CN107589217B - Hydrogen sensor with alloy protective structure - Google Patents
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- CN107589217B CN107589217B CN201710721497.XA CN201710721497A CN107589217B CN 107589217 B CN107589217 B CN 107589217B CN 201710721497 A CN201710721497 A CN 201710721497A CN 107589217 B CN107589217 B CN 107589217B
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Abstract
The invention relates to a hydrogen sensor with an alloy protection structure, and belongs to the technical field of gas concentration measurement. The hydrogen sensor comprises a catalytic reactor, a protective filtering device, a reaction temperature sensitive element, an environment temperature sensitive element, a positioning rod, an installation rod, a supporting plate, a protective outer cylinder, an upper pattern plate and a lower pattern plate; still include upper flower plate protective structure, lower flower plate protective structure, calibration gas air inlet sealing member and calibration gas outlet sealing member. The surface of an upper pattern plate and a lower pattern plate in the hydrogen sensor are provided with alloy film materials with melting points of 70-120 ℃ as upper and lower pattern plate protection structures, the alloy film materials can quickly sense the environmental temperature change after an accident and are quickly melted to expose through holes on the surface of the upper and lower pattern plates, a natural diffusion environment is formed inside the hydrogen sensor, and a hydrogen sensitive component is protected from the influence of gas flow field change.
Description
Technical Field
The invention relates to a hydrogen sensor with an alloy protection structure, which is mainly used for measuring the concentration of hydrogen in a containment after a serious accident of a nuclear power station and belongs to the technical field of gas concentration measurement.
Background
When a nuclear power station generates a loss of coolant accident, the zirconium alloy cladding of the fuel rod reacts with water at a high temperature to generate a large amount of hydrogen, so that the concentration level of the hydrogen in the containment vessel is increased, the average concentration of the hydrogen in the limited containment vessel space can reach the explosion limit, and the structural integrity of the containment vessel is seriously threatened. Therefore, it is necessary to provide a reliable hydrogen monitoring device to evaluate the accident status and provide a decision basis for accident management.
At present, a device for measuring the concentration of hydrogen in a serious accident in a containment comprises two modes of in-situ measurement and extraction measurement; among them, in-situ measurement is the mainstream of technical development. The in-situ measurement mode is that the hydrogen sensor is directly arranged in the containment vessel for standby, the main technical principles at present comprise a thermal conduction principle, an electrochemical principle and a catalytic hydrogen sensor, the catalytic hydrogen sensor can be used for realizing passive starting, and the in-situ measurement mode has the characteristics of good anti-seismic performance, good stability and the like, so that the in-situ measurement mode has great technical advantages.
In the initial construction stage and the overhaul period of the conventional nuclear power station, a large amount of volatile organic compounds and dust are generated in the construction and overhaul process, so that the atmosphere composition in a containment vessel is complex, and the dust and organic volatile substances can enter a hydrogen sensor through free diffusion, so that the hydrogen sensor fails. At present, the catalytic hydrogen sensor adopts a protection scheme that a powder metallurgy cover is used, or a protection filtering device is formed by inorganic materials with high adsorption capacity. However, during the construction or overhaul of the nuclear power plant, toxic atmosphere or dust may adhere to the surface of the protective filter, in extreme cases may enter the hydrogen sensor core component and poison the hydrogen sensitive material, resulting in a reduction in the start-up speed of the hydrogen sensor and even a failure of the hydrogen sensor.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a hydrogen sensor with an alloy protection structure, wherein an alloy film material is used as the protection structure of an upper pattern plate and a lower pattern plate of the hydrogen sensor; the reliable opening under the accident state is ensured by controlling the thickness and the size of the alloy film material, and the selected alloy film material does not generate chemical reaction with water vapor, so that the explosion risk of the combustible gas of the containment vessel cannot be increased. In a non-accident state, the protection structure can isolate the hydrogen sensor from contacting the environment when the hydrogen sensor is in a standby state; when a serious accident occurs, the protective structure can sense the change of the environmental temperature and can be quickly opened, so that the hydrogen sensor can be quickly put into operation, and the service life and the reliability of the hydrogen sensor are improved.
The purpose of the invention is realized by the following technical scheme.
The utility model provides a hydrogen sensor with alloy protective structure, hydrogen sensor includes catalytic reactor, protection filter equipment, reaction temperature sensing element, ambient temperature sensing element, locating lever, installation pole, layer board, protection urceolus, goes up card, lower card, its characterized in that: the device also comprises an upper pattern plate protection structure, a lower pattern plate protection structure, a calibration gas inlet sealing element and a calibration gas outlet sealing element.
Wherein, catalytic reactor is the cylinder structure of one end open-ended, and the open end has the external screw thread.
The protective filtering device is of a cylindrical structure with an opening at one end, the opening end is provided with internal threads, the inner diameter of the opening end is matched with the outer diameter of the opening end of the catalytic reactor, the side wall of the protective filtering device is of a double-layer structure which is formed by an inner side wall and an outer side wall and has a gap in the middle, and the inner diameter of the inner side wall is larger than the outer diameter of the catalytic reactor.
The supporting plate is a circular plate, and the diameter of the supporting plate is larger than the outer diameter of the outer side wall of the protective filtering device.
The protective outer cylinder is of a cylinder structure with openings at two ends; a calibration gas inlet through hole is formed in one side wall of the protection outer barrel close to the bottom, a calibration gas inlet sealing element is used for sealing, a calibration gas outlet through hole is formed in the other side wall of the protection outer barrel close to the top, and a calibration gas outlet sealing element is used for sealing.
The diameter of the upper flower plate is the same as the outer diameter of the protective outer cylinder, the diameter of the lower flower plate is the same as the inner diameter of the protective outer cylinder, and through holes which are uniformly distributed are formed in the upper flower plate and the lower flower plate and used for gas diffusion.
The upper flower plate protection structure and the lower flower plate protection structure are respectively disc-shaped alloy film materials, and the alloy film materials do not react with water vapor and have a melting point of 70-120 ℃.
The connection relation of each component in the hydrogen sensor is as follows:
the upper pattern plate is positioned above the protective outer cylinder, the lower surface of the upper pattern plate is fixedly connected with the top end of the cylinder wall of the protective outer cylinder, an upper pattern plate protective structure is laminated on the whole upper surface or the lower surface of the upper pattern plate, the lower pattern plate is positioned on the inner side of the bottom of the protective outer cylinder and is fixedly connected with the inner side of the cylinder wall of the protective outer cylinder, and a lower pattern plate protective structure is laminated on the whole upper surface or the lower surface of the lower pattern plate; the calibration gas inlet sealing element and the calibration gas outlet sealing element are respectively arranged in the calibration gas inlet through hole and the calibration gas outlet through hole on the protective outer cylinder.
The catalytic reactor is sleeved in the protective filtering device, the open end of the catalytic reactor and the open end of the protective filtering device are upward and are connected through threads, a gap is reserved between the bottom of the catalytic reactor and the bottom of the protective filtering device, a gap is reserved between the inner side wall of the protective filtering device and the side wall of the catalytic reactor, and the catalytic reactor and the protective filtering device form a hydrogen sensitive component; the supporting plate is positioned below the hydrogen sensitive component and is fixedly connected with the bottom of the protective filtering device; the hydrogen sensitive component is fixed in the protective outer cylinder through the mounting rod, the top end of the mounting rod is fixedly connected with the upper pattern plate, the bottom end of the mounting rod is fixedly connected with the supporting plate, and more than two mounting rods are uniformly distributed on the outer side of the hydrogen sensitive component; the environment temperature sensitive element penetrates through the upper pattern plate and extends into the protective outer cylinder, a gap is reserved between the bottom end of the environment temperature sensitive element and the bottom of the protective outer cylinder, and the upper end of the environment temperature sensitive element is positioned outside the protective outer cylinder and fixedly connected with the upper pattern plate through a clamping sleeve; the upper end of the positioning rod is fixedly connected with the upper card, the lower end of the positioning rod is opposite to the opening center of the catalytic reactor, the reaction temperature sensitive element penetrates through the upper card and extends into the protective outer cylinder, the positioning rod is used for positioning, the lower end of the positioning rod extends into the catalytic reactor, a gap is reserved between the lower end of the positioning rod and the bottom of the catalytic reactor, and the upper end of the positioning rod is located outside the protective outer cylinder and is fixedly connected with the upper card through a clamping sleeve.
Preferably, the hydrogen sensor further comprises an ear type support, a vertical welding support and a shower prevention cover, wherein one end of the ear type support is fixedly connected with the protection outer cylinder, the other end of the ear type support is fixedly connected with the vertical welding support to form a group of support structures, and more than two groups of support structures are uniformly distributed on the outer side of the protection outer cylinder; the diameter of the anti-drenching cover is larger than that of the upper pattern plate and is fixedly connected with the protective outer cylinder.
Preferably, the catalytic reactor has an outer diameter of 10mm to 50mm, a thickness of 0.5mm to 2mm and a height of 40mm to 90 mm; the internal diameter of the opening of the catalytic reactor is 1 mm-8 mm.
Preferably, the height of the protective filtering device is 80-120 mm, the outer diameter of the outer side wall is 60-100 mm, the total thickness of the outer side wall, the inner side wall and the gap between the outer side wall and the inner side wall is 5-20 mm, and the gap between the outer side wall and the inner side wall is 3-8 mm.
Preferably, the reaction temperature sensitive element is a thermocouple or a platinum resistance temperature measuring element, the diameter is 2 mm-6 mm, and the depth of the reaction temperature sensitive element extending into the protective outer cylinder is 160 mm-200 mm; for measuring the reaction temperature of the oxyhydrogen reaction.
Preferably, the environment temperature sensitive element is a thermocouple or a platinum resistance temperature measuring element, the diameter is 2 mm-6 mm, and the depth of the environment temperature sensitive element extending into the protective outer cylinder is 260 mm-320 mm; the method is used for measuring the ambient temperature in the containment vessel of the nuclear power plant.
Preferably, the diameter of the positioning rod is 6 mm-8 mm, the thickness is 1 mm-2 mm, and the length is 110 mm-130 mm.
Preferably, the mounting rod has a diameter of 4mm to 8mm and a length of 250mm to 280 mm.
The diameter of the supporting plate is preferably 100 mm-150 mm, and the thickness of the supporting plate is preferably 3 mm-8 mm.
Preferably, the outer diameter of the protective outer cylinder is 160 mm-200 mm, and the thickness is 2 mm-5 mm; the height is 300 mm-500 mm.
The diameter of the upper flower plate is preferably 160 mm-200 mm, the thickness is 3 mm-6 mm, and the diameter of the upper through hole is preferably 4 mm-8 mm.
Preferably, the diameter of the lower pattern plate is 160 mm-190 mm, the thickness is 2 mm-5 mm, and the diameter of the upper through hole is 4 mm-8 mm.
The thickness of the upper flower plate protection structure is preferably 0.1 mm-1 mm, and the used material is an alloy material consisting of more than one element of bismuth, tin, lead, cadmium and indium.
The thickness of the lower flower plate protective structure is preferably 0.1 mm-1 mm, and the used material is an alloy material consisting of more than one element of bismuth, tin, lead, cadmium and indium.
The catalytic reactor is filled with a catalyst which can enable hydrogen and oxygen to react at normal temperature.
The filler is arranged between the inner layer side wall and the outer layer side wall of the protective and protective filtering device and is spherical A12O3And/or spherical SiO2。
Preferably, all parts of the hydrogen sensor except the reaction temperature sensitive element, the environment temperature sensitive element, the upper flower plate protection structure and the lower flower plate protection structure are made of stainless steel or metal oxide; wherein, the catalytic reactor adopts a stainless steel wire mesh, and the protective filtering device adopts a stainless steel wire mesh with 30-100 meshes; the reaction temperature sensitive element and the environment temperature sensitive element adopt stainless steel shells.
Preferably, the upper ends of the reaction temperature sensitive element and the environment temperature sensitive element are fixedly connected with the upper flower plate through welding or threads by the clamping sleeve.
The calibration gas inlet and outlet seals include, but are not limited to, threaded stainless steel rods.
The preferred shower-proof cover is a disc-shaped structure, and rod-shaped supports are annularly arranged on the surface of the shower-proof cover.
The hydrogen sensor is arranged in a compartment or the top of a water evaporator in a containment in a wall-mounted or ground-mounted mode, is connected with a reaction temperature sensitive element and an environment temperature sensitive element through armored cables and an electric penetrating piece in the containment, transmits an environment temperature signal and a reaction temperature signal to the electric penetrating piece in the containment, connects the electric penetrating piece with a Programmable Logic Controller (PLC) in a signal processing cabinet through a compensation cable outside the containment, the signal processing cabinet is arranged in an electric plant, and a display is further arranged in the signal processing cabinet to display the hydrogen concentration.
The invention relates to a monitoring method of a hydrogen sensor with an alloy protection structure, which comprises the following steps:
1) when a serious accident occurs, the environmental temperature in the containment vessel rises rapidly, the surface temperature of the hydrogen sensor rises along with the rise of the environmental temperature, and when the surface temperature of alloy film materials adopted by the upper and lower flower plate protection structures rises to the melting temperature, the upper and lower flower plate protection structures are melted down, and the through holes on the upper and lower flower plates are exposed;
2) the hydrogen and air mixed gas ladder in the containment enters the hydrogen sensor in a free diffusion mode and diffuses to the core area of the sensor, namely the catalytic reactor;
3) hydrogen and oxygen are adsorbed on the surface of the catalyst, and further undergo a chemical reaction to form water and release heat, and the temperature of the hydrogen sensor rises;
4) the environment temperature and the reaction temperature are respectively monitored by an environment temperature sensitive element and a reaction temperature sensitive element, and response signals are transmitted to a signal processing cabinet through an armored cable, an electric penetration piece and a compensation lead in sequence;
5) the PLC in the signal processing cabinet obtains an ambient temperature signal and a reaction temperature signal through the signal acquisition module, an arithmetic unit in the PLC calculates a temperature rise value of catalytic reaction according to a difference value between the ambient temperature and the reaction temperature, and further calculates the volume concentration of hydrogen through a formula (1).
C(H2)＝K×(T1-T2) (1)
Wherein, C (H)2) Hydrogen concentration in%; k is an experimental summary calculation coefficient, and the K value is 0.04; t is1Is ambient temperature in units of; t is2Is the reaction temperature in degrees Celsius.
Principle of operation
When a reactor core loss-of-coolant accident occurs in a containment vessel of a nuclear power station, the residual heat of the reactor core cannot be led out, so that the environmental temperature in the containment vessel rises integrally, and when the residual heat exceeds the melting point of alloy film materials adopted by an upper flower plate protection structure and a lower flower plate protection structure in the hydrogen sensor, the protection structures are melted down, so that the internal environment of the hydrogen sensor is communicated with the atmospheric environment in the containment vessel.
When explosive mixed gas containing hydrogen occurs, a catalytic reactor in the hydrogen sensor starts to operate, the hydrogen and oxygen generate chemical combination reaction, heat is released, the temperature of the catalytic reactor rises, the temperature of the catalytic reactor can be measured by a reaction temperature sensitive element, the ambient temperature in a containment vessel of the nuclear power plant can be measured by an ambient temperature sensitive element, signals are transmitted to an electrical penetration piece of the containment vessel through an armored cable and are sequentially transmitted to a signal processing cabinet through the electrical penetration piece and a compensation wire outside the containment vessel, a PLC signal acquisition module in the signal processing cabinet acquires signals of the temperature sensitive element, an arithmetic unit in the PLC calculates the temperature rise value of the catalytic reaction according to the difference between the two temperatures, and further calculates the volume concentration of the hydrogen through a formula (1).
C(H2)＝K×(T1-T2) (1)
Wherein, C (H)2) Hydrogen concentration in%; k is an experimental summary calculation coefficient, and the K value is 0.04; t is1Is ambient temperature in units of; t is2Is the reaction temperature in degrees Celsius.
During the overhaul of the nuclear power station, the hydrogen sensor can be calibrated through the calibration gas inlet through hole and the calibration gas outlet through hole which are arranged on the protective outer cylinder.
Advantageous effects
1. The invention provides a hydrogen sensor with an alloy protection structure, wherein a catalytic reactor filled with a noble metal catalyst is arranged in the hydrogen sensor, so that the hydrogen sensor has the characteristics of strong normal-temperature starting capability, high stability and the like, external power supply is not needed, the overall safety and reliability are improved, the combustion and explosion caused by power supply or a heating process when the hydrogen concentration is higher are avoided, and the stability and the safety of the hydrogen sensor in the using process are ensured;
2. the invention provides a hydrogen sensor with an alloy protection structure, wherein a protection filtering device is arranged in the hydrogen sensor, so that the diffusion rate of hydrogen can be effectively limited, and the hydrogen sensor can not ignite surrounding high-concentration hydrogen in the working process to cause hydrogen deflagration or explosion; the device also has a blocking effect on aerosol and particles in the containment mixed gas;
4. the invention provides a hydrogen sensor with an alloy protection structure, wherein alloy thin film materials with the melting point of 70-120 ℃ are arranged on the surfaces of an upper flower plate and a lower flower plate in the hydrogen sensor and are used as the upper flower plate protection structure and the lower flower plate protection structure, so that the change of the environmental temperature after an accident can be quickly sensed and the alloy thin film materials are quickly melted to expose through holes on the surfaces of the upper flower plate and the lower flower plate, a natural diffusion environment is formed in the hydrogen sensor, and a hydrogen sensitive component is protected from the influence of the change of a gas flow field;
5. the invention provides a hydrogen sensor with an alloy protection structure, wherein an upper flower plate protection structure and a lower flower plate protection structure in the hydrogen sensor can keep the inside of the hydrogen sensor isolated from the atmospheric environment in a containment vessel during the construction and overhaul of a nuclear power station, so that dust and other volatile organic compounds can be prevented from entering the hydrogen sensor, and the service life and the reliability of the hydrogen sensor are improved;
6. the invention provides a hydrogen sensor with an alloy protection structure, wherein a mechanism for calibrating the hydrogen sensor during overhaul is arranged on a protection outer cylinder of the hydrogen sensor, so that the hydrogen sensor can be quickly opened and blocked;
7. the invention provides a hydrogen sensor with an alloy protection structure, wherein all parts except a reaction temperature sensitive element, an environment temperature sensitive element, an upper flower plate protection structure and a lower flower plate protection structure in the hydrogen sensor can be made of stainless steel or metal oxide, and the hydrogen sensor has the advantages of high temperature resistance, high pressure resistance, strong irradiation capability and high reliability;
8. the invention provides a hydrogen sensor with an alloy protection structure, wherein the size of each component in the hydrogen sensor can be adjusted, so that the measuring range of the hydrogen sensor can be adjusted, and the hydrogen sensor can adapt to the measurement of different hydrogen concentrations;
9. the invention provides a hydrogen sensor with an alloy protection structure, which can be provided with a spray-proof cover, wherein the spray-proof cover can prevent the hydrogen sensor from being sprayed due to a spray system in an accident condition of a nuclear power plant, so that the normal measurement and use of the hydrogen sensor can be ensured.
Drawings
Fig. 1 is a sectional view of the hydrogen sensor described in example 1.
Fig. 2 is a plan view of the lower faceplate of the hydrogen sensor described in example 1.
Fig. 3 is a sectional view of the lower plate and the lower plate guard structure of the hydrogen sensor described in example 1.
Fig. 4 is a graph of the hydrogen sensor test results described in example 1.
The device comprises a catalytic reactor 1, a protective filtering device 2, a reaction temperature sensitive element 3, an environment temperature sensitive element 4, a positioning rod 5, an installation rod 6, a supporting plate 7, a protective outer cylinder 8, an upper pattern plate 9, a lower pattern plate 10, an upper pattern plate protective structure 12, a lower pattern plate protective structure 13, a calibration gas inlet sealing piece 14, a calibration gas outlet sealing piece 15, an ear type support 16, a vertical welding support 17 and a drench-proof cover 17
Detailed Description
The present invention will be described in detail below with reference to examples and drawings, but the present invention is not limited to these examples.
The following is a detailed description of preferred embodiments of the invention.
Example 1
A hydrogen sensor with an alloy protection structure is shown in figure 1 and comprises a catalytic reactor 1, a protection filtering device 2, a reaction temperature sensitive element 3, an environment temperature sensitive element 4, a positioning rod 5, a mounting rod 6, a supporting plate 7, a protection outer cylinder 8, an upper flower plate 9, a lower flower plate 10, an upper flower plate protection structure 11, a lower flower plate protection structure 12, a calibration gas inlet sealing piece 13 and a calibration gas outlet sealing piece 14.
Wherein, catalytic reactor 1 is the cylinder structure of one end open-ended, and the open end has the external screw thread. The catalytic reactor 1 has an outer diameter of 10mm, a thickness of 0.5mm and a height of 40 mm; the inside diameter of the opening of the catalytic reactor 1 was 1 mm. The catalytic reactor 1 is filled with a catalyst which can enable hydrogen and oxygen to react at normal temperature; the catalyst is catalyst A or catalyst B. Catalyst A is Al2O3The catalyst with Co, Au and Pt as active components as the carrier has the mass fractions of Co, Au and Pt of 6.4%, 0.45% and 0.35% respectively in sequence, wherein the total mass of the catalyst is 100%. Catalyst B is Al2O3The catalyst with Pt, Pd and Rh as active components is taken as a carrier, and the mass fractions of the Pt, Pd and Rh are respectively 0.3%, 0.7% and 0.3% in sequence, wherein the total mass of the catalyst is 100%.
The protective filtering device 2 is a cylinder structure with an opening at one end, the opening end is provided with internal threads, and the inner diameter of the opening end is equal to that of the catalytic reactorThe outer diameters of the opening ends of the protective filter devices 1 are matched, and the side wall of the protective filter device 2 is of a double-layer structure which is formed by an inner layer side wall and an outer layer side wall and has a gap in the middle. The height of the protective filtering device 2 is 80mm, the outer diameter of the outer side wall is 60mm, the total thickness of the outer side wall, the inner side wall and the middle space between the outer side wall and the inner side wall is 5mm, and the middle space between the outer side wall and the inner side wall is 3 mm. The filler is arranged between the inner layer side wall and the outer layer side wall of the protective and protective filtering device and is spherical A12O3And/or spherical SiO2。
The reaction temperature sensitive element 3 is a K-type thermocouple, has the diameter of 2mm, extends into the protective outer cylinder 8 to the depth of 160mm, and is used for measuring the temperature of the oxyhydrogen reaction.
The environment temperature sensitive element 4 is a K-type thermocouple, the diameter of the environment temperature sensitive element is 2mm, the depth of the environment temperature sensitive element extending into the protective outer cylinder 8 is 260mm, and the environment temperature sensitive element is used for measuring the environment temperature in the containment vessel of the nuclear power plant.
The diameter of locating lever 5 is 6mm, and thickness is 1mm, and length is 110 mm.
The mounting rod 6 has a diameter of 4mm and a length of 250 mm.
The supporting plate 7 is a circular plate with a diameter of 100mm and a thickness of 3 mm.
The protective outer cylinder 8 is a cylinder structure with openings at two ends; a calibration gas inlet through hole is formed in the position, close to the bottom, of one side wall of the protection outer cylinder 8, the calibration gas inlet sealing element 13 is used for sealing, a calibration gas outlet through hole is formed in the position, close to the top, of the other side wall of the protection outer cylinder 8, and the calibration gas outlet sealing element 14 is used for sealing. The outer diameter of the protective outer cylinder 8 is 160mm, and the thickness is 2 mm; the height is 300mm, and the diameters of the calibration air inlet through hole and the calibration air outlet through hole on the surface of the protective outer cylinder 8 are 4 mm. Calibration gas inlet seal 13 and calibration gas outlet seal 14 are threaded stainless steel rods.
The diameter of the upper flower plate 9 is the same as the outer diameter of the protective outer cylinder 8, the diameter of the lower flower plate 10 is the same as the inner diameter of the protective outer cylinder 8, through holes are uniformly distributed on the upper flower plate 9 and the lower flower plate 10 and used for gas diffusion, as shown in fig. 2, the diameter of the upper flower plate 9 is 160mm, the thickness is 3mm, and the diameter of the uniformly distributed through holes is 4 mm; the lower card 10 has a diameter of 160mm and a thickness of 2mm, wherein the uniformly distributed through holes have a diameter of 4 mm.
The thickness of the upper flower plate protective structure 11 is 0.5mm, a disc-shaped SnPbBi film material is used, wherein the mass fractions of Sn, Pb and Bi are respectively 25.8%, 14.8% and 59.4%, and the melting point is 95 ℃.
The thickness of the lower flower plate protective structure 12 is 0.5mm, a disc-shaped SnPbBi film material is used, wherein the mass fractions of Sn, Pb and Bi are respectively 25.8%, 14.8% and 59.4%, and the melting point is 95 ℃.
Except for the reaction temperature sensitive element 3, the environment temperature sensitive element 4, the upper pattern plate protection structure 11 and the lower pattern plate protection structure 12, all the components of the hydrogen sensor are made of stainless steel; wherein, catalytic reactor 1 adopts the stainless steel net, and protection filter equipment 2 adopts the stainless steel net of 30 meshes, and reaction temperature sensing element 3 and ambient temperature sensing element 4 adopt the stainless steel shell.
The connection relation of each component in the hydrogen sensor is as follows:
the upper pattern plate 9 is positioned above the protective outer cylinder 8, the lower surface of the upper pattern plate 9 is welded with the top end of the cylinder wall of the protective outer cylinder 8, the whole upper surface or the lower surface of the upper pattern plate 9 is laminated with an upper pattern plate protective structure 11, the lower pattern plate 10 is positioned at the inner side of the bottom of the protective outer cylinder 8 and is welded with the inner side of the cylinder wall of the protective outer cylinder 8, and the whole upper surface or the lower surface of the lower pattern plate 10 is laminated with a lower pattern plate protective structure 12, as shown in fig. 3; the calibration gas inlet seal 13 and the calibration gas outlet seal 14 are respectively installed in the calibration gas inlet through hole and the calibration gas outlet through hole on the protection outer cylinder 8.
The catalytic reactor 1 is sleeved in the protective filtering device 2, the open end of the catalytic reactor 1 and the open end of the protective filtering device 2 are both upward and are connected through threads, a gap is reserved between the bottom of the catalytic reactor 1 and the bottom of the protective filtering device 2, a gap is reserved between the inner side wall of the protective filtering device 2 and the side wall of the catalytic reactor 1, and the catalytic reactor 1 and the protective filtering device 2 form a hydrogen sensitive component; the supporting plate 7 is positioned below the hydrogen sensitive component and is fixedly connected with the bottom of the protective filtering device 2; the hydrogen sensitive component is fixed in the protective outer cylinder 8 through the mounting rods 6, the top ends of the mounting rods 6 are welded with the upper flower plate 9, the bottom ends of the mounting rods 6 are fixedly connected with the supporting plate 7, and the three mounting rods 6 are uniformly distributed on the outer side of the hydrogen sensitive component; the environment temperature sensitive element 4 penetrates through the upper flower plate 9 and extends into the protective outer cylinder 8, a gap is reserved between the bottom end of the environment temperature sensitive element and the bottom of the protective outer cylinder 8, and the upper end of the environment temperature sensitive element is positioned outside the protective outer cylinder 8 and is in threaded connection with the upper flower plate 9 through a clamping sleeve; the upper end of locating lever 5 and last card 9 fixed connection, the lower extreme is relative with the opening center of catalytic reactor 1, and reaction temperature sensing element 3 passes last card 9 and stretches into in the protection urceolus 8 to fix a position through locating lever 5, the lower extreme stretches into in the catalytic reactor 1, and leaves the space between the bottom of catalytic reactor 1, and the upper end is located the protection urceolus 8 outsidely, and through cutting ferrule and last card 9 threaded connection.
The hydrogen sensor also comprises two ear type supports 15, two vertical welding supports 16 and a drench-proof cover 17, wherein one end of each ear type support 15 is fixedly connected with the protection outer cylinder 8, the other end of each ear type support is fixedly connected with the corresponding vertical welding support 16 to form a group of support structures, and the two groups of support structures are uniformly distributed on the outer side of the protection outer cylinder 8; the diameter of the shower-proof cover 17 is larger than that of the upper flower plate 9 and is fixedly connected with the protective outer cylinder 8. The shower-proof cover 17 is a disc-shaped structure, and rod-shaped supports are annularly arranged on the surface.
A monitoring method of the hydrogen sensor with the alloy protection structure according to the embodiment includes the following steps:
1) when a serious accident occurs, the environmental temperature in the containment vessel rapidly rises, the surface temperature of the hydrogen sensor rises, and when the surface temperature of the alloy film materials adopted by the upper flower plate protection structure 11 and the lower flower plate protection structure 12 rises to the melting temperature, the upper flower plate protection structure 11 and the lower flower plate protection structure 12 are melted down, and the through holes on the upper flower plate 9 and the lower flower plate 10 are exposed;
2) the hydrogen and air mixed gas ladder in the containment vessel enters the hydrogen sensor in a free diffusion mode and diffuses to the core area of the hydrogen sensor, namely the catalytic reactor 1;
3) hydrogen and oxygen are adsorbed on the surface of the catalyst, and further undergo a chemical reaction to form water and release heat, and the temperature of the hydrogen sensor rises;
4) the environment temperature and the reaction temperature are respectively monitored by the environment temperature sensitive element 4 and the reaction temperature sensitive element 3, and response signals are transmitted to the signal processing cabinet through the armored cable, the electric penetration piece and the compensation lead in sequence;
5) the PLC in the signal processing cabinet obtains an ambient temperature signal and a reaction temperature signal through the signal acquisition module, an arithmetic unit in the PLC calculates a temperature rise value of catalytic reaction according to a difference value between the ambient temperature and the reaction temperature, and further calculates the volume concentration of hydrogen through a formula (1).
C(H2)＝K×(T1-T2) (1)
Wherein, C (H)2) Hydrogen concentration in%; k is an experimental summary calculation coefficient, and the K value is 0.04; t is1Is ambient temperature in units of; t is2Is the reaction temperature in degrees Celsius.
The test experiment performed on the hydrogen sensor of this example was as follows:
preparing hydrogen-air mixed gas with different concentrations by adopting a gas mass flow meter Smart Trak 100 of SIERRA company in America; the response of the reaction temperature sensitive element 3 and the response of the environment temperature sensitive element 4 are obtained by monitoring through a Hangzhou American control automation technology company No-paper recorder RX6008DC, and are displayed or uploaded to a computer for recording; data was processed and plotted using origin8.0 software.
The data of the test results are shown in fig. 4, and it can be seen that: as the hydrogen concentration is gradually increased, the reaction temperature is gradually increased while the ambient temperature is unchanged, and at the same time, the concentration calculation coefficient is also kept unchanged or changes negligibly. The hydrogen concentration can be calculated by the following method:
C(H2)＝K×(T1-T2)
wherein, C (H)2) Hydrogen concentration in%; k is an experimental summary calculation coefficient, and the K value is 0.04; t is1Is ambient temperature in units of; t is2Is the reaction temperature in℃。
The present invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the principle of the spirit of the present invention are considered to be within the scope of the present invention.
Claims (10)
1. The utility model provides a hydrogen sensor with alloy protective structure which characterized in that: the hydrogen sensor comprises a catalytic reactor (1), a protective filtering device (2), a reaction temperature sensitive element (3), an environment temperature sensitive element (4), a positioning rod (5), a mounting rod (6), a supporting plate (7), a protective outer cylinder (8), an upper pattern plate (9) and a lower pattern plate (10); the device also comprises an upper pattern plate protection structure (11), a lower pattern plate protection structure (12), a calibration gas inlet sealing piece (13) and a calibration gas outlet sealing piece (14);
the catalytic reactor (1) is of a cylindrical structure with an opening at one end, and the opening end is provided with an external thread;
the protective filtering device (2) is of a cylindrical structure with an opening at one end, the opening end is provided with internal threads, the inner diameter of the opening end is matched with the outer diameter of the opening end of the catalytic reactor (1), the side wall of the protective filtering device (2) is of a double-layer structure which is formed by an inner side wall and an outer side wall and has a gap in the middle, and the inner diameter of the inner side wall is larger than the outer diameter of the catalytic reactor (1);
the supporting plate (7) is a circular plate, and the diameter of the supporting plate is larger than the outer diameter of the outer side wall of the protective filtering device (2);
the protective outer cylinder (8) is of a cylinder structure with openings at two ends; a calibration gas inlet through hole is formed in one side wall of the protective outer cylinder (8) close to the bottom, and is sealed by a calibration gas inlet sealing element (13), a calibration gas outlet through hole is formed in the other side wall of the protective outer cylinder (8) close to the top, and is sealed by a calibration gas outlet sealing element (14);
the diameter of the upper flower plate (9) is the same as the outer diameter of the protective outer cylinder (8), the diameter of the lower flower plate (10) is the same as the inner diameter of the protective outer cylinder (8), and through holes are uniformly distributed on the upper flower plate (9) and the lower flower plate (10);
the upper flower plate protection structure (11) and the lower flower plate protection structure (12) are respectively and independently disc-shaped alloy film materials, and the alloy film materials do not react with water vapor and have melting points of 70-120 ℃;
the upper pattern plate (9) is positioned above the protective outer cylinder (8), the lower surface of the upper pattern plate (9) is fixedly connected with the top end of the cylinder wall of the protective outer cylinder (8), an upper pattern plate protective structure (11) is laminated on the whole upper surface or lower surface of the upper pattern plate (9), the lower pattern plate (10) is positioned on the inner side of the bottom of the protective outer cylinder (8) and is fixedly connected with the inner side of the cylinder wall of the protective outer cylinder (8), and a lower pattern plate protective structure (12) is laminated on the whole upper surface or lower surface of the lower pattern plate (10); a calibration gas inlet sealing element (13) and a calibration gas outlet sealing element (14) are respectively arranged in the calibration gas inlet through hole and the calibration gas outlet through hole on the protective outer cylinder (8);
the catalytic reactor (1) is sleeved in the protective filtering device (2), the open end of the catalytic reactor (1) and the open end of the protective filtering device (2) are upward and are connected through threads, a gap is reserved between the bottom of the catalytic reactor (1) and the bottom of the protective filtering device (2), a gap is reserved between the inner side wall of the protective filtering device (2) and the side wall of the catalytic reactor (1), and the catalytic reactor (1) and the protective filtering device (2) form a hydrogen sensitive component; the supporting plate (7) is positioned below the hydrogen sensitive component and is fixedly connected with the bottom of the protective filtering device (2); the hydrogen sensitive component is fixed in the protective outer cylinder (8) through the mounting rod (6), the top end of the mounting rod (6) is fixedly connected with the upper pattern plate (9), the bottom end of the mounting rod is fixedly connected with the supporting plate (7), and more than two mounting rods (6) are uniformly distributed on the outer side of the hydrogen sensitive component; the environment temperature sensitive element (4) penetrates through the upper pattern plate (9) and extends into the protective outer cylinder (8), a gap is reserved between the bottom end of the environment temperature sensitive element and the bottom of the protective outer cylinder (8), and the upper end of the environment temperature sensitive element is positioned outside the protective outer cylinder (8) and is fixedly connected with the upper pattern plate (9) through a clamping sleeve; the upper end of locating lever (5) and last card (9) fixed connection, the lower extreme is relative with the opening center of catalytic reactor (1), reaction temperature sensing element (3) pass last card (9) and stretch into in protection urceolus (8) to fix a position through locating lever (5), the lower extreme stretches into in catalytic reactor (1), and leave the space between the bottom with catalytic reactor (1), the upper end is located protection urceolus (8) outside, and through cutting ferrule and last card (9) fixed connection.
2. The hydrogen sensor with an alloy protective structure according to claim 1, wherein: the upper flower plate (9) and the lower flower plate (10) are made of alloy materials composed of more than one element of bismuth, tin, lead, cadmium and indium respectively and independently.
3. The hydrogen sensor with an alloy protective structure according to claim 1, wherein: the outer diameter of the catalytic reactor (1) is 10 mm-50 mm, the thickness is 0.5 mm-2 mm, the height is 40 mm-90 mm, and the inner diameter of the opening of the catalytic reactor (1) is 1 mm-8 mm;
the height of the protective filtering device (2) is 80 mm-120 mm, the outer diameter of the outer side wall is 60 mm-100 mm, the total thickness of the outer side wall, the inner side wall and the gap between the outer side wall and the inner side wall is 5 mm-20 mm, and the gap between the outer side wall and the inner side wall is 3 mm-8 mm;
the diameter of the positioning rod (5) is 6-8 mm, the thickness is 1-2 mm, and the length is 110-130 mm;
the diameter of the mounting rod (6) is 4 mm-8 mm, and the length is 250 mm-280 mm;
the diameter of the supporting plate (7) is 100 mm-150 mm, and the thickness is 3 mm-8 mm;
the outer diameter of the protective outer cylinder (8) is 160 mm-200 mm, the thickness is 2 mm-5 mm, and the height is 300 mm-500 mm;
the diameter of the upper pattern plate (9) is 160 mm-200 mm, the thickness is 3 mm-6 mm, and the diameter of the upper through hole is 4 mm-8 mm;
the diameter of the lower pattern plate (10) is 160 mm-190 mm, the thickness is 2 mm-5 mm, and the diameter of the upper through hole is 4 mm-8 mm;
the thickness of the upper pattern plate protective structure (11) is 0.1 mm-1 mm;
the thickness of the lower pattern plate protective structure (12) is 0.1 mm-1 mm.
4. The hydrogen sensor with an alloy protective structure according to claim 1, wherein: the reaction temperature sensitive element (3) is a thermocouple or platinum resistance temperature measuring element, the diameter is 2 mm-6 mm, and the depth of extending into the protective outer cylinder (8) is 160 mm-200 mm;
the environment temperature sensitive element (4) is a thermocouple or platinum resistance temperature measuring element, the diameter is 2 mm-6 mm, and the depth of extending into the protective outer cylinder (8) is 260 mm-320 mm.
5. The hydrogen sensor with an alloy protective structure according to claim 1, wherein: the catalytic reactor (1) is filled with a catalyst, and the catalyst is a catalyst capable of enabling hydrogen and oxygen to react at normal temperature;
a filler is arranged between the inner side wall and the outer side wall of the protective filtering device (2), and the filler is spherical A12O3And/or spherical SiO2。
6. The hydrogen sensor with an alloy protective structure according to claim 1, wherein: the hydrogen sensor is characterized in that all parts except a reaction temperature sensitive element (3), an environment temperature sensitive element (4), an upper pattern plate protective structure (11) and a lower pattern plate protective structure (12) are made of stainless steel or metal oxide; wherein the catalytic reactor (1) adopts a stainless steel wire mesh, and the protective filtering device (2) adopts a stainless steel wire mesh with 30-100 meshes; the reaction temperature sensitive element (3) and the environment temperature sensitive element (4) adopt stainless steel shells.
7. The hydrogen sensor with an alloy protective structure according to claim 1, wherein: the hydrogen sensor also comprises an ear type support (15), a vertical welding support (16) and a drench-proof cover (17), wherein one end of the ear type support (15) is fixedly connected with the protective outer cylinder (8), the other end of the ear type support is fixedly connected with the vertical welding support (16) to form a group of support structures, and more than two groups of support structures are uniformly distributed on the outer side of the protective outer cylinder (8); the diameter of the shower-proof cover (17) is larger than that of the upper flower plate (9) and is fixedly connected with the protective outer cylinder (8).
8. The hydrogen sensor with an alloy protective structure according to claim 1, wherein: the shower-proof cover (17) is of a disc-shaped structure, and rod-shaped supports are annularly arranged on the surface of the shower-proof cover.
9. The hydrogen sensor with an alloy protective structure according to claim 2, wherein: the outer diameter of the catalytic reactor (1) is 10 mm-50 mm, the thickness is 0.5 mm-2 mm, the height is 40 mm-90 mm, and the inner diameter of the opening of the catalytic reactor (1) is 1 mm-8 mm;
the height of the protective filtering device (2) is 80 mm-120 mm, the outer diameter of the outer side wall is 60 mm-100 mm, the total thickness of the outer side wall, the inner side wall and the gap between the outer side wall and the inner side wall is 5 mm-20 mm, and the gap between the outer side wall and the inner side wall is 3 mm-8 mm;
the diameter of the positioning rod (5) is 6-8 mm, the thickness is 1-2 mm, and the length is 110-130 mm;
the diameter of the mounting rod (6) is 4 mm-8 mm, and the length is 250 mm-280 mm;
the diameter of the supporting plate (7) is 100 mm-150 mm, and the thickness is 3 mm-8 mm;
the outer diameter of the protective outer cylinder (8) is 160 mm-200 mm, the thickness is 2 mm-5 mm, and the height is 300 mm-500 mm;
the diameter of the upper pattern plate (9) is 160 mm-200 mm, the thickness is 3 mm-6 mm, and the diameter of the upper through hole is 4 mm-8 mm;
the diameter of the lower pattern plate (10) is 160 mm-190 mm, the thickness is 2 mm-5 mm, and the diameter of the upper through hole is 4 mm-8 mm;
the thickness of the upper pattern plate protective structure (11) is 0.1 mm-1 mm;
the thickness of the lower pattern plate protective structure (12) is 0.1 mm-1 mm;
the reaction temperature sensitive element (3) is a thermocouple or platinum resistance temperature measuring element, the diameter is 2 mm-6 mm, and the depth of extending into the protective outer cylinder (8) is 160 mm-200 mm;
the environment temperature sensitive element (4) is a thermocouple or platinum resistance temperature measuring element, the diameter is 2 mm-6 mm, and the depth of extending into the protective outer cylinder (8) is 260 mm-320 mm;
the catalytic reactor (1) is filled with a catalyst, and the catalyst is a catalyst capable of enabling hydrogen and oxygen to react at normal temperature;
a filler is arranged between the inner side wall and the outer side wall of the protective filtering device (2), and the filler is spherical A12O3And/or spherical SiO2；
The hydrogen sensor is characterized in that all parts except a reaction temperature sensitive element (3), an environment temperature sensitive element (4), an upper pattern plate protective structure (11) and a lower pattern plate protective structure (12) are made of stainless steel or metal oxide; wherein the catalytic reactor (1) adopts a stainless steel wire mesh, and the protective filtering device (2) adopts a stainless steel wire mesh with 30-100 meshes; the reaction temperature sensitive element (3) and the environment temperature sensitive element (4) adopt stainless steel shells;
the hydrogen sensor also comprises an ear type support (15), a vertical welding support (16) and a drench-proof cover (17), wherein one end of the ear type support (15) is fixedly connected with the protective outer cylinder (8), the other end of the ear type support is fixedly connected with the vertical welding support (16) to form a group of support structures, and more than two groups of support structures are uniformly distributed on the outer side of the protective outer cylinder (8); the diameter of the anti-drenching cover (17) is larger than that of the upper flower plate (9) and is fixedly connected with the protective outer cylinder (8);
the anti-drenching cover (17) is of a disc-shaped structure, and rod-shaped supports are annularly arranged on the surface of the anti-drenching cover;
the upper ends of the reaction temperature sensitive element (3) and the environment temperature sensitive element (4) are fixedly connected with the upper flower plate (9) through welding or threads by a clamping sleeve; the calibration gas inlet seal (13) and the calibration gas outlet seal (14) include, but are not limited to, threaded stainless steel rods.
10. A monitoring method of a hydrogen sensor with an alloy protection structure according to any one of claims 1 to 9, wherein: the hydrogen sensor is arranged inside or at the top of a compartment of the water evaporator in the containment, the reaction temperature sensitive element (3) and the environment temperature sensitive element (4) are connected with an electric penetration piece in the containment through an armored cable, the electric penetration piece is connected with a PLC (programmable logic controller) in a signal processing cabinet through a compensation cable outside the containment, the signal processing cabinet is arranged in an electric plant, and a display is further arranged in the signal processing cabinet to display the hydrogen concentration;
the method comprises the following steps:
1) when a serious accident occurs, the environmental temperature in the containment vessel rises rapidly, the surface temperature of the hydrogen sensor rises, when the surface temperature of alloy film materials adopted by the upper flower plate protection structure (11) and the lower flower plate protection structure (12) rises to the melting temperature, the upper flower plate protection structure (11) and the lower flower plate protection structure (12) are melted down, and the through holes on the upper flower plate (9) and the lower flower plate (10) are exposed;
2) the mixed gas of hydrogen and air in the containment enters the hydrogen sensor in a free diffusion mode and diffuses to the catalytic reactor (1);
3) hydrogen and oxygen are adsorbed on the surface of the catalyst, and further undergo a chemical reaction to form water and release heat, and the temperature of the hydrogen sensor rises;
4) the environment temperature and the reaction temperature are respectively monitored by an environment temperature sensitive element (4) and a reaction temperature sensitive element (3), and response signals are transmitted to a signal processing cabinet through an armored cable, an electric penetration piece and a compensation wire in sequence;
5) the PLC in the signal processing cabinet obtains an ambient temperature signal and a reaction temperature signal through the signal acquisition module, an arithmetic unit in the PLC calculates a temperature rise value of catalytic reaction through a difference value between the ambient temperature and the reaction temperature, and the volume concentration of hydrogen is calculated through a formula (1):
C(H2)=K×(T1-T2) （1）
C(H2) Hydrogen concentration in%; k is the total number of experimentsCalculating the coefficient, wherein the K value is 0.04; t is1Is ambient temperature in units of; t is2Is the reaction temperature in degrees Celsius.
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| CN108169293A (en) * | 2018-02-11 | 2018-06-15 | 中国工程物理研究院总体工程研究所 | High-precision film resistor hydrogen gas sensor calibration device and Calibration Method |
| CN108732212B (en) * | 2018-05-23 | 2020-12-15 | 哈尔滨工程大学 | Manufacturing method of multi-effect detection integrated gas sensor, sensor and application of sensor |
| CN110018277B (en) * | 2019-04-18 | 2022-05-03 | 北京今日蓝天科技有限公司 | Protective housing, protection device and detection device |
| CN114038585A (en) * | 2021-11-17 | 2022-02-11 | 中国核动力研究设计院 | Arc-top multilayer-structure passive hydrogen recombiner |
| CN113893689A (en) * | 2021-11-17 | 2022-01-07 | 中国核动力研究设计院 | Passive hydrogen recombiner with protection structure |
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