CN111781088B - Method for detecting hydrogen content in solid metal - Google Patents
Method for detecting hydrogen content in solid metal Download PDFInfo
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Abstract
The invention relates to a method for detecting hydrogen content in solid metal, which mainly comprises the following steps: placing solid metal into a hydrogen evolution chamber; after vacuumizing the hydrogen evolution chamber, introducing carrier gas into the hydrogen evolution chamber to replace the hydrogen evolution chamber with carrier gas atmosphere, and then continuing introducing the carrier gas at a certain flow rate; heating the hydrogen separation chamber to separate out hydrogen from the solid metal, and continuously acquiring the real-time hydrogen concentration in the hydrogen separation chamber through a high-temperature hydrogen sensor in the hydrogen separation chamber; and integrating the hydrogen concentration in the hydrogen evolution time according to the real-time hydrogen concentration and the flow speed of the carrier gas to obtain the hydrogen content in the solid metal. The hydrogen content online detection is carried out while the solid metal sample is separated out, and hydrogen is not required to be collected secondarily.
Description
Technical Field
The invention relates to the technical field of material content detection, in particular to a method for detecting hydrogen content in solid metal, such as a method for detecting hydrogen content in steel blocks, aluminum blocks and metal welding joints.
Background
Hydrogen in metals such as steel, aluminum alloys, titanium alloys, and the like is generally considered a detrimental element. After steel smelting or hot working, residual hydrogen can influence the mechanical property and chemical property of materials, especially high-strength structural steel, hydrogen embrittlement generated by the residual hydrogen directly endangers the structural safety of components, and too high content of diffusion hydrogen in a steel welding joint can lead to hydrogen induced cracking of a container. The detection of the content of the diffused hydrogen can be used for classifying the grade of the welding material, and meanwhile, the dehydrogenation heat treatment process of the welding component with reasonable design can be referred to, so that the cracking in the use process of the pressure-bearing special equipment can be prevented. Therefore, the detection of the hydrogen content in the solid metal is of great importance to ensure the quality of the metal raw material and the stability of the hot working process.
The method for detecting the hydrogen content in the common solid metal mainly comprises a mercury method, a gas chromatography method and a carrier gas thermal extraction method. The first two methods are commonly used for detecting the content of the diffused hydrogen, and the mercury method is used for evaluating the content of the total diffused hydrogen by collecting the hydrogen separated from a welded joint immersed in mercury for a plurality of days. The gas chromatography is used for testing the content of hydrogen which is heated and separated out from the welding joint at a certain temperature by using the gas chromatograph, so that the result accuracy is high, the testing range is wide, but the testing time is long due to the fact that the temperature for extracting hydrogen is relatively low, and in addition, the hydrogen testing operation process is complex and the cost is relatively high. At present, a carrier gas thermal extraction method is adopted as a method for detecting the hydrogen content in solid metal, and a detector can test the content of diffusion hydrogen in a welded joint and also can test the total hydrogen content including molecular hydrogen and diffusion hydrogen in the metal by changing different hydrogen precipitation heating temperatures. The carrier gas thermal extraction method brings the separated hydrogen into the thermal conductivity cell or the infrared detection module for testing by inert gas, and can finish one sample test within tens of minutes due to the higher hydrogen extraction temperature, but the total efficiency is relatively low because about 1 hour is needed for the stability of the thermal conductivity cell before testing. In addition, because the price of the thermal conductivity detection pool and the infrared detection module is high, the hydrogen detection cost of the method is increased, and the structure of the hydrogen detection device is complex.
The hydrogen sensor prepared by taking the functional ceramic as a core element is a high-temperature sensor which has relatively rapid development in recent years, and the sensor is gradually applied to the detection of the hydrogen content in high-temperature media such as liquid metal, molten salt and the like. The high temperature at which the hydrogen gas is evolved from each material varies depending on the type of material. For the detection of hydrogen content in solid metal, if a high temperature hydrogen sensor is used, the hydrogen precipitated at high temperature (typically 300-500 ℃ or higher) can be directly detected without cooling and secondary collection of hydrogen. Compared with a thermal conductivity cell, a weather chromatograph and an infrared element detection module, the adoption of the high-temperature hydrogen sensor for detecting the hydrogen content in the solid metal is expected to enable the hydrogen measuring device to be smaller and portable, higher in hydrogen measuring efficiency and lower in relative cost. Therefore, the invention provides a novel detection method based on a high-temperature in-situ hydrogen detection technology, and the high-temperature hydrogen sensor is applied to the detection of the hydrogen content in solid metal, so that the method has innovation and important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for detecting the hydrogen content in solid metal, which adopts a high-temperature hydrogen sensor to be directly arranged in a hydrogen separation chamber, carries out on-line detection of the hydrogen content while separating out hydrogen from a solid metal sample, and does not need to collect hydrogen for the second time.
In order to solve at least one of the above technical problems, the technical scheme adopted by the invention is as follows:
the method for detecting the hydrogen content in the solid metal is characterized by comprising the following steps of:
s1: placing solid metal into a hydrogen evolution chamber;
s2: after vacuumizing the hydrogen evolution chamber, introducing carrier gas into the hydrogen evolution chamber to replace the hydrogen evolution chamber with carrier gas atmosphere, and then continuing introducing the carrier gas at a certain flow rate;
s3: heating the hydrogen separation chamber to separate out hydrogen from the solid metal, and continuously acquiring the real-time hydrogen concentration C in the hydrogen separation chamber through a high-temperature hydrogen sensor in the hydrogen separation chamber 1 (t)；
S4: according to the real-time hydrogen concentration C 1 (t) and flow velocity v of carrier gas 1 Integrating in hydrogen evolution time to obtain solid metalA hydrogen content of (a) comprising: the hydrogen evolution time is t 1 Ending hydrogen evolution time t 2 The hydrogen content q precipitated during the hydrogen evolution process 1 Is that
Further, in step S3: the frequency of acquiring data by the high-temperature hydrogen sensor is not lower than 10 times/s.
Further, the method further includes a blank detection step without placing solid metal before the step S1, including:
s01: after vacuumizing the hydrogen evolution chamber, introducing carrier gas into the hydrogen evolution chamber to replace the hydrogen evolution chamber with carrier gas atmosphere, and then continuing introducing the carrier gas at a certain flow rate;
s02: heating the hydrogen separation chamber to reach hydrogen separation temperature, and continuously acquiring real-time hydrogen concentration C in the hydrogen separation chamber through a high-temperature hydrogen sensor in the hydrogen separation chamber 0 (t)；
S03: according to the real-time hydrogen concentration C 0 (t) and flow velocity v of carrier gas 0 Integrating the hydrogen in the hydrogen separation time to obtain the hydrogen content in the hydrogen separation chamber, wherein the method comprises the following steps: the hydrogen evolution time is t 3 Ending hydrogen evolution time t 4 The hydrogen content q precipitated during the hydrogen evolution process 0 Is that
Namely the hydrogen content at blank detection.
Further, the method further comprises the step S5: hydrogen content q obtained by detecting solid metal hydrogen content 1 And hydrogen content q obtained by blank detection 0 And obtaining the actual hydrogen content in the solid metal by differencing.
Further, according to the actual hydrogen content in the solid metal and the mass of the solid metal, the hydrogen content in each 100g of the solid metal is obtained and is used as a judging index of the hydrogen content in the solid metal.
Further, after the detection is finished, carrier gas is introduced to sweep and cool the hydrogen evolution chamber, and meanwhile, the cooling element is used for cooling the hydrogen evolution chamber.
Further, the hydrogen separation chamber is provided with a heating zone for solid metal hydrogen separation and a sample pre-discharge zone for purging the solid metal before heating.
Further, the heating zone is provided with the high-temperature hydrogen sensor and the temperature sensor.
Further, a heating element and a cooling element are arranged outside the heating area, the heating element is used for heating the hydrogen separation chamber, so that the hydrogen content in the solid metal is separated out at high temperature, and the cooling element is used for quickly cooling the hydrogen separation chamber.
Further, the carrier gas includes nitrogen or an inert gas.
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 adopted as a hydrogen measuring element, so that the precipitation and detection of hydrogen in solid metal are synchronously carried out, the detection of the hydrogen content is not required to be carried out after the precipitated hydrogen is collected, and the device is more portable and simpler by adopting the design scheme;
(2) The structural form that the barrel body is provided with the barrel body branch is adopted, a sample pre-placing area and a heating area are arranged for the hydrogen evolution chamber, and a metal sample to be tested is temporarily placed in the sample pre-placing area and is fully purged by carrier gas before heating hydrogen evolution, so that the interference of adsorption gas on the surface of the sample on the hydrogen content detection result can be greatly reduced;
(3) The cooling element can rapidly cool the hydrogen separation chamber, so that the sample analysis time is shortened, and the test efficiency is improved;
(4) By adding the blank test, the influence of the self factors of the detection device on the metal hydrogen content detection accuracy is reduced, and the detection accuracy of the data is improved;
(5) The gas supply device can provide carrier gas for the detection of the hydrogen content of the solid metal sample, and can also provide hydrogen-containing calibration gas for the calibration of a high-temperature hydrogen sensor in the detection device, and the gas supply flow is matched with the test flow, so that 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 sensor factors on the metal hydrogen content detection accuracy is avoided, and the data detection accuracy 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 evolution chamber can be met, the accuracy of gas flow control is improved, and the accuracy of the calibration process and the solid metal hydrogen content detection data is further improved.
Drawings
FIG. 1 is a block diagram of a detecting device according to the present invention.
FIG. 2 is a schematic view of the hydrogen generating chamber structure of the present invention.
FIG. 3 is a schematic diagram of solid metal sample placement according to the present invention.
FIG. 4 is a flow chart of the blank test for hydrogen content in accordance with the present invention.
FIG. 5 is a flow chart of the solid metal hydrogen content detection of the present invention.
Fig. 6 is a graph of hydrogen concentration versus time.
Fig. 7 is a schematic view of a gas supply apparatus according to an embodiment of the present invention.
Fig. 8 is a control schematic block diagram of a control module in the air supply device according to an embodiment of the present invention.
In the above figures: 1-a cylinder; 2-a first barrel end cap; 3-a second barrel end cap; 4-a barrel 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-heating zone; 103-barrel branching; 104-pushing rod; 11-heating zone gas inlet; 12-heating zone gas outlet; 13-cartridge sealing element one; 14-a second cylinder sealing element; 15-sample pre-release zone gas inlet; 16-a barrel branch sealing element; 17-sample push rod channel; 18-a temperature sensor sensing element; 19-a high temperature hydrogen sensor sensing element; 20-a vacuum pump; 21-hydrogen concentration-time curve; 22-geometric area surrounded by curve and time coordinate axis; 231-a carrier gas source; 232-a high hydrogen concentration calibration gas source; 233-a low hydrogen concentration calibration gas source; 241-a first pressure relief valve; 242-a second pressure relief valve; 243-a third pressure relief valve; 251-a 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 air source pressure gauge; 262-a second air source pressure gauge; 271-a water vapor removal unit; 272-a carbon dioxide removal unit; 281-a first gas flow controller; 282-first gas solenoid valve; 291-high flow gas solenoid valve; 292-high flow gas flow controller; 293-a small flow gas solenoid valve; 294-low flow gas flow controller; 30-a hydrogen evolution chamber pressure gauge; 31-a processor; a 32-signal conversion module; 33-a switching value input/output module; 34-an analog input module; 35-an air outlet electromagnetic valve; 36-hydrogen evolution chamber.
Detailed Description
In order to enable those skilled in the art to better understand the technical scheme of the present invention, the present invention will be further described in detail with reference to specific embodiments. The following examples are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product.
Example 1: according to this 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 device according to the present invention, and as shown in fig. 1, the device mainly includes: the hydrogen generation device comprises a gas supply control unit, a gas supply unit, a hydrogen generation 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 is used for supplying carrier gas for carrying the hydrogen carrier in the process of purging and hydrogen evolution to the solid metal sample before heating to the hydrogen evolution chamber. The air supply control unit and the air supply unit form an air supply device together, the air supply control unit is connected with the air supply unit to realize the control of the air supply unit, and particularly, the air supply control unit is used for controlling the on-off of related valves in the air supply unit, setting the flow of the air flow control element and acquiring air pressure signals in the air supply unit.
In this embodiment of the present invention, the specific kind of the air supply device (air supply control unit and air supply unit) is not particularly limited as long as 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 will be appreciated that the sensing elements of the high temperature hydrogen sensor and the temperature sensor of the present invention are disposed within the hydrogen evolution chamber, and in particular within 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 electric signal data of the high-temperature hydrogen sensor and electric signal data of the temperature sensor.
The specific kind of the signal acquisition unit according to this embodiment of the present invention is not particularly limited as long as signal acquisition can be achieved, such as a usual signal acquisition instrument or a related signal acquisition sensor or the like.
The temperature control unit is used for controlling the internal temperature of the hydrogen evolution chamber and consists of 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, the cooling element can be used for controlling the internal temperature lowering process of the hydrogen evolution chamber, and preparation is made for the next sample test after the test of one sample is finished, so that 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 type of heating device; the cooling element may be a fan, chiller or other cooling device. In this embodiment, the temperature control scheme is preferably a "proportional-integral-derivative" control scheme, which is a conventional technique and will not be 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 system that can realize the same function, and the PLC control processing system is preferred.
More specifically, the control processing system includes an electrical control unit, a signal acquisition unit, and a processing unit. The control processing system is electrically connected with the control processing systemThe gas control unit is respectively connected with the gas supply control unit and the temperature control unit, and the signal acquisition unit is connected with the signal acquisition unit and is used for controlling the related units and acquiring data, and specifically: the on-off of the related electromagnetic valve in the air supply control unit is controlled, so that the control of the air flow speed and the through flow is realized, and the air supply process is further controlled; the electrical control unit precisely controls the temperature control unit to control the temperature in the hydrogen evolution chamber through the data detected by the temperature sensor; the signal acquisition unit is communicated with the signal acquisition unit in a serial port or parallel port communication mode to indirectly acquire detection data of the digitized high-temperature hydrogen sensor and the temperature sensor; the processing unit is respectively connected with the electrical 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, and more specifically: integrating the obtained real-time hydrogen concentration C (t) and carrier gas flow velocity v in the hydrogen separation chamber within a certain hydrogen separation time to obtain the hydrogen content in the solid metal, wherein the method comprises the following steps: the hydrogen evolution time is t Start to Ending hydrogen evolution time t Ending The content of hydrogen precipitated from the solid metal in the hydrogen evolution process is
Fig. 2 is a schematic view of the structure of the hydrogen separation chamber of the present invention, fig. 3 is a schematic view of the placement of the solid metal sample of the present invention, and as shown in fig. 2 and 3, the hydrogen separation chamber 36 of the present invention mainly comprises the following parts: barrel 1, barrel branch 103, first barrel end cap 2, second barrel end cap 3, barrel branch end cap 4, sample pre-placement zone 101, heating zone 102, barrel seal element one 13, barrel seal element two 14, barrel branch seal element 16. The cylinder branch 103 is vertically installed 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 installed at two ends of the cylinder 1, the cylinder branch end cover 4 is installed 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, and the embodiment of the invention is preferably cylindrical, so that the processing and the manufacturing are convenient, and the heating area is heated uniformly. The internal space of the cylinder 1 is a heating zone 102, and the internal space of the cylinder branch is a sample pre-placing zone 101. A first cylinder sealing element 13 and a second cylinder sealing element 14 are respectively arranged between the first cylinder end cover 2, the second cylinder end cover 3 and the cylinder 1, and a cylinder branch sealing element 16 is arranged between the cylinder branch end cover 4 and the cylinder branch 103, and it is understood that all sealing elements are used for preventing gas leakage of the hydrogen generating chamber, and the specific types are not limited, and in this embodiment, a high-temperature resistant sealing ring or a sealing gasket is preferable.
With continued reference to fig. 2 and 3, the first barrel end cap 2 is provided with a heating zone gas inlet 11 connected to the gas supply unit 100 for supplying a carrier gas for purging and a hydrogen carrier to the hydrogen evolution chamber. The temperature sensor 5 and the high-temperature hydrogen sensor 6 are simultaneously installed and fixed on the first barrel end cover 2, and the temperature sensor sensing element 18 and the high-temperature hydrogen sensor sensing element 19 are positioned in a 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. The second cylinder end cover 3 is provided with a heating zone gas outlet 12 for discharging gas in the hydrogen evolution chamber. The cylinder branch end cover 4 is provided with a sample pre-placing area gas inlet 15 and a sample push rod channel 17, the sample pre-placing area gas inlet 15 is connected with the gas supply unit 100, carrier gas for purging is provided for the sample pre-placing area and the heating area, the sample push rod channel 17 is used for an operator to extend a push rod 104 into the sample pre-placing area 101 from outside to inside, and the solid metal sample to be tested is pushed to the heating area 102 from the sample pre-placing area 101 for subsequent heating hydrogen evolution process.
According to some embodiments of the present invention, the sample pusher channel 17 is externally fitted with a pass-through valve that can be opened when pushing the sample, so that the pusher 104 pushes the solid metal sample 7 through the sample pusher channel 17.
The heating element 8 is arranged outside the cylinder 1 where the heating zone 102 is arranged, 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 is used for rapidly cooling the heating area after the sample test is finished, so as to prepare for the next sample detection process and improve the detection efficiency.
Example 2: according to this embodiment of the present invention, there is provided a method of detecting hydrogen content by using the solid metal hydrogen content detecting device described in the foregoing embodiment 1, wherein the solid metal sample 7 is first placed in the sample pre-placement area 101 of the hydrogen separation chamber, and the temperature and hydrogen concentration in the hydrogen separation chamber are detected by the temperature sensor 5 and the high-temperature hydrogen sensor 6. The sample preparation area 101 and the heating area 102 of the hydrogen evolution chamber are supplied with carrier gas by the gas supply unit 100. The carrier gas is selected from nitrogen or inert gases that do not react with the hydrogen and the solid metal. Before hydrogen measurement, air in the hydrogen evolution chamber needs to be exhausted, the hydrogen evolution chamber can be vacuumized by a vacuum pump 20 outside the hydrogen evolution chamber before carrier gas is introduced, and then the carrier gas is introduced, so that the rapid replacement of the gas in the hydrogen evolution chamber is achieved.
In order to reduce the influence of the self factors of the detection device on the accuracy of detecting the hydrogen content in the metal, at least one blank test of the hydrogen content is needed before the detection of the hydrogen content is started (i.e. a solid metal sample is not placed, the detection device is detected), and then the subsequent detection of the hydrogen content in the solid metal is carried out, so that the accuracy of detection data is improved.
FIG. 4 is a flow chart of the blank test for detecting the hydrogen content according to the present invention, as shown in FIG. 4, the blank test flow mainly comprises: performing gas replacement (specifically comprising the steps of vacuumizing a hydrogen evolution chamber through a vacuum pump, and then introducing high-purity carrier gas to replace original air in the hydrogen evolution chamber with high-purity carrier gas atmosphere); then continuously introducing high-purity carrier gas at a certain flow rate; the hydrogen separation chamber is then heated to a hydrogen separation temperature, and the hydrogen concentration C in the hydrogen separation chamber is measured by a high-temperature hydrogen sensor 0 (t) continuous measurement, real-time Hydrogen concentration C 0 (t) the unit is ppm, i.e., the volume of hydrogen in the gas per 100 kilomilliliters of hydrogen evolution chamber; when the detected hydrogen concentration is zero and is not changed after the high-temperature heating is carried out for a certain time, the control processing system calculates the hydrogen content according to the acquired carrier gas flow velocity and continuously acquired hydrogen concentration data to obtain the hydrogen content q in blank test 0 The unit is milliliter; and then carrying out high-flow purging and cooling on the hydrogen evolution chamber by using carrier gas, and simultaneously cooling the hydrogen evolution chamber from the outside by using a cooling element to finish the blank testing process.
FIG. 5 is a flow chart of the solid metal hydrogen content detection of the present invention, as shown in FIG. 5, the flow chart of the solid metal hydrogen content detection mainly comprises: preparing a solid metal sample to be detected, so that the surface of the solid metal sample is free of impurities such as greasy dirt, moisture and the like, the size of the solid metal sample is not more than 10mm multiplied by 40mm for a strip-shaped metal sample, the diameter of the solid metal sample is not more than 10mm, and the length of the solid metal sample is not more than 40mm for a cylindrical sample; weighing a sample to obtain the mass of the sample m in grams; pre-placing a sample into a sample pre-defense area of a hydrogen evolution chamber; performing gas replacement (specifically comprising the steps of vacuumizing a hydrogen evolution chamber by a vacuum pump, then introducing high-purity carrier gas, and replacing original air in the hydrogen evolution chamber with high-purity carrier gas atmosphere); then continuously introducing high-purity carrier gas at a certain flow rate; subsequently advancing the sample from the sample preparation zone to the heating zone; starting the signal acquisition unit and the high-temperature hydrogen sensor to continuously acquire the real-time hydrogen concentration C in the hydrogen evolution chamber 1 (t) the data acquisition frequency is not lower than 10 times/second, continuously acquired data are sent to a control processing system, then a heating element is controlled to heat a hydrogen separation chamber to reach the hydrogen separation temperature, the hydrogen content is separated into the hydrogen separation chamber, and the hydrogen concentration C is real-time 1 (t) the unit is ppm, i.e., the volume of hydrogen in the gas per 100 kilomilliliters of hydrogen evolution chamber; after a certain time, when the hydrogen in the solid metal is completely released, the hydrogen concentration detected by the high-temperature hydrogen sensor is reduced to zero and is not changed, and the control processing system calculates the hydrogen content separated out in the test according to the carrier gas flow rate obtained in the hydrogen separation process and continuously obtained hydrogen concentration data to obtain the hydrogen content q 1 In milliliters, q 1 Subtracting q 0 Obtaining the actual total hydrogen content q (q=q 1 -q 0 ) The unit is milliliter, and the hydrogen concentration in the metal to be detected is Q=100×q/m, namely, the hydrogen content in each 100g of solid metal is used as a judging index of the hydrogen content in the solid metal; and after the test is finished, introducing carrier gas with a large flow rate to sweep and cool the hydrogen evolution chamber, simultaneously, cooling the hydrogen evolution chamber by an external cooling element of the hydrogen evolution chamber, taking out a sample after the hydrogen evolution chamber is cooled to a temperature below 100 ℃, and ending hydrogen measurement.
In this example of the invention, the purity of the high purity carrier gas should be no less than 99.99% by volume.
FIG. 6 is a graph showing the concentration of hydrogen versus time, C (t) versus the hydrogen content q in a hydrogen separation chamber continuously obtained from a sensor during blank testing and hydrogen content detection in solid metal 0 And q 1 The principle of the calculation is shown in fig. 6, including: and respectively drawing continuous curves of the hydrogen content measured by the high-temperature hydrogen sensor during blank test and hydrogen content detection in solid metal with respect to 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 last of hydrogen evolution and the heating ending. Assuming that the flow velocity of carrier gas flowing through a hydrogen separation chamber in the hydrogen separation process is constant to v, the unit is milliliter/second, and the hydrogen separation starting time is t Start to Ending hydrogen evolution time t Ending The content of hydrogen precipitated in the total hydrogen evolution process is
Namely, the geometric area 22 surrounded by the hydrogen concentration-time curve 21 and the time coordinate axis is
And v×10 -6 Is a product of (a) and (b). The method can respectively calculate and obtain the hydrogen content q in blank test 0 And hydrogen content q at the time of solid metal hydrogen content test 1 The difference is the actual hydrogen content in the metal, more specifically: when the hydrogen content in the solid metal is detected: according to the real-time hydrogen concentration C 1 (t) and flow velocity v of carrier gas 1 Integrating the hydrogen in the hydrogen evolution time to obtain the hydrogen content in the solid metal, wherein the method comprises the following steps: the hydrogen evolution time is t 1 /s, ending hydrogen evolution time of t 2 /s, the hydrogen content q precipitated during hydrogen evolution 1 Is->
Similarly, in blank test: according to the real-time hydrogen concentration C 0 (t) and flow velocity v of carrier gas 0 Integrating the hydrogen in the hydrogen separation time to obtain the hydrogen content in the hydrogen separation chamber, wherein the method comprises the following steps: start hydrogen evolution timeAt t 3 /s, ending hydrogen evolution time of t 4 /s, the hydrogen content q precipitated during hydrogen evolution 0 Is that
Namely the hydrogen content at blank detection. Will q 1 Subtracting q 0 Obtaining the actual total hydrogen content q (q=q 1 -q 0 ) In milliliters.
Example 3: according to the embodiment of the invention, a gas supply device for detecting the hydrogen content in the solid metal in the foregoing embodiment 1 and embodiment 2 is provided, and the gas supply device provided in the embodiment not only can provide carrier gas for detecting the hydrogen content in the solid metal sample, but also can provide hydrogen-containing calibration gas for calibrating the detection device, and the gas supply flow is matched with the test flow, so that 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 sensor factors on the metal hydrogen content detection accuracy is avoided, and the data detection accuracy 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 evolution chamber can be met, the accuracy of gas flow control is improved, and the accuracy of the calibration process and the solid metal hydrogen content detection data is further improved.
Fig. 7 is a schematic diagram of the structure of a gas supply device according to the embodiment of the present invention, and as shown in fig. 7, the gas supply device according to the present invention is a part of the device for detecting hydrogen content in solid metal according to embodiment 1, and is used for supplying gas to a hydrogen separation chamber. The air supply device of this embodiment mainly includes eight modules: the device comprises an air source module, a pressure reducing valve module, a gas solenoid valve module, a pressure display module, a gas purifying 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 to be tested and hydrogen, preferably an inert gas such as nitrogen or argon, and the bottle of hydrogen-containing calibration gas is a high hydrogen concentration mixed gas, specifically: the hydrogen-inert gas mixture is preferably a hydrogen-argon mixture, such as a 10% hydrogen-argon mixture by volume, and the other bottle of hydrogen-containing calibration gas is a low hydrogen concentration mixture, specifically: the hydrogen-inert gas mixture is preferably a hydrogen-argon mixture, such as a hydrogen-argon mixture having a volume fraction of 0.1%. It will be appreciated that the gas source of the present invention is a gas storage container, and the specific type is not limited, and the vertical gas cylinder is preferred in this embodiment.
In this embodiment, the pressure reducing valve module includes three pressure reducing valves matched with the air source, specifically: the first, second and third pressure reducing valves 241, 242 and 243 are used to control 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, the second gas solenoid valve including: a large flow gas solenoid valve 291 and a small flow gas solenoid valve 293 for controlling the flow of gas in the gas supply device or shut off.
In this embodiment, the pressure display module includes a first air source pressure gauge 261, a second air source pressure gauge 262 and a hydrogen-generating chamber pressure gauge 30, where the first air source pressure gauge and the hydrogen-generating chamber pressure gauge are electronic pressure gauges, and can output pressure signals to the control module, and the second air source pressure gauge is a dial display pressure gauge, and can be directly observed.
In this embodiment, the gas cleaning module includes a water vapor removal unit 271 and a carbon dioxide removal unit 272, it being understood that the water vapor removal unit and the carbon dioxide removal unit can remove water vapor and carbon dioxide, respectively, and specific treatment measures are not particularly limited, and are conventional techniques, and are not specifically described herein.
In this embodiment, the flow control module includes a first gas flow controller 281 and a second gas flow controller, where the first gas flow controller is used to control the replacement purge rate of the carrier gas or the hydrogen-containing calibration gas to air before hydrogen measurement and heating in the hydrogen separation chamber, the purge rate of the carrier gas to the solid metal sample before hydrogen measurement and heating, and the cooling rate of the hydrogen separation chamber after the sample test is finished, it can be understood that the larger the flow is, the faster the corresponding purge rate is, and the faster the cooling rate of the hydrogen separation chamber is; the second gas flow controller includes: a large-flow gas flow controller 292 and a small-flow gas flow controller 294 for controlling the flow rate of carrier gas introduced into the hydrogen separation chamber during hydrogen measurement or the flow rate of hydrogen-containing calibration gas introduced into the hydrogen separation chamber during calibration. According to this 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 implemented, and it is understood that the large flow and the small flow of the present invention are relatively speaking, and the specific requirements are based on, for example: when the flow rate of the small flow rate is 0-200mL/min, the flow rate of the large flow rate exceeds 200mL/min.
In this embodiment, the evacuation module is a vacuum pump 20.
With continued reference to fig. 7, the air path connection manner of each module of the air supply device is specifically 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 air 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 air outlet ends of the first pressure reducing valve 241, the second pressure reducing valve 242 and the third pressure reducing valve 243, and the outlet air paths of the three electromagnetic valves are combined and then are simultaneously connected with the inlet of the water vapor removing unit 271, the first air source pressure gauge 261 and the second air source pressure gauge 262. The outlet of the water vapor removing unit 271 is connected with the inlet end of the carbon dioxide removing unit 272, and the outlet gas path of the carbon dioxide removing unit 272 is simultaneously connected with the first gas flow controller 281, the high-flow gas electromagnetic valve 291 and the low-flow gas electromagnetic 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 separation chamber. The outlet of the high-flow gas solenoid valve 291 is connected with the inlet of the high-flow gas flow controller 292, and the outlet of the high-flow gas flow controller 292 is connected with the heating zone gas inlet 11 of the hydrogen separation chamber. The gas outlet of the small-flow gas solenoid valve 293 is connected with the gas inlet of the small-flow gas flow controller 294, and the gas outlet of the small-flow gas flow controller 294 is connected with the gas inlet 11 of the heating zone of the hydrogen evolution chamber. A hydrogen-separating chamber pressure gauge 30 is provided at the heating-zone gas inlet 11 of the hydrogen separating chamber 36 for acquiring the gas pressure in the hydrogen separating chamber. The heating zone gas outlet 12 of the hydrogen separation 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 control schematic block diagram of a control module in the air supply device according to the embodiment of the present invention, and as shown in fig. 8, when the air supply device according to the embodiment is used in the detection device according to the embodiment 1, the control module is connected to the control processing system of the detection device according to the embodiment 1, and it is understood that the control module and the control processing system may be combined and configured as a control processing unit to perform control in a unified manner.
The control module may be a PLC, an industrial control computer, a personal computer or an embedded processor, in which case an industrial control computer is preferred, as shown in fig. 8, and comprises: a processor 31, a signal conversion module 32, a switching value input/output module 33 and an analog value input module 34. And each module is controlled by the processor when the air supply device works. The processor 31 is connected with the switching value input/output module 33, the analog value 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 acquire pressure signal data transmitted back by the first gas source pressure gauge 261 and the hydrogen-extracting 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 realized.
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 device described in the foregoing embodiment 3, specifically including: before starting to detect the hydrogen content in the solid metal, the control module controls the on-off value input/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 slightly more than one atmosphere. After the solid metal sample is placed in the sample pre-placing area 101 of the hydrogen separation chamber, the first gas solenoid valve 282, the large-flow gas solenoid valve 291 and the small-flow gas solenoid valve 293 are closed, the gas outlet solenoid valve 35 is opened, the first gas flow controller 281 is set to reach a certain gas flow rate, the vacuum pump 20 is opened to vacuumize the hydrogen separation chamber, most of air is discharged from the hydrogen separation chamber, then the gas outlet solenoid valve 35 and the vacuum pump 20 are closed, the hydrogen separation chamber is in a certain vacuum state, then the first gas solenoid valve 282 is opened, the carrier gas in the carrier gas source 231 flows into the hydrogen separation chamber through the first gas solenoid valve 282, the pressure of the hydrogen separation chamber pressure gauge 30 gradually increases in the flowing process, the gas outlet solenoid valve 35 is opened when the pressure is larger than one atmosphere, the carrier gas continuously flows out through the hydrogen separation chamber in a purging mode, the impurity gas adsorbed on the surface of the solid metal sample is purged, and the hydrogen separation chamber is filled with flowing carrier gas. After purging for a certain time, after the solid metal sample is moved from the sample pre-discharge area 101 of the hydrogen separation chamber into the heating area 102 of the hydrogen separation chamber, the high-flow gas electromagnetic valve 291 or the low-flow gas electromagnetic valve 293 is opened according to the carrier gas flow rate required by the test, the first gas electromagnetic valve 282 is closed, and the high-flow gas flow controller 292 or the low-flow gas flow controller 294 is regulated, so that the carrier gas reaches a proper flow rate in the hydrogen separation chamber, flows in the hydrogen separation chamber at a certain flow rate, and the carrier gas gradually separates out hydrogen from the hydrogen separation chamber through the gas outlet electromagnetic valve 35 in the hydrogen separation process. After all hydrogen in the metal sample is separated out, the high-flow gas electromagnetic valve 291 or the low-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 preparation is made for the next sample test.
Example 5: according to this embodiment of the present invention, there is provided a gas supply method for performing high-temperature hydrogen sensor calibration using the gas supply device described in the foregoing embodiment 3, specifically including: before starting to calibrate the hydrogen content detection device, the control module controls the on-off 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 (open the first hydrogen-containing calibration gas solenoid valve 252 and close the second hydrogen-containing calibration gas solenoid valve 253 if a high hydrogen concentration calibration gas is required, and open the second hydrogen-containing calibration gas solenoid valve 253 and close the first hydrogen-containing calibration gas solenoid valve 252 if a low hydrogen concentration calibration gas is required). The second pressure relief valve 242 or the third pressure relief valve 243 is adjusted accordingly while observing the pressure value displayed by the second air source pressure gauge 262 until the pressure value is slightly greater than one atmosphere. Closing a first gas solenoid valve 282, a large-flow gas solenoid valve 291 and a small-flow gas solenoid valve 293, opening an air outlet solenoid valve 35, setting a first gas flow controller 281 by a control module to achieve a certain gas flow rate, opening a vacuum pump 20 to vacuumize a hydrogen separation chamber so as to drain most of air from the hydrogen separation chamber, closing the air outlet solenoid valve 35 and the vacuum pump 20 to enable the hydrogen separation chamber to be in a certain vacuum state, then opening the first gas solenoid valve 282 to enable hydrogen-containing calibration gas in a high-hydrogen concentration calibration gas source 232 or a low-hydrogen concentration calibration gas source 233 to flow into the hydrogen separation chamber through the first gas solenoid valve 282, gradually increasing the pressure of a pressure gauge 30 of the hydrogen separation chamber in the flowing process, opening the air outlet solenoid valve 35 when the pressure is larger than one atmosphere, continuously blowing and flowing the hydrogen-containing calibration gas through the hydrogen separation chamber, and filling the hydrogen separation chamber with the flowing hydrogen-containing calibration gas. After purging for a certain time, the high-flow gas solenoid valve 291 or the low-flow gas solenoid valve 293 is opened according to the flow rate of the hydrogen-containing calibration gas required during calibration, the first gas solenoid valve 282 is closed, and the high-flow gas flow controller 292 or the low-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-separating chamber at a certain flow rate. When the temperature in the hydrogen separation chamber rises to reach the test temperature of the high-temperature hydrogen sensor 6, the high-temperature hydrogen sensor 6 detects the hydrogen concentration in the hydrogen separation 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 calibration of the high-temperature hydrogen sensor is performed before the detection of the hydrogen content in the solid metal, so that the detection data of the detection device in embodiment 1 can be improved, and the calibration of the hydrogen content data in the solid metal is further realized.
In summary, the high-temperature hydrogen sensor which can be directly used at high temperature is adopted as the hydrogen measuring element, so that the precipitation and detection of hydrogen in solid metal are synchronously carried out, the detection of the hydrogen content is carried out after the precipitated hydrogen is not required to be collected, and the device is more portable and simpler by adopting the design scheme; the structural form that the barrel body is provided with the barrel body branch is adopted, a sample pre-placing area and a heating area are arranged for the hydrogen evolution chamber, and a metal sample to be tested is temporarily placed in the sample pre-placing area and is fully purged by carrier gas before heating hydrogen evolution, so that the interference of adsorption gas on the surface of the sample on the hydrogen content detection result can be greatly reduced; the cooling element can rapidly cool the hydrogen separation chamber, so that the sample analysis time is shortened, and the test efficiency is improved; by adding the blank test, the influence of the self factors of the detection device on the metal hydrogen content detection accuracy is reduced, and the detection accuracy of the data is improved; the gas supply device can provide carrier gas for the detection of the hydrogen content of the solid metal sample, and can also provide hydrogen-containing calibration gas for the calibration of a high-temperature hydrogen sensor in the detection device, and the gas supply flow is matched with the test flow, so that 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 sensor factors on the metal hydrogen content detection accuracy is avoided, and the data detection accuracy 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 solid metal hydrogen content detection accuracy are further improved.
In the present invention, unless explicitly specified and limited otherwise, the terms "connected," "connected," and the like are to be construed broadly, and may be fixedly connected, detachably connected, or integrally formed, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the description of the present invention, it should 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 as implicitly indicating the number of technical features indicated. Thus, a feature defining "a first", "a second", or a third "may explicitly or implicitly include one or more such feature.
In the description of the present specification, reference to the term "one embodiment," "some embodiments," etc., means 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, schematic representations of the above terms are not necessarily directed 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, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it should be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by those of ordinary skill in the art within the scope of the invention, as well as variations in the detailed description and application of the invention, as would be apparent to those of ordinary skill in the art in light of the teachings of this application.
Claims (7)
1. The method for detecting the hydrogen content in the solid metal is characterized by comprising the following steps of:
s1: placing solid metal into a hydrogen evolution chamber;
s2: after vacuumizing the hydrogen evolution chamber, introducing carrier gas into the hydrogen evolution chamber to replace the hydrogen evolution chamber with carrier gas atmosphere, and then continuing introducing the carrier gas at a certain flow rate;
s3: heating the hydrogen separation chamber to separate out hydrogen from the solid metal, and continuously acquiring the real-time hydrogen concentration C in the hydrogen separation chamber through a high-temperature hydrogen sensor in the hydrogen separation chamber 1 (t)；
S4: according to the real-time hydrogen concentration C 1 (t) and flow velocity v of carrier gas 1 Integrating the hydrogen in the hydrogen evolution time to obtain the hydrogen content in the solid metal, wherein the method comprises the following steps: the hydrogen evolution time is t 1 Ending hydrogen evolution time t 2 The hydrogen content q precipitated during the hydrogen evolution process 1 Is that
The method further comprises a blank detection step without placing solid metal before the step S1, and the blank detection step comprises the following steps:
s01: after vacuumizing the hydrogen evolution chamber, introducing carrier gas into the hydrogen evolution chamber to replace the hydrogen evolution chamber with carrier gas atmosphere, and then continuing introducing the carrier gas at a certain flow rate;
s02: heating the hydrogen separation chamber to reach hydrogen separation temperature, and continuously acquiring real-time hydrogen concentration C in the hydrogen separation chamber through a high-temperature hydrogen sensor in the hydrogen separation chamber 0 (t)；
S03: according to the real-time hydrogen concentration C 0 (t) and flow velocity v of carrier gas 0 Integrating the hydrogen in the hydrogen separation time to obtain the hydrogen content in the hydrogen separation chamber, wherein the method comprises the following steps: the hydrogen evolution time is t 3 Ending hydrogen evolution time t 4 The hydrogen content q precipitated during the hydrogen evolution process 0 Is that
Namely the hydrogen content in blank detection;
further comprising step S5: hydrogen content q obtained by detecting solid metal hydrogen content 1 And hydrogen content q obtained by blank detection 0 Obtaining the actual hydrogen content in the solid metal by taking the difference; obtaining the hydrogen content in each 100g of solid metal as the actual hydrogen content in the solid metal and the mass of the solid metalAnd determining the hydrogen content in the solid metal.
2. The method for detecting hydrogen content in solid metal according to claim 1, wherein in step S3: the frequency of acquiring data by the high-temperature hydrogen sensor is not lower than 10 times/s.
3. The method for detecting the hydrogen content in the solid metal according to claim 1, wherein after the detection is finished, a carrier gas is introduced to purge and cool the hydrogen evolution chamber, and the cooling element is used for cooling the hydrogen evolution chamber.
4. A method for detecting hydrogen content in solid metal according to claim 3, wherein the hydrogen separation chamber is provided with a heating zone for solid metal hydrogen separation and a sample pre-discharge zone for purging the solid metal before heating.
5. The method for detecting hydrogen content in solid metal according to claim 4, wherein the high-temperature hydrogen sensor and the temperature sensor are provided in the heating area.
6. The method according to claim 4, wherein a heating element for heating the hydrogen evolution chamber to precipitate hydrogen content in the solid metal at a high temperature and a cooling element for rapidly cooling the hydrogen evolution chamber are provided outside the heating zone.
7. A method for detecting hydrogen content in solid metal according to claim 3, wherein the carrier gas comprises nitrogen or an inert gas.
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