area and the heating area are arranged for the hydrogen evolution chamber, the metal sample to be detected is temporarily placed in the sample pre-release area before heating and hydrogen evolution and is fully swept by carrier gas, and the interference of the adsorbed gas on the surface of the sample on the hydrogen content detection result can be greatly weakened;
(3) the cooling element can quickly cool the hydrogen evolution chamber, so that the sample analysis time is shortened, and the test efficiency is improved;
(4) by adding blank tests, the influence of the self factors of the detection device on the detection accuracy of the metal hydrogen content is reduced, and the detection precision of data is improved;
(5) the gas supply device can provide carrier gas for detecting the hydrogen content of the solid metal sample, and also can provide hydrogen-containing calibration gas for calibrating a high-temperature hydrogen sensor in the detection device, the gas supply process is matched with the test process, and the automation degree is high;
(6) the high-hydrogen concentration calibration gas or the low-hydrogen concentration calibration gas can be provided, the calibration requirements of different hydrogen concentrations are met, the calibration of the high-temperature hydrogen sensor is realized, the influence of the factors of the sensor on the detection accuracy of the metal hydrogen content is avoided, and the detection precision of data is improved;
(7) by selecting the large-flow gas flow controller and the small-flow gas flow controller, the requirements of different gas flows entering the hydrogen analysis chamber can be met, the gas flow control accuracy is improved, and the calibration process and the accuracy of the detection data of the solid metal hydrogen content are further improved.
Drawings
FIG. 1 is a block diagram of the detecting device of the present invention.
FIG. 2 is a schematic view of the hydrogen evolution chamber of the present invention.
FIG. 3 is a schematic view of the placement of a solid metal sample according to the present invention.
FIG. 4 is a flow chart of the hydrogen content blank test detection of the present invention.
FIG. 5 is a flow chart of the solid metal hydrogen content detection method of the present invention.
Fig. 6 is a graph of hydrogen concentration versus time.
Fig. 7 is a schematic structural diagram of an air supply device according to an embodiment of the present invention.
Fig. 8 is a control schematic block diagram of a control module in the air supply apparatus according to an embodiment of the present invention.
In the above figures: 1-a cylinder body; 2-first barrel end cap; 3-a second cylinder end cover; 4-cylinder branch end cover; 5-a temperature sensor; 6-high temperature hydrogen sensor; 7-solid metal sample; 8-a heating element; 9-a cooling element; 100-an air supply unit; 101-a sample pre-placement area; 102-a heating zone; 103-cylinder branch; 104-a push rod; 11-heating zone gas inlet; 12-heating zone gas outlet; 13-cylinder sealing element one; 14-cylinder sealing element two; 15-sample pre-discharge area gas inlet; 16-a cylinder branch sealing element; 17-sample pusher channel; 18-temperature sensor sensing element; 19-high temperature hydrogen sensor sensing element; 20-a vacuum pump; 21-hydrogen concentration-time curve; 22-the area of a geometric region enclosed by the curve and the time coordinate axis; 231-a carrier gas source; 232-high hydrogen concentration calibration gas source; 233-low hydrogen concentration calibration gas source; 241-a first pressure reducing valve; 242-a second pressure relief valve; 243-third pressure reducing valve; 251-carrier gas solenoid valve; 252-a first hydrogen containing calibration gas solenoid valve; 253-a second hydrogen-containing calibration gas solenoid valve; 261-a first gas source pressure gauge; 262-a second gas source pressure gauge; 271-water vapor removal unit; 272-a carbon dioxide removal unit; 281-first gas flow controller; 282-first gas solenoid valve; 291-large flow gas electromagnetic valve; 292-a high flow gas flow controller; 293-low flow gas solenoid valve; 294-small flow gas flow controller; 30-hydrogen evolution chamber pressure gauge; 31-a processor; 32-a signal conversion module; 33-switching value input and output module; 34-analog input module; 35-air outlet electromagnetic valve; 36-hydrogen separation chamber.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to specific examples. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications.
Example 1: according to the embodiment of the present invention, there is provided a device for detecting hydrogen content in solid metal, fig. 1 is a block diagram of the structure of the detection device of the present invention, and as shown in fig. 1, the device mainly includes: the device comprises an air supply control unit, an air supply unit, a hydrogen separation chamber, a signal acquisition unit, a temperature control unit and a control processing system.
During testing, the solid metal sample is placed in the hydrogen evolution chamber, and the gas supply unit is connected with the hydrogen evolution chamber and used for providing the hydrogen evolution chamber with carrier gas for carrying a hydrogen carrier in the processes of purging the solid metal sample before heating and hydrogen evolution. The gas supply control unit and the gas supply unit jointly form a gas supply device, the gas supply control unit is connected with the gas supply unit to realize control over the gas supply unit, and specifically, the gas supply control unit is used for controlling the on-off of a relevant valve in the gas supply unit, setting the flow of the gas flow control element and acquiring a gas pressure signal in the gas supply unit.
In this embodiment of the invention, the specific kind of the air supply means (the air supply control unit and the air supply unit) is not particularly limited as long as the air supply can be achieved.
According to this embodiment of the invention, the carrier gas should be selected to be nitrogen or an inert gas that does not react with hydrogen and the solid metal.
It is understood that the high-temperature hydrogen sensor and the sensing element of the temperature sensor according to the present invention are disposed inside the hydrogen evolution chamber, specifically, in the heating zone of the hydrogen evolution chamber.
The signal acquisition unit is respectively connected with the high-temperature hydrogen sensor and the temperature sensor and is used for acquiring the electric signal data of the high-temperature hydrogen sensor and the electric signal data of the temperature sensor.
According to the embodiment of the present invention, the specific type of the signal acquisition unit is not particularly limited as long as signal acquisition can be achieved, such as a commonly used signal acquisition instrument or a related signal acquisition sensor.
The temperature control unit is used for controlling the internal temperature of the hydrogen evolution chamber and comprises a heating element and a cooling element, the heating element can control the internal temperature rising process of the hydrogen evolution chamber so as to indirectly control the hydrogen evolution process in the solid metal sample, and the cooling element can be used for controlling the internal temperature lowering process of the hydrogen evolution chamber, so that the preparation for the next sample test after the test of one sample is finished is realized, and the test efficiency is improved.
According to this embodiment of the invention, the heating element may be a resistance wire, a heating carbon rod, a silicon-molybdenum rod, a microwave heating element, an infrared heating element, or the like, or other types of heating devices; the cooling element may be a fan, a chiller, or other cooling device. In this embodiment, the temperature control scheme is preferably a "proportional-integral-derivative" control scheme, which is conventional and not described in detail herein.
In this embodiment of the present invention, the specific type of the control processing system is not limited, and may be a PLC, an industrial control computer, a personal computer or an embedded processor, or other systems that can achieve the same function, and this embodiment is preferably a PLC control processing system.
More specifically, the control processing system comprises an electrical control unit, a signal acquisition unit and a processing unit. The electric control unit of the control processing system is respectively connected with the gas supply control unit and the temperature control unit, the signal acquisition unit is connected with the signal acquisition unit and used for controlling the relevant units and acquiring data, and the control processing system is specific: the on-off of a relevant electromagnetic valve in the gas supply control unit is controlled, the control of the gas flow rate and the flow passing through is realized, and the gas supply process is further controlled; through data detected by the temperature sensor, the electrical control unit accurately controls the temperature control unit to realize control of the temperature in the hydrogen evolution chamber; the signal acquisition unit is communicated with the signal acquisition unit through communication modes such as a serial port or a parallel port and the like so as to indirectly acquire the detection data of the digital high-temperature hydrogen sensor and the temperature sensor; the processing unit is respectively connected with the electric control unit and the signal acquisition unit, analyzes the acquired carrier gas flow speed and hydrogen concentration data, and calculates the hydrogen content in the solid metal, more specifically: according to the continuously acquired real-time hydrogen concentration C (t) in the hydrogen evolution chamber and the carrier gas flow velocity v, the hydrogen content in the solid metal is obtained by integration treatment in a certain hydrogen evolution time, and the method comprises the following steps: the time for starting hydrogen evolution is tStart ofAnd the hydrogen evolution ending time is tEnd upThe hydrogen content of the solid metal is then evolved during the hydrogen evolution processIs composed of
Fig. 2 is a schematic structural diagram of a hydrogen evolution chamber of the present invention, fig. 3 is a schematic layout diagram of a solid metal sample of the present invention, and as shown in fig. 2 and 3, the hydrogen evolution chamber 36 of the present invention mainly comprises the following parts: the device comprises a cylinder 1, a cylinder branch 103, a first cylinder end cover 2, a second cylinder end cover 3, a cylinder branch end cover 4, a sample pre-discharge area 101, a heating area 102, a cylinder sealing element I13, a cylinder sealing element II 14 and a cylinder branch sealing element 16. The cylinder branch 103 is vertically arranged on the cylinder 1 and is in an integral communication structure with the cylinder 1, the first cylinder end cover 2 and the second cylinder end cover 3 are arranged at two ends of the cylinder 1, the cylinder branch end cover 4 is arranged at the end part of the cylinder branch 103, the installation method is threaded installation, or other detachable installation modes, the shapes of the cylinder and the cylinder branch are not limited, the cylinder is preferably cylindrical, and the processing, the manufacturing and the heating area uniform heating are convenient. The inner space of the cylinder 1 is a heating area 102, and the inner space of the cylinder branch is a sample prearranged area 101. The first cylinder end cover 2, the second cylinder end cover 3 and the cylinder 1 are respectively provided with a first cylinder sealing element 13 and a second cylinder sealing element 14, and the cylinder branch sealing element 16 is provided between the cylinder branch end cover 4 and the cylinder branch 103, it can be understood that all sealing elements are used for preventing the gas leakage of the hydrogen evolution chamber, the specific type is not limited, and in this embodiment, a high-temperature resistant sealing ring or a sealing gasket is preferred.
With continued reference to fig. 2 and 3, the first cylinder end cap 2 is provided with a heating zone gas inlet 11, which is connected to a gas supply unit 100 for supplying a carrier gas for purging and hydrogen carrier gas to the hydrogen evolution chamber. The temperature sensor 5 and the high-temperature hydrogen sensor 6 are simultaneously installed and fixed on the first cylinder end cover 2, and the temperature sensor sensing element 18 and the high-temperature hydrogen sensor sensing element 19 are positioned in the heating zone 102 of the hydrogen evolution chamber and are respectively used for measuring the temperature of the heating zone and the hydrogen concentration in the hydrogen evolution chamber. And a heating zone gas outlet 12 is formed in the second cylinder end cover 3 and used for discharging gas in the hydrogen evolution chamber. A sample pre-discharge area gas inlet 15 and a sample push rod channel 17 are formed in the cylinder branch end cover 4, the sample pre-discharge area gas inlet 15 is connected with the gas supply unit 100 and provides carrier gas for purging for the sample pre-discharge area and the heating area, and the sample push rod channel 17 is used for enabling an operator to stretch a push rod 104 into the sample pre-discharge area 101 from the outside to the inside and push a solid metal sample to be detected from the sample pre-discharge area 101 to the heating area 102 to perform a subsequent heating hydrogen evolution process.
According to some embodiments of the present invention, the exterior of the sample push rod channel 17 is equipped with a pass-through valve that can be opened when pushing the sample, allowing the push rod 104 to push the solid metal sample 7 through the sample push rod channel 17.
The heating element 8 is arranged outside the cylinder 1 with the heating zone 102 and is used for heating the solid metal sample 7 in the heating zone 102, so that hydrogen in the sample is separated out at high temperature. The cooling element 9 is arranged near the heating element 8 and used for rapidly cooling the heating area after the sample test is finished, so that preparation is made for the next sample detection process, and the detection efficiency is improved.
Example 2: according to this embodiment of the present invention, there is provided a detection method using the apparatus for detecting hydrogen content in solid metal according to embodiment 1, wherein in the detection of hydrogen content, a solid metal sample 7 is first placed in the sample pre-discharge region 101 of the hydrogen evolution chamber, and the temperature and the hydrogen concentration in the hydrogen evolution chamber are detected by the temperature sensor 5 and the high-temperature hydrogen sensor 6. The carrier gas is supplied to the sample prevention region 101 and the heating region 102 of the hydrogen evolution chamber through the gas supply unit 100. The carrier gas is selected to be nitrogen or an inert gas that does not react with hydrogen and the solid metal. Before measuring hydrogen, air in the hydrogen evolution chamber needs to be exhausted, before introducing carrier gas, the hydrogen evolution chamber can be vacuumized by a vacuum pump 20 outside the hydrogen evolution chamber, and then carrier gas is introduced, so that the gas in the hydrogen evolution chamber can be quickly replaced.
In order to reduce the influence of the self factors of the detection device on the detection accuracy of the hydrogen content in the metal, at least one hydrogen content blank test (namely, a solid metal sample is not placed, and the detection device is used for detecting) is required before the hydrogen content detection is started, and then the subsequent hydrogen content detection in the solid metal is carried out, so that the accuracy of detection data is favorably improved.
FIG. 4 is a flow chart of the hydrogen content blank test detection of the present invention, as shown in the figure4, the blank test flow mainly comprises: performing gas replacement (specifically, the method comprises vacuumizing the hydrogen evolution chamber by a vacuum pump, introducing high-purity carrier gas, and replacing the original air in the hydrogen evolution chamber with high-purity carrier gas atmosphere); then, high-purity carrier gas is continuously introduced at a certain flow rate; heating the hydrogen evolution chamber to reach hydrogen evolution temperature, and measuring hydrogen concentration C in the hydrogen evolution chamber by a high-temperature hydrogen sensor0(t) continuous measurement, real-time Hydrogen concentration C0(t) in ppm, i.e. the volume of hydrogen in the gas in each 100 ten thousand ml hydrogen evolution chamber; after the high-temperature heating is carried out for a certain time, when the detected hydrogen concentration is zero and does not change any more, the control processing system calculates the hydrogen content according to the obtained carrier gas flow rate and the continuously collected hydrogen concentration data to obtain the hydrogen content q during blank test0In units of milliliters; and then, carrying out large-flow purging and cooling on the hydrogen evolution chamber by using carrier gas, simultaneously cooling the hydrogen evolution chamber from the outside by using a cooling element, and finishing the blank test process.
FIG. 5 is a flow chart of the hydrogen content detection of the solid metal according to the present invention, as shown in FIG. 5, the hydrogen content detection process of the solid metal mainly comprises the steps of preparing a solid metal sample to be detected, making the surface of the solid metal sample free of oil stain, water and other impurities, making the size of the strip metal sample be not more than 10mm, × 10mm, × 40mm, making the diameter of the strip metal sample be not more than 10mm, making the length of the strip metal sample be not more than 40mm, weighing the strip metal sample to obtain the mass m in grams, pre-placing the strip metal sample in a sample pre-prevention area of a hydrogen evolution chamber, performing gas replacement (specifically, a vacuum pump is used for vacuumizing the hydrogen evolution chamber, then introducing high purity carrier gas, replacing the original air in the hydrogen evolution chamber with high purity carrier gas atmosphere), then continuously introducing the high purity carrier gas at a certain flow rate, then pushing the strip metal sample from the sample prevention area to a heating area, and starting a signal acquisition unit and1(t) the data acquisition frequency is not less than 10 times/second, the continuously acquired data are sent to a control processing system, then a heating element is controlled to heat the hydrogen evolution chamber to reach the hydrogen evolution temperature, the hydrogen content is evolved into the hydrogen evolution chamber, and the real-time hydrogen concentration C is1(t) in ppm, i.e. per 100 ten thousand ml of gas in the hydrogen-evolving chamberThe volume of hydrogen gas; after all hydrogen in the solid metal is released after a certain time, the hydrogen concentration detected by the high-temperature hydrogen sensor is reduced to zero and does not change any more, and at the moment, the control processing system calculates the content of the hydrogen separated out in the test according to the flow rate of carrier gas obtained in the hydrogen separation process and the continuously obtained hydrogen concentration data to obtain the hydrogen content q1In units of ml, q1Subtracting q0The actual total hydrogen content q (q ═ q) in the solid sample was obtained1-q0) The unit is milliliter, and finally the hydrogen concentration in the metal to be measured is Q100Q/m, namely the hydrogen content in every 100 grams of solid metal is used as the judgment index of the hydrogen content in the solid metal; and after the test is finished, introducing carrier gas with a larger flow velocity to blow and cool the hydrogen evolution chamber, simultaneously cooling the hydrogen evolution chamber by using a cooling element outside the hydrogen evolution chamber, taking out the sample after the temperature is cooled to be below 100 ℃, and finishing the hydrogen measurement.
In this embodiment of the invention, the purity of the high purity carrier gas should be not less than 99.99% by volume.
FIG. 6 is a graph showing hydrogen concentration-time distribution of hydrogen content q (t) versus hydrogen concentration c in a hydrogen evolution chamber continuously obtained by a sensor during a blank test and a process of detecting hydrogen content in solid metal0And q is1The principle of calculation is shown in fig. 6, and includes: and respectively drawing continuous curves of the hydrogen content measured by the high-temperature hydrogen sensor in blank test and solid metal hydrogen content detection versus time, wherein the curves record the real-time hydrogen concentration C (t) in the hydrogen evolution chamber from the beginning of heating to the beginning of hydrogen evolution, to the end of hydrogen evolution and to the end of heating. Assuming that the flow speed of the flowing carrier gas passing through the hydrogen evolution chamber in the hydrogen evolution process is constant v and the unit is milliliter per second, the time for starting hydrogen evolution is tStart ofAnd the hydrogen evolution ending time is tEnd upThe content of hydrogen evolved in the overall process of hydrogen evolution isThat is, the area 22 of the geometric region defined by the hydrogen concentration-time curve 21 and the time axis isAnd v × 10-6The product of (a). The hydrogen content q in blank test can be respectively calculated by the method0And hydrogen content q in the solid metal hydrogen content test1The difference between the two is the actual hydrogen content in the metal, more specifically: when detecting the hydrogen content in the solid metal: according to the real-time hydrogen concentration C1(t) and the flow velocity v of the carrier gas1And performing integration treatment in the hydrogen evolution time to obtain the hydrogen content in the solid metal, wherein the integration treatment comprises the following steps: the time for starting hydrogen evolution is t1S, the time for ending hydrogen evolution is t2S, the hydrogen content q evolved in the course of hydrogen evolution1Is composed ofSimilarly, during blank test: according to the real-time hydrogen concentration C0(t) and the flow velocity v of the carrier gas0And performing integration treatment in the hydrogen evolution time to obtain the hydrogen content in the hydrogen evolution chamber, wherein the integration treatment comprises the following steps: the time for starting hydrogen evolution is t3S, the time for ending hydrogen evolution is t4S, the hydrogen content q evolved in the course of hydrogen evolution0Is composed ofNamely the hydrogen content in blank detection. Q is to be1Subtracting q0The actual total hydrogen content q (q ═ q) in the solid sample was obtained1-q0) In units of milliliters.
Example 3: according to the embodiment of the invention, the gas supply device for detecting the hydrogen content in the solid metal in the embodiments 1 and 2 is provided, the gas supply device provided by the embodiment can provide a carrier gas for detecting the hydrogen content of the solid metal sample, and can also provide a calibration gas containing hydrogen for calibrating the detection device, the gas supply process is matched with the test process, and the automation degree is high; the high-hydrogen concentration calibration gas or the low-hydrogen concentration calibration gas can be provided, the calibration requirements of different hydrogen concentrations are met, the calibration of the high-temperature hydrogen sensor is realized, the influence of the factors of the sensor on the detection accuracy of the metal hydrogen content is avoided, and the detection precision of data is improved; by selecting the large-flow gas flow controller and the small-flow gas flow controller, the requirements of different gas flows entering the hydrogen analysis chamber can be met, the gas flow control accuracy is improved, and the calibration process and the accuracy of the detection data of the solid metal hydrogen content are further improved.
Fig. 7 is a schematic structural diagram of a gas supply device according to the embodiment of the present invention, and as shown in fig. 7, the gas supply device provided by the present invention is a part of the device for detecting the hydrogen content in the solid metal according to embodiment 1, and is used for supplying gas to the hydrogen evolution chamber. The gas supply device of this embodiment mainly includes eight modules: the device comprises an air source module, a pressure reducing valve module, a gas electromagnetic valve module, a pressure display module, a gas purification module, a flow control module, a vacuumizing module and a control module.
In this embodiment, the gas source module includes a bottle of carrier gas source 231, a bottle of high hydrogen concentration calibration gas source 232, and a bottle of low hydrogen concentration calibration gas source 233, the carrier gas is a gas that does not react with the solid metal and hydrogen to be measured, preferably inert gas such as nitrogen or argon, and a bottle of hydrogen-containing calibration gas is a mixed gas with high hydrogen concentration, specifically: the hydrogen-inert gas mixture is preferably a hydrogen-argon mixture, such as a hydrogen-argon mixture with a volume fraction of 10%, and the other bottle of hydrogen-containing calibration gas is a mixture with a low hydrogen concentration, specifically: the hydrogen-inert gas mixture is preferably a hydrogen-argon mixture, for example a 0.1% hydrogen-argon mixture by volume fraction. It is understood that the gas source of the present invention is a gas storage container, and the specific type is not limited, and a vertical gas cylinder is preferred in this embodiment.
In this embodiment, the pressure reducing valve module includes three pressure reducing valves that cooperate with the air supply, specifically is: a first pressure reducing valve 241, a second pressure reducing valve 242, and a third pressure reducing valve 243 for controlling the output gas pressure of the gas source module.
In this embodiment, the gas solenoid valve module includes a carrier gas solenoid valve 251, a first hydrogen-containing calibration gas solenoid valve 252, a second hydrogen-containing calibration gas solenoid valve 253, a first gas solenoid valve 282, a second gas solenoid valve, and an outlet gas solenoid valve 35, and the second gas solenoid valve includes: a large flow rate gas solenoid valve 291 and a small flow rate gas solenoid valve 293 for controlling the gas flow or cut-off in the gas supply device.
In this embodiment, the pressure display module includes a first gas source pressure gauge 261, a second gas source pressure gauge 262 and a hydrogen evolution chamber pressure gauge 30, wherein the first gas source pressure gauge and the hydrogen evolution chamber pressure gauge are electronic pressure gauges capable of outputting pressure signals to the control module, and the second gas source pressure gauge is a dial display type pressure gauge capable of being directly observed.
In this embodiment, the gas purification module includes a water vapor removal unit 271 and a carbon dioxide removal unit 272, and it is understood that the water vapor removal unit and the carbon dioxide removal unit can remove water vapor and carbon dioxide, respectively, and the specific treatment measures are not particularly limited and are not specifically described in the conventional art.
In this embodiment, the flow control module includes a first gas flow controller 281 and a second gas flow controller, the first gas flow controller is configured to control a replacement purge rate of the carrier gas before hydrogen measurement and heating or the calibration gas containing hydrogen to air in the hydrogen evolution chamber, a purge rate of the carrier gas before hydrogen measurement and heating to the solid metal sample, and a cooling rate of the hydrogen evolution chamber after the sample test is finished, it is understood that the larger the flow rate is, the faster the corresponding purge speed is, and the faster the cooling speed of the hydrogen evolution chamber is; the second gas flow controller comprises: the large-flow gas flow controller 292 and the small-flow gas flow controller 294 are used for controlling the flow rate of carrier gas introduced into the hydrogen separation chamber in the hydrogen separation process during hydrogen measurement, or the flow rate of hydrogen-containing calibration gas introduced into the hydrogen separation chamber during calibration. According to the embodiment of the present invention, the specific type of the corresponding flow controller is not limited as long as the flow control function can be realized, and it can be understood that the large flow rate and the small flow rate of the present invention are relative, and the specific requirements are subject to actual requirements, for example: when the flow rate of the small flow is 0-200mL/min, the flow rate of the large flow exceeds 200 mL/min.
In this embodiment, the evacuation module is a vacuum pump 20.
With continued reference to fig. 7, the gas path connection mode of each module of the gas supply device is as follows: the carrier gas source 231, the high hydrogen concentration calibration gas source 232 and the low hydrogen concentration calibration gas source 233 are respectively connected with the gas inlet ends of the first pressure reducing valve 241, the second pressure reducing valve 242 and the third pressure reducing valve 243, the carrier gas electromagnetic valve 251, the first hydrogen-containing calibration gas electromagnetic valve 252 and the second hydrogen-containing calibration gas electromagnetic valve 253 are respectively connected with the gas outlet ends of the first pressure reducing valve 241, the second pressure reducing valve 242 and the third pressure reducing valve 243, and the three electromagnetic valve outlet gas circuits are simultaneously connected with the inlet of the water vapor removal unit 271, the first gas source pressure gauge 261 and the second gas source pressure gauge 262 after being combined. The outlet of the water vapor removal unit 271 is connected with the inlet of the carbon dioxide removal unit 272, and the outlet gas circuit of the carbon dioxide removal unit 272 is simultaneously connected with a first gas flow controller 281, a large flow gas solenoid valve 291 and a small flow gas solenoid valve 293. The gas outlet of the first gas flow controller 281 is connected with the gas inlet of the first gas solenoid valve 282, and the gas outlet of the first gas solenoid valve 282 is connected with the gas inlet 15 of the sample pre-discharge area of the hydrogen evolution chamber. The gas outlet of the large-flow gas electromagnetic valve 291 is connected with the gas inlet of the large-flow gas flow controller 292, and the gas outlet of the large-flow gas flow controller 292 is connected with the gas inlet 11 of the heating zone of the hydrogen evolution chamber. The outlet of the small flow gas solenoid valve 293 is connected with the inlet of the small flow gas flow controller 294, and the outlet of the small flow gas flow controller 294 is connected with the heating zone gas inlet 11 of the hydrogen evolution chamber. And a hydrogen evolution chamber pressure gauge 30 is arranged at a heating zone gas inlet 11 of the hydrogen evolution chamber 36 and is used for acquiring the gas pressure in the hydrogen evolution chamber. The gas outlet 12 of the heating zone of the hydrogen evolution chamber 36 is connected with the gas inlet of the gas outlet electromagnetic valve 35, and the gas outlet of the gas outlet electromagnetic valve 35 is connected with the vacuum pump 20.
Fig. 8 is a schematic block diagram of a control module in the gas supply device according to the embodiment of the present invention, and as shown in fig. 8, when the gas supply device in this embodiment is used in the detection device according to embodiment 1, the control module is connected to the control processing system of the detection device according to embodiment 1, it can be understood that the control module and the control processing system may also be combined to be a control processing unit for performing control in a unified manner.
The control module may be a PLC, an industrial control computer, a personal computer or an embedded processor, in this embodiment, an industrial control computer is preferred, and as shown in fig. 8, the control module includes: the device comprises a processor 31, a signal conversion module 32, a switching value input-output module 33 and an analog value input module 34. And when the air supply device works, each module is controlled by the processor. The processor 31 is connected with the switching value input/output module 33, the analog input module 34, the first gas flow controller 281, the large flow gas flow controller 292, and the small flow gas flow controller 294 through the signal conversion module 32, so as to control each solenoid valve of the gas solenoid valve module and the vacuum pump 20, and obtain pressure signal data returned by the first gas source pressure gauge 261 and the hydrogen evolution chamber pressure gauge 30.
It is to be understood that, in this embodiment of the present invention, the kinds of the signal conversion module, the switching value input/output module and the analog value input module are not particularly limited as long as the corresponding functions thereof can be achieved.
Example 4: according to this embodiment of the present invention, there is provided a gas supply method for detecting hydrogen content in solid metal by using the gas supply apparatus described in embodiment 3, specifically including: before the content of hydrogen in the solid metal is detected, the control module controls the switching value input and output module to close the first hydrogen-containing calibration gas electromagnetic valve 252 and the second hydrogen-containing calibration gas electromagnetic valve 253, open the carrier gas electromagnetic valve 251, adjust the first pressure reducing valve 241 and observe the second gas source pressure gauge 262 until the pressure reaches a value slightly larger than one atmosphere. After a solid metal sample is placed in a sample pre-discharge area 101 of a hydrogen evolution chamber, a first gas electromagnetic valve 282, a large-flow gas electromagnetic valve 291 and a small-flow gas electromagnetic valve 293 are closed, a gas outlet electromagnetic valve 35 is opened, a first gas flow controller 281 is set to reach a certain gas flow rate, a vacuum pump 20 is opened to vacuumize the hydrogen evolution chamber so that most of air is exhausted from the hydrogen evolution chamber, then the gas outlet electromagnetic valve 35 and the vacuum pump 20 are closed to enable the hydrogen evolution chamber to be in a certain vacuum state, then the first gas electromagnetic valve 282 is opened to enable carrier gas in a carrier gas source 231 to flow into the hydrogen evolution chamber through the first gas electromagnetic valve 282, the pressure of a pressure gauge 30 of the hydrogen evolution chamber is gradually increased in the flowing process, the gas outlet electromagnetic valve 35 is opened when the pressure is more than one atmosphere, the carrier gas is continuously blown out through the hydrogen evolution chamber to purge impurity gas adsorbed on the surface of, and the hydrogen evolution chamber is filled with a flowing carrier gas. After purging for a certain time, moving the solid metal sample from the sample pre-discharge area 101 of the hydrogen evolution chamber into the heating area 102 of the hydrogen evolution chamber, opening the large-flow gas electromagnetic valve 291 or the small-flow gas electromagnetic valve 293 according to the flow rate of the carrier gas required by the test, closing the first gas electromagnetic valve 282, and adjusting the large-flow gas flow controller 292 or the small-flow gas flow controller 294, so that the carrier gas reaches the proper flow rate in the hydrogen evolution chamber and flows at a certain flow rate in the hydrogen evolution chamber, and in the hydrogen evolution process, the carrier gas gradually separates the evolved hydrogen gas into the hydrogen chamber through the gas outlet electromagnetic valve 35. After all hydrogen in the metal sample is separated out, the large-flow gas electromagnetic valve 291 or the small-flow gas electromagnetic valve 293 is in a closed state, and then the first gas electromagnetic valve 282 is opened, so that the carrier gas can rapidly cool the inside of the hydrogen separation chamber, and the next sample test is prepared.
Example 5: according to this embodiment of the present invention, there is provided a gas supply method for calibrating a high-temperature hydrogen sensor by using the gas supply apparatus described in embodiment 3, including: before the calibration of the hydrogen content detection device is started, the control module controls the switching value input/output module to open the first hydrogen-containing calibration gas solenoid valve 252 or the second hydrogen-containing calibration gas solenoid valve 253, and close the carrier gas solenoid valve 251 (if the high hydrogen concentration calibration gas is required, the first hydrogen-containing calibration gas solenoid valve 252 is opened and the second hydrogen-containing calibration gas solenoid valve 253 is closed, and if the low hydrogen concentration calibration gas is required, the second hydrogen-containing calibration gas solenoid valve 253 is opened and the first hydrogen-containing calibration gas solenoid valve 252 is closed). The second pressure relief valve 242 or the third pressure relief valve 243 are adjusted accordingly while observing the pressure value indicated by the second air supply pressure gauge 262 until the pressure value is slightly greater than one atmosphere. Closing the first gas electromagnetic valve 282, the large-flow gas electromagnetic valve 291 and the small-flow gas electromagnetic valve 293, opening the gas outlet electromagnetic valve 35, setting a first gas flow controller 281 by the control module to reach a certain gas flow rate, opening the vacuum pump 20 to vacuumize the hydrogen evolution chamber to exhaust most of air from the hydrogen evolution chamber, then closing the gas outlet electromagnetic valve 35 and the vacuum pump 20 to enable the hydrogen evolution chamber to be in a certain vacuum state, then opening the first gas electromagnetic valve 282 to enable the hydrogen-containing calibration gas in the high-hydrogen-concentration calibration gas source 232 or the low-hydrogen-concentration calibration gas source 233 to flow into the hydrogen evolution chamber through the first gas electromagnetic valve 282, gradually increasing the pressure of the pressure gauge 30 of the hydrogen evolution chamber in the flowing process, opening the gas outlet electromagnetic valve 35 when the pressure is more than one atmosphere, continuously blowing and flowing the hydrogen-containing calibration gas out through the hydrogen evolution chamber, and filling the flowing hydrogen-containing calibration. After purging for a certain time, according to the flow rate of the hydrogen-containing calibration gas required during calibration, the large-flow gas electromagnetic valve 291 or the small-flow gas electromagnetic valve 293 is opened, the first gas electromagnetic valve 282 is closed, and the large-flow gas flow controller 292 or the small-flow gas flow controller 294 is adjusted to enable the hydrogen-containing calibration gas to reach a proper flow rate, so that the hydrogen-containing calibration gas flows in the hydrogen evolution chamber at a certain flow rate. When the temperature of the interior of the hydrogen evolution chamber rises to reach the testing temperature of the high-temperature hydrogen sensor 6, the high-temperature hydrogen sensor 6 detects the hydrogen concentration in the hydrogen evolution chamber, and the detection result is compared with the actual hydrogen concentration of the hydrogen-containing calibration gas to realize the calibration of the high-temperature hydrogen sensor 6.
It can be understood that, in this embodiment, the detection data of the detection device in embodiment 1 can be improved by calibrating the high-temperature hydrogen sensor before detecting the hydrogen content in the solid metal, so as to calibrate the hydrogen content data in the solid metal.
In conclusion, the high-temperature hydrogen sensor which can be directly used at high temperature is used as a hydrogen measuring element, so that the separation and detection of hydrogen in solid metal are synchronously carried out, and the detection of hydrogen content is not required after the separated hydrogen is collected, and the design scheme ensures that the device is more portable and simple; the structure form that the cylinder body is provided with the cylinder body branch is adopted, the sample pre-release area and the heating area are arranged for the hydrogen evolution chamber, the metal sample to be detected is temporarily placed in the sample pre-release area before heating and hydrogen evolution and is fully swept by carrier gas, and the interference of the adsorbed gas on the surface of the sample on the hydrogen content detection result can be greatly weakened; the cooling element can quickly cool the hydrogen evolution chamber, so that the sample analysis time is shortened, and the test efficiency is improved; by adding blank tests, the influence of the self factors of the detection device on the detection accuracy of the metal hydrogen content is reduced, and the detection precision of data is improved; the gas supply device can provide carrier gas for detecting the hydrogen content of the solid metal sample, and also can provide hydrogen-containing calibration gas for calibrating a high-temperature hydrogen sensor in the detection device, the gas supply process is matched with the test process, and the automation degree is high; the high-hydrogen concentration calibration gas or the low-hydrogen concentration calibration gas can be provided, the calibration requirements of different hydrogen concentrations are met, the calibration of the high-temperature hydrogen sensor is realized, the influence of the factors of the sensor on the detection accuracy of the metal hydrogen content is avoided, and the detection precision of data is improved; by selecting the large-flow controller and the small-flow controller, the requirements of different gas flows entering the hydrogen separation chamber can be met, the gas flow control accuracy is improved, and the calibration process and the detection accuracy of the solid metal hydrogen content are further improved.
In the present invention, unless otherwise expressly stated or limited, the terms "connected" and "connected" are to be construed broadly, e.g., as meaning either a fixed connection or a removable connection, or an integral part; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the description of the present invention, it is to be understood that the terms "first", "second", "third", and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, features defined as "first", "second", "third" may explicitly or implicitly include one or more of the features.
In the description herein, references to the description of "one embodiment," "some embodiments," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described, it is understood that the embodiments are illustrative and not restrictive, that various changes, modifications, substitutions and alterations may be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A gas supply device for detecting the hydrogen content in solid metal, characterized in that the gas supply device is used for connecting with a hydrogen evolution chamber for hydrogen evolution of solid metal, the gas supply device comprises:
the gas source module comprises a hydrogen-containing calibration gas source and a carrier gas source;
a gas solenoid valve module, the gas solenoid valve module comprising: the hydrogen-containing calibration gas source comprises a carrier gas electromagnetic valve, a hydrogen-containing calibration gas electromagnetic valve, a first gas electromagnetic valve, a second gas electromagnetic valve and a gas outlet electromagnetic valve, wherein the carrier gas electromagnetic valve is connected with the carrier gas source, and the hydrogen-containing calibration gas electromagnetic valve is connected with the hydrogen-containing calibration gas source;
the inlet of the gas purification module is respectively connected with the carrier gas electromagnetic valve and the hydrogen-containing calibration gas electromagnetic valve, the outlet of the gas purification module is connected with the inlet of the first gas electromagnetic valve through a first gas flow controller, the outlet of the first gas electromagnetic valve is connected with the gas inlet of the sample preamplification area of the hydrogen analysis chamber, the outlet of the gas purification module is connected with the inlet of a second gas flow controller through the second gas electromagnetic valve, and the outlet of the second gas flow controller is connected with the gas inlet of the heating area of the hydrogen analysis chamber;
the vacuumizing module is connected with a gas outlet of a heating area of the hydrogen separation chamber through the gas outlet electromagnetic valve;
and the control module is used for the integral operation of the gas supply device.
2. The gas supply apparatus according to claim 1, further comprising: and the carrier gas electromagnetic valve is connected with the carrier gas source through the pressure reducing valve module, and the hydrogen-containing calibration gas electromagnetic valve is connected with the hydrogen-containing calibration gas source through the pressure reducing valve module.
3. The gas supply apparatus according to claim 2, further comprising: a pressure display module, the pressure display module comprising: the gas source pressure gauge and the hydrogen evolution chamber pressure gauge are arranged at the inlet of the gas purification module, and the hydrogen evolution chamber pressure gauge is arranged at the gas inlet of the heating area of the hydrogen evolution chamber.
4. The gas supply apparatus according to claim 3, wherein the gas purification module comprises: the device comprises a water vapor removal unit and a carbon dioxide removal unit, wherein an inlet of the water vapor removal unit is respectively connected with the carrier gas electromagnetic valve and the hydrogen-containing calibration gas electromagnetic valve, an inlet of the carbon dioxide removal unit is connected with an outlet of the water vapor removal unit, and an outlet of the carbon dioxide removal unit is respectively connected with the first gas flow controller and the second gas electromagnetic valve.
5. The gas supply device according to claim 4, wherein a high-temperature hydrogen gas sensor for detecting a concentration of hydrogen evolved from the solid metal is provided in the heating zone.
6. The gas supply device according to claim 1, wherein the hydrogen-containing calibration gas source comprises: the volume fraction of the high hydrogen concentration calibration gas source is 10 percent, and the volume fraction of the low hydrogen concentration calibration gas source is 0.1 percent.
7. The gas supply device according to claim 6, wherein the carrier gas source stores a carrier gas comprising: the hydrogen-containing calibration gas stored in the hydrogen-containing calibration gas source is hydrogen-inert gas mixed gas.
8. The gas supply apparatus according to claim 1, wherein the control module is a PLC, an industrial control computer, or a personal computer.
9. A gas supply method for detecting the hydrogen content in solid metal by using the gas supply device according to claim 5, characterized by comprising the steps of:
s1: closing the hydrogen-containing calibration gas electromagnetic valve through the control module, opening the carrier gas electromagnetic valve, and adjusting the pressure reducing valve module to enable the pressure to be slightly greater than one atmosphere;
s2: putting a solid metal sample into a sample pre-discharge area of a hydrogen evolution chamber, closing a first gas electromagnetic valve and a second gas electromagnetic valve, simultaneously opening a gas outlet electromagnetic valve, setting a first gas flow controller to reach a certain gas flow rate, controlling a vacuumizing module to vacuumize the hydrogen evolution chamber, and closing the gas outlet electromagnetic valve and the vacuumizing module to enable the hydrogen evolution chamber to be in a vacuum state;
s3: opening a first gas electromagnetic valve to enable carrier gas in a carrier gas source to flow into a hydrogen evolution chamber through the first gas electromagnetic valve, and opening a gas outlet electromagnetic valve to enable the carrier gas to continuously purge and flow out a solid metal sample and the hydrogen evolution chamber when the pressure in the hydrogen evolution chamber is more than one atmosphere, so as to replace the hydrogen evolution chamber with a carrier gas atmosphere;
s4: moving the solid metal sample into a heating area of the hydrogen evolution chamber, opening a second gas electromagnetic valve, closing a first gas electromagnetic valve, adjusting a second gas flow controller to enable carrier gas to flow in the hydrogen evolution chamber, and enabling the carrier gas to gradually isolate the evolved hydrogen into the hydrogen chamber through an air outlet electromagnetic valve belt in the process of heating the solid metal sample to evolve the hydrogen;
s5: and after all hydrogen in the solid metal sample is separated out, closing the second gas electromagnetic valve, then opening the first gas electromagnetic valve, and continuously purging and cooling the inside of the hydrogen separation chamber by carrier gas.
10. A gas supply method for calibrating a high-temperature hydrogen sensor by using the gas supply device according to claim 5, comprising the steps of:
s1: the hydrogen-containing calibration gas electromagnetic valve is opened through the control module, the carrier gas electromagnetic valve is closed, and the pressure reducing valve module is adjusted to enable the pressure to be slightly larger than one atmosphere;
s2: closing the first gas electromagnetic valve and the second gas electromagnetic valve, simultaneously opening the gas outlet electromagnetic valve, setting the first gas flow controller to reach a certain gas flow rate, controlling the vacuumizing module to vacuumize the hydrogen evolution chamber, and closing the gas outlet electromagnetic valve and the vacuumizing module to enable the hydrogen evolution chamber to be in a vacuum state;
s3: opening a first gas electromagnetic valve to enable the hydrogen-containing calibration gas in the hydrogen-containing calibration gas source to flow into the hydrogen evolution chamber through the first gas electromagnetic valve, and opening a gas outlet electromagnetic valve to enable the hydrogen-containing calibration gas to continuously purge and flow out of the hydrogen evolution chamber when the pressure in the hydrogen evolution chamber is greater than one atmosphere, so that the hydrogen evolution chamber is replaced by the hydrogen-containing calibration gas atmosphere;
s4: and opening the second gas electromagnetic valve, closing the first gas electromagnetic valve, adjusting the second gas flow controller to enable the hydrogen-containing calibration gas to flow in the hydrogen evolution chamber, detecting the hydrogen concentration in the hydrogen evolution chamber by the high-temperature hydrogen sensor when the internal temperature of the hydrogen evolution chamber reaches the test temperature of the high-temperature hydrogen sensor, and comparing the detection result with the actual hydrogen concentration of the hydrogen-containing calibration gas to realize the calibration of the high-temperature hydrogen sensor.
CN202010672081.5A 2020-07-14 2020-07-14 Gas supply method and device for detecting hydrogen content in solid metal Pending CN111751246A (en)

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CN202010672081.5A CN111751246A (en) 2020-07-14 2020-07-14 Gas supply method and device for detecting hydrogen content in solid metal

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