CN204594926U - A kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle - Google Patents
A kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle Download PDFInfo
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- CN204594926U CN204594926U CN201520344969.0U CN201520344969U CN204594926U CN 204594926 U CN204594926 U CN 204594926U CN 201520344969 U CN201520344969 U CN 201520344969U CN 204594926 U CN204594926 U CN 204594926U
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Abstract
The utility model discloses a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle, comprise pressure equilibrium film, internal layer shell, to electrode, working electrode, concentrated sulphuric acid electrolyte, hydrogen semi-permeable diaphragm and Signal connector, the equal opening in the upper and lower two ends of internal layer shell, pressure equilibrium film and hydrogen semi-permeable diaphragm close the opening at the upper and lower two ends of internal layer shell respectively, region between pressure equilibrium film, internal layer shell and hydrogen semi-permeable diaphragm three forms electrolyte cavity volume, and concentrated sulphuric acid electrolyte is filled in electrolyte cavity volume.All there is one end to embed in electrolyte cavity volume to electrode, working electrode and Signal connector three, electrode, Signal connector are all connected with working electrode.Be coated with titanium dioxide platinum layer to the substrate surface of electrode, the substrate surface of working electrode is coated with platinum black layer.During the utility model application, measurement accuracy is high, and selectivity is strong, possess 220 DEG C, irradiation, continous-stable ability to work under the harsh conditions such as high concentration water's steam.
Description
Technical field
The utility model relates to density of hydrogen field of measuring technique, specifically a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle.
Background technology
After Fukushima, Japan nuclear power plant accident, State Bureau of Nuclear Safety requires in hydrogen control system, to increase density of hydrogen on-line monitoring system under severe accident conditions, for the continuous on-line monitoring of density of hydrogen under major accident.Density of hydrogen in current nuclear power station mainly adopts the technology of off-line monitoring.The containment hydrogen control system at AP1000 and CAP1400 generation Ⅲ nuclear power station requires using the density of hydrogen value of on-line monitoring as the condition controlling hydrogen igniter startup, and this will the realistic function showing density of hydrogen on-line real time monitoring.Current hydrogen gas concentration sensor both domestic and external generally based on thermal conductivity method principle of work realize, these sensors be mainly applicable to sampling type measure, measure high temperature, complex component gas time measuring accuracy low, and cannot to hydrogen in environment realize on-line continuous monitoring.Obviously, existing density of hydrogen sensing is inapplicable in the containment hydrogen control system at AP1000 and CAP1400 generation Ⅲ nuclear power station, design a kind of sensor that can realize on-line continuous monitoring to hydrogen in environment, this becomes current people's question of common concern, but, there is no corresponding device now, have no relevant report yet.
Utility model content
the purpose of this utility model is to overcome the deficiencies in the prior art, provide a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle, it can realize on-line continuous monitoring of density of hydrogen in environment, and then can meet the demand of containment hydrogen control system at AP1000 and CAP1400 generation Ⅲ nuclear power station.
The utility model solves the problem and is achieved through the following technical solutions: a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle, comprise pressure equilibrium film, internal layer shell, to electrode, working electrode, concentrated sulphuric acid electrolyte, hydrogen semi-permeable diaphragm and Signal connector, the equal opening in the upper and lower two ends of described internal layer shell, described pressure equilibrium film and hydrogen semi-permeable diaphragm are individually fixed in the upper and lower two ends of internal layer shell and close the opening at the upper and lower two ends of internal layer shell, pressure equilibrium film, region between internal layer shell and hydrogen semi-permeable diaphragm three forms electrolyte cavity volume, described concentrated sulphuric acid electrolyte is filled in electrolyte cavity volume, described all have one end to pass internal layer shell to electrode, working electrode and Signal connector three and embed in electrolyte cavity volume, be connected by power transmission line one end that electrode and working electrode are positioned at outside internal layer shell, one end that Signal connector is positioned at electrolyte cavity volume is connected with working electrode, the described substrate surface to electrode is coated with titanium dioxide platinum layer, and the substrate surface of working electrode is coated with platinum black layer.Connect in the utility model on the power transmission line to electrode and working electrode and be serially connected with resistance or load, the current signal that the utility model produces is exported by Signal connector.Pressure equilibrium film of the present utility model is mainly used in balancing pressure in the pressure of ambient atmosphere and electrolyte cavity volume, pressure in air and electrolyte cavity volume is consistent, eliminate pressure to the impact of measurement result, to ensure that hydrogen is mainly derived from density of hydrogen difference by the power of hydrogen semi-permeable diaphragm, hydrogen semi-permeable diaphragm Main Function is isolation electrolyte cavity volume and measurement gas, and makes the hydrogen in measurement gas enter electrolyte cavity volume through hydrogen semi-permeable diaphragm.
Based on catalytic reaction electrochemical analysis principle during the utility model application, the dividing potential drop of the current measurement hydrogen produced under utilizing the chemical reaction of hydrogen on the working electrode scribbling catalyzer and electrolyte effect.Measure sample gas and enter electrolytic cell through hydrogen semi-permeable diaphragm, and there is ionization reaction immediately 1. with during working electrode contact, the platinum black layer of working electrode surface is as the catalyzer making hydrogen that ionization occur.PtO is contained to electrode
2(reaction 2.), be immersed in acid concentrated sulphuric acid electrolyte electrode, this electrolyte does not seethe with excitement under 210 DEG C of hot conditions, and possesses conducting function.Concentrated sulphuric acid electrolyte provides ionic conduction path, connects two interelectrode resistance or load provides electronic conduction path.Concentrated sulphuric acid electrolyte is separated with ambient atmosphere by hydrogen semi-permeable diaphragm.After hydrogen enters electrolyte cavity volume, electrolyte cavity volume dividing potential drop is made to be zero.Therefore, the hydrogen dividing potential drop of hydrogen semi-permeable diaphragm air side is that transmission hydrogen makes it by the driving force of hydrogen semi-permeable diaphragm.Non-essential resistance or load voltage, for sensing atmospheric hydrogen dividing potential drop being converted to current signal, are directly proportional to driving force.
working electrode reaction 1.
to electrode reaction 2.
Electric current---intrinsic standoff ratio is special electrodes configuration constant and constant temperature constant, and with regard to temperature inversion, hydrogen semi-permeable diaphragm is not identical to the air penetrability of hydrogen, thus the induction current of sensor is also changed thereupon.The change of air penetrability, the change being converted into electric current afterwards raises along with temperature and increases.
Further, describedly noble metal is all adopted to be base material to electrode and working electrode.
Further, describedly platinized platinum or platinum guaze is all adopted to be base material to electrode and working electrode.
Further, a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle, also comprises temperature element, and described temperature element passes internal layer shell and its temperature-sensitive end contacts with concentrated sulphuric acid electrolyte.By temperature element, the temperature in electrolyte cavity volume is monitored during the utility model application, be convenient to calibrate the density of hydrogen in electrolyte cavity volume.The signal produced because of the utility model is relevant with temperature, and set temperature calibration can meet the requirement that density of hydrogen is monitored under different temperatures.
Further, described pressure equilibrium film adopts polytetrafluoroethylene film, and described hydrogen semi-permeable diaphragm adopts PET semi-permeable diaphragm.So, pressure equilibrium film of the present utility model and hydrogen semi-permeable diaphragm have sulfuric acid corrosion resistant, resistance to 220 DEG C of characteristics such as high temperature, resistance to irradiation, pressure equilibrium film, can equilibrium electrolyte cavity volume and ambient pressure when atmospheric pressure change, and hydrogen semi-permeable diaphragm possesses hydrogen molecule through function.
Further, a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle, also comprise circular top cover labyrinth plate and lower seal cover plate, described internal layer shell is cylindric, the equal evagination in the upper and lower two ends of internal layer shell is configured with the locating platform of annular, described pressure equilibrium film circumferential edge all contacts with the upper surface of internal layer shell upper end locating platform and presses down fixing by top cover labyrinth plate, and described hydrogen semi-permeable diaphragm circumferential edge contacts with the lower surface of internal layer shell lower end locating platform and determines by lower seal cover plate presses solidly.So, pressure equilibrium film can fixedly positioning by the utility model under the effect of top cover labyrinth plate, and fixedly positioning hydrogen semi-permeable diaphragm under the effect of lower seal cover plate.
Because teflon has high temperature resistant, corrosion resistant performance, in order to meet corrosion and the insulating requirements of the concentrated sulphuric acid under the high temperature resistant condition of internal layer shell, further, the material of described internal layer shell is teflon.
Further, a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle, also comprises outer casing, and described internal layer shell is located in outer casing.During the utility model application, internal layer shell provides pressure boundary for concentrated sulphuric acid electrolyte, and outer casing provides pressure boundary during calibration.
Further, the material of described outer casing is copper or 316L stainless steel.
In sum, the utility model has following beneficial effect: (1) sensor of the present utility model is a kind of self-powered chemical devices, the current signal being divided into direct ratio with hydrogen in air can be produced, during the utility model application, selectivity is strong, measuring error is less by background gas components influence, the impact of water vapor on measurement result can be eliminated, pre-service need not be carried out to sample gas during measurement, continuous on-line measurement can be realized, and then the demand of containment hydrogen control system at AP1000 and CAP1400 generation Ⅲ nuclear power station can be met.
(2) the utility model possess 220 DEG C, irradiation, continous-stable ability to work under the harsh conditions such as high concentration water's steam.
(3) during application of the present utility model, the response time is fast, is less than 180s.
Accompanying drawing explanation
fig. 1 is the sectional structure schematic diagram of the utility model specific embodiment.
Name in accompanying drawing corresponding to Reference numeral is called: 1, outer casing, 2, top cover labyrinth plate, 3, pressure equilibrium film, 4, internal layer shell, 5, to electrode, 6, mounting seat, 7, temperature element, 8, working electrode, 9, concentrated sulphuric acid electrolyte, 10, hydrogen semi-permeable diaphragm, 11, lower seal cover plate, 12, Signal connector.
Embodiment
Below in conjunction with embodiment and accompanying drawing, detailed description is further done to the utility model, but embodiment of the present utility model is not limited thereto.
Embodiment 1:
As shown in Figure 1, a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle, comprise pressure equilibrium film 3, internal layer shell 4, to electrode 5, working electrode 8, concentrated sulphuric acid electrolyte 9, hydrogen semi-permeable diaphragm 10 and Signal connector 12, wherein, the material of internal layer shell 4 is teflon, the equal opening in internal layer shell about 4 two ends, pressure equilibrium film 3 is fixed on two ends on internal layer shell 4 and closes the opening of internal layer shell 4 upper end, and hydrogen semi-permeable diaphragm 10 is fixed on internal layer shell 4 times two ends and closes the opening of internal layer shell 4 lower end.Region between pressure equilibrium film 3 in the present embodiment, internal layer shell 4 and hydrogen semi-permeable diaphragm 10 three forms electrolyte cavity volume, and concentrated sulphuric acid electrolyte 9 is filled in electrolyte cavity volume.All the having one end to pass internal layer shell 4 to electrode 5, working electrode 8 and Signal connector 12 three and embed in electrolyte cavity volume of the present embodiment, one end that electrode 5 and both working electrodes 8 are positioned at outside internal layer shell 4 is connected by power transmission line, this power transmission line is serially connected with resistance or load, one end that Signal connector 12 is positioned at electrolyte cavity volume is connected with working electrode 8.All adopt noble metal to be base material to electrode 5 and working electrode 8 in the present embodiment, preferably adopt platinized platinum or platinum guaze to be base material, be coated with titanium dioxide platinum layer to the substrate surface of electrode 5, the substrate surface of working electrode 8 is coated with platinum black layer.Pressure equilibrium film 3 in the present embodiment adopts polytetrafluoroethylene film, and hydrogen semi-permeable diaphragm 10 adopts PET semi-permeable diaphragm.
In the present embodiment internal layer shell 4 through to the position of electrode 5 and to electrode 5, internal layer shell 4 is provided with sealed insulation pad through the position of working electrode 8 and working electrode 8, wherein, the material of sealed insulation pad is teflon.The present embodiment is under the effect of sealed insulation pad, working electrode 8 can be ensured, both electrodes 5 and internal layer shell 4 are insulated and working electrode 8 and insulating between electrode 5, sealed insulation pad plays fixed support to working electrode 8 with to electrode 5, and is sealed in internal layer shell 4 by the concentrated sulphuric acid electrolyte 9 in internal layer shell 4.
During the present embodiment application, in environment, hydrogen enters electrolyte cavity volume by hydrogen semi-permeable diaphragm 10, and electrolysis electrode occurs catalytic reaction generation current, and this electric current is directly proportional to the amounts of hydrogen entering electrolyte cavity volume.Data processing equipment is equipped with, the signal that data processing equipment sends in conjunction with the sensor of general pressure signal and the present embodiment, by calculating hydrogen volume percentage in measurement environment during the present embodiment application.
Embodiment 2:
The present embodiment has made following restriction further on the basis of embodiment 1: the present embodiment also comprises temperature element 7, and wherein, temperature element 7 passes internal layer shell 4 and its temperature-sensitive end contacts with concentrated sulphuric acid electrolyte 9.
Embodiment 3:
The present embodiment have been made and have been limited further as follows on the basis of embodiment 1 or embodiment 2: the present embodiment also comprises top cover labyrinth plate 2 and lower seal cover plate 11, and top cover labyrinth plate 2 and lower seal cover plate 11 are circular.The internal layer shell 4 of the present embodiment is cylindric, the equal evagination in internal layer shell about 4 two ends is configured with the locating platform of annular, pressure equilibrium film 3 circumferential edge all contacts with the upper surface of internal layer shell 4 upper end locating platform and presses down fixing by top cover labyrinth plate 2, and hydrogen semi-permeable diaphragm 10 circumferential edge contacts with the lower surface of internal layer shell 4 lower end locating platform and determines by lower seal cover plate 11 presses solidly.Both, when being fixed pressure equilibrium film 3 and hydrogen semi-permeable diaphragm 10, first tiling and both circumferential edge are contacted with the locating platform of internal layer shell 4, then pressing down fixing by top cover labyrinth plate 2 and lower seal cover plate 11 by the present embodiment.In order to make pressure equilibrium film 3 and hydrogen semi-permeable diaphragm 10 fixation, the present embodiment is strengthened fixing by many through the bolt of top cover labyrinth plate 2, pressure equilibrium film 3 and internal layer shell 4 upper end locating platform and the nut be set on bolt again to pressure equilibrium film 3, and strengthens fixing by many to hydrogen semi-permeable diaphragm 10 through the bolt of lower seal cover plate 11, hydrogen semi-permeable diaphragm 10 and internal layer shell 4 lower end locating platform and the nut be set on bolt.
Embodiment 4:
The basis of the present embodiment any one embodiment in embodiment 1 ~ embodiment 3 is made following restriction further: the present embodiment also comprises outer casing 1, wherein, the material of outer casing 1 is copper or 316L stainless steel, and the parts of internal layer shell 4 and upper connection thereof are all located in outer casing 1.For the ease of positioning outer casing 1, the present embodiment is also provided with mounting seat 6, and outer casing 1 is fixed in mounting seat 6.
As mentioned above, the utility model can be realized preferably.
Claims (9)
1. the hydrogen gas concentration sensor based on catalytic reaction electrochemical principle, it is characterized in that, comprise pressure equilibrium film (3), internal layer shell (4), to electrode (5), working electrode (8), concentrated sulphuric acid electrolyte (9), hydrogen semi-permeable diaphragm (10) and Signal connector (12), described internal layer shell (4) is the equal opening in two ends up and down, described pressure equilibrium film (3) and hydrogen semi-permeable diaphragm (10) are individually fixed in the upper and lower two ends of internal layer shell (4) and close the opening at the upper and lower two ends of internal layer shell (4), pressure equilibrium film (3), region between internal layer shell (4) and hydrogen semi-permeable diaphragm (10) three forms electrolyte cavity volume, described concentrated sulphuric acid electrolyte (9) is filled in electrolyte cavity volume, described all have one end to pass internal layer shell (4) to electrode (5), working electrode (8) and Signal connector (12) three and embed in electrolyte cavity volume, be positioned at internal layer shell (4) one end outward to both electrode (5) and working electrode (8) to be connected by power transmission line, one end that Signal connector (12) is positioned at electrolyte cavity volume is connected with working electrode (8), the described substrate surface to electrode (5) is coated with titanium dioxide platinum layer, and the substrate surface of working electrode (8) is coated with platinum black layer.
2. a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle according to claim 1, is characterized in that, describedly all adopts noble metal to be base material to electrode (5) and working electrode (8).
3. a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle according to claim 2, is characterized in that, describedly all adopts platinized platinum or platinum guaze to be base material to electrode (5) and working electrode (8).
4. a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle according to claim 1, it is characterized in that, also comprise temperature element (7), described temperature element (7) through internal layer shell (4) and its temperature-sensitive end contact with concentrated sulphuric acid electrolyte (9).
5. a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle according to claim 1, is characterized in that, described pressure equilibrium film (3) adopts polytetrafluoroethylene film, and described hydrogen semi-permeable diaphragm (10) adopts PET semi-permeable diaphragm.
6. a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle according to claim 1, it is characterized in that, also comprise circular top cover labyrinth plate (2) and circular lower seal cover plate (11), described internal layer shell (4) is cylindric, internal layer shell (4) the up and down equal evagination in two ends is configured with the locating platform of annular, described pressure equilibrium film (3) circumferential edge all contacts with the upper surface of internal layer shell (4) upper end locating platform and presses down fixing by top cover labyrinth plate (2), described hydrogen semi-permeable diaphragm (10) circumferential edge contacts with the lower surface of internal layer shell (4) lower end locating platform and determines by lower seal cover plate (11) presses solidly.
7. a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle according to claim 1, is characterized in that, the material of described internal layer shell (4) is teflon.
8. according to a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle in claim 1 ~ 7 described in any one, it is characterized in that, also comprise outer casing (1), described internal layer shell (4) is located in outer casing (1).
9. a kind of hydrogen gas concentration sensor based on catalytic reaction electrochemical principle according to claim 8, is characterized in that, the material of described outer casing (1) is copper or 316L stainless steel.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104914145A (en) * | 2015-05-26 | 2015-09-16 | 中国核动力研究设计院 | Catalytic reaction electrochemical principle-based hydrogen concentration sensor |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104914145A (en) * | 2015-05-26 | 2015-09-16 | 中国核动力研究设计院 | Catalytic reaction electrochemical principle-based hydrogen concentration sensor |
| CN104914145B (en) * | 2015-05-26 | 2018-06-15 | 中国核动力研究设计院 | A kind of hydrogen gas concentration sensor based on catalysis reaction electrochemical principle |
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