CN101363813B - Gas sensor for monitoring gas content in insulating oil - Google Patents
Gas sensor for monitoring gas content in insulating oil Download PDFInfo
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- CN101363813B CN101363813B CN2007100755957A CN200710075595A CN101363813B CN 101363813 B CN101363813 B CN 101363813B CN 2007100755957 A CN2007100755957 A CN 2007100755957A CN 200710075595 A CN200710075595 A CN 200710075595A CN 101363813 B CN101363813 B CN 101363813B
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Abstract
The invention relates to a gas sensor for monitoring the gas content in insulating oil, in particular to a gas sensor for the online monitoring of the acetylene gas content in insulating oil. The gas sensor comprises a hollow-structure integrated casing, and combined type oil-gas separation membrane and a fuel cell type gas sensing component which are installed inside the casing; wherein a selective electrocatalysis filtering layer for filtering interfering gas is also installed between the combined type oil-gas separation membrane and the fuel cell. Identical gas diffusion electrodes formed by gold alloy (Au) clectrocatalyst are adopted for the anode and the cathode of the selective acetylene fuel cell. The activity of the selective electrocatalysis filtering layer to the interfering gas is higher than the fuel cell itself to the interfering gas; with the increasing of the activity ratio, the filtering effect is also improved. The gas sensor is resistant to various ambient pressure and temperature changes, and the content of low concentration acetylene gas can be correctly and stably monitored in the environment with high concentration interfering gas such as hydrogen gas, carbon monoxide and ethylene gas.
Description
Technical field
The present invention relates to a kind of oil-immersed and high-voltage electrical equipment malfunction on-line monitoring technique, more particularly, relate to the micro-integrated selectivity feulcell prototype acetylene gas sensor that is used for on-line continuous monitoring insulating oil acetylene gas concentration.
Background technology
Electric system is safeguarded (rules) in the works to high voltage electric equipment such as transformer, reactor, mutual inductor etc., and the analysis result that extensively adopts oil dissolved gas is as the leading indicator of judging its internal fault.Wherein, acetylene gas content is to judge whether transformer inside exists the important evidence of high-energy discharge.Even the acetylene of very small amount is also indicating oil-filled electrical equipment and serious potential faults occurring.So it is significant for the reliable and secure operation of oil-filled electrical equipment accurately and timely to detect in the oil dissolved acetylene gas concentration.
Traditional acetylene gas content analysis is accomplished in the laboratory, and it comprises regular on-site sampling, sample presentation, the degassing and gas chromatographic analysis.Based on regular detection, be sense cycle with 3 months to 1 year generally consequently, this mode is powerless to the fast fault of evolving speed, can't accomplish to check erroneous ideas at the outset, and prevents trouble before it happens.
Gas in the oil (being commonly called as oil chromatography) on-line monitoring has been set up bridge between regular sampling analysis.It can be under the condition that does not influence the normal operation of monitored transformer; Failure gas in the transformer oil is carried out continuous monitoring; In addition, also can be on existing monitoring historical data basis, through the analysis that Monitoring Data is changed; Infer transformer inside or the variation of occurent fault or evolving trend, so that in time take measures.
One of means of on-line monitoring acetylene gas are to be similar to the gas chromatography that use in the laboratory; But gas chromatographic technique is used for on-line monitoring exists limitation; As complicacy is installed, needs shortcoming such as, cost height big, so be difficult to large-scale popularization with consumables and consumable accessory, maintenance.
And have highly sensitive, characteristics such as reaction velocity fast, the dynamic measurement scope big, stable performance, good reproducibility based on On-Line Monitor Device of Gas in the oil of fuel cell gas sensing technology; On reliability, repeatability and cost, having incomparable advantage (specifically can be referring to Qin Renyan, the new development of gas on-line monitoring technique in the feulcell prototype oil, " transformer "; V44; No.6, June2007, pp45-50).But the feulcell prototype acetylene gas sensor faces following challenge:
(1) improves selectivity-mean and the raising accuracy will in the environment of the non-object gas of high concentration (like hydrogen, carbon monoxide), accurately detect low concentration object gas, i.e. acetylene; For example in the Co mixed gas of the hydrogen of hundreds of μ L/L concentration, thousands of μ L/L concentration, detect the acetylene gas of several μ L/L concentration; This is that main characteristic gas is hydrogen, carbon monoxide, carbon dioxide, methane, ethane, ethene and acetylene when breaking down because of high voltage electric equipment; Wherein the content of hydrogen, carbon monoxide and ethene is usually much larger than the content of acetylene; And have electrochemical activity at normal temperatures, can produce the detection of acetylene usually and disturb;
(2) improve stability-mean raising reliability, long-term stable operation under no maintenance condition.
Raising object gas optionally one of method is to adopt the selectivity acetylene gas sensor, and the electrode of for example processing as eelctro-catalyst with pure crystallite gold (Au) is a selectivity acetylene electrode commonly used in the electrochemical sensor; However; The cross sensitivity of other gas still can not be ignored, for example Peter C.Hauser find that the relative sensitivity of ethene on the Au electrode can reach 14% (specifically can be referring to Amperometric Gas Sensors of High Sensitivity, Electroanalysis1999; 11; No10-11, pp782-787), and ethene also is one of common faults gas in the insulating oil..
In U.S. Pat 6436257B1 (corresponding to Chinese patent CN00808500.5), a kind of feulcell prototype acetylene sensor is disclosed.Its design concept has adopted the work of above-mentioned Hauser basically.Be characterized in the Au electrode that deposits to Nafion proton film as anode, as negative electrode, lean on the acidic electrolyte bath of gel (gel) shape to guarantee to contact between the proton film of anode and the Pt electrode of negative electrode with the Pt electrode.But the long-time stability and the reliability of this sensor are relatively poor, be embodied in following some:
(1) uses solid and liquid mixing electrolyte; Because Nafion proton film lacks the hydrophobic nature that gas-diffusion electrode had; Therefore gel electrolyte can produce leakage phenomenon under the influence of temperature, pressure, causes the performance of sensor to change finally causing malfunctioning;
(2) owing to the asymmetric electrode that uses Au and Pt, so the dynamic stability of sensor is relatively poor;
(3) contact of the Au electrode of this method preparation of usefulness and Nafion proton film is poor; Because electrochemical reaction relates to the migration of proton; Metal electrode layer must contact with Nafion proton film could produce electric signal; Metal A u electrode most surfaces with this method preparation can not contact with Nafion, so efficient is low, and depositing metal layers comes off easily;
(4) the cross sensitivity problem of other gas of Au electrode pair such as H2, CO and C2H4 can't solve, and therefore influences the acetylene gas monitoring accuracy;
(5) owing to adopting macromolecule membrane as the gas-oil separation film, when receiving certain environment malleation, negative pressure or high temperature, plastic yield easily; Be permanent elongation distortion even break; Its result gently then causes pick up calibration to be lost efficacy, and is heavy then cause oil impregnate, and sensor is scrapped.
Improve object gas optionally method two be to remove the non-object gas (also claiming interference gas) in (or reducing at least) mixed gas with the method that selective chemical purifies, promptly improve the relative content of object gas.Selective chemical purifies and is divided into two kinds again, and a kind of is consumption-type, and promptly active agent itself is participated in reaction and generated non-active compound.At U.S. Pat 6284545B1, introduced this type cleanser among Chinese patent CN02104274.8, CN02104277.2, CN200310115871.X, CN200310115872.4 and the CN200410011271.3 in detail and prepared the method for this type cleanser.But the shortcoming of this cleanser is it from constantly consuming, and activating component can be fewer and feweri, therefore can't satisfy the needs of gas sensor long-term work.
The another kind of scheme that selective chemical purifies is a catalytic type, and promptly active agent itself is participated in reacting but can not changed self activated state, can be recycled.A kind of catalyzing carbon monoxide filtering agent that is used for the ethylene sensor of mine safety is disclosed among the Chinese patent CN98113813.6.But this oxidation catalyst filter agent has activity to acetylene molecule, therefore can not be used for acetylene gas sensor, and the used sensor of On-Line Monitor Device of Gas requires to differ greatly in the structure of this sensor and the oil in addition.
Summary of the invention
To the defective that existing acetylene gas sensor exists, the present invention will provide a kind of good reliability, selectivity height, can carry out the long-term all-in-one micro feulcell prototype acetylene gas sensor of on-line monitoring continuously to the acetylene gas in the high voltage electric equipment insulating oil.
For solving the problems of the technologies described above; The present invention is provided for monitoring the gas sensor of gas content in the insulating oil; The integrated casing that comprises hollow structure is equipped with combined type gas-oil separation film and is used for the air-sensitive parts of sensing gas with the output corresponding electric signal in said shell; Wherein, the selectivity electro-catalysis filtering layer that is used for filtering interfering gas also is housed between said combined type gas-oil separation film and air-sensitive parts; First end of said shell is used for being connected with oil-filled electrical equipment; The body membrane one side of said combined type gas-oil separation film is towards said first end; Said air-sensitive parts then are contained in the porous metals sintered sheets one side of said gas-oil separation film, and outwards export electric signal through metal lead wire.
Said combined type gas-oil separation film is formed by macromolecule body membrane and porous metals sintered sheets high temperature sintering, allows gas molecule (comprising acetylene) to see through, but does not allow insulating oil to see through.The outstanding feature of combined type gas-oil separation film is to have the opposing malleation, the ability of negative pressure and varying environment temperature.Said macromolecule body membrane can be polytetrafluoroethylene (PTFE), gathered one or more the combination in PVF (PVDF), teflon/hexafluoropropylene copolymer (PFEP), teflon/perfluor third vinyl ether copolymers (PFA), tygon/TFE copolymer (PETFE), silicon rubber (SR) or the silicon fluoride rubber (FSR).Preferably adopt the mode of lamination (Lamination) combination.
In order to obtain being used for monitoring the selectivity acetylene gas sensor of insulating oil acetylene gas concentration; Among the present invention; Said air-sensitive parts are the miniature acetylene fuel cell of selectivity preferably, comprises anode, anode metal lead-in wire, electrolyte, negative electrode and cathodic metal lead-in wire.Anode in the said fuel cell and negative electrode are preferably same porous gas diffusive electrode (symmetry electrode); Active component wherein, promptly eelctro-catalyst is two or more the combination in gold (Au), ruthenium (Ru), rhodium (Rh), platinum (Pt), palladium (Pd), silver (Ag), the iridium (Ir); And wherein the weight content of gold (Au) is 10-99%.
To said selectivity acetylene gas sensor, among the present invention, a side of said electro-catalysis filtering layer is near said gas-oil separation film, and opposite side is near said fuel cell; Said electro-catalysis filtering layer preferably adopts the method preparation of gas-diffusion electrode, and its active component comprises two or more the combination in gold (Au), ruthenium (Ru), rhodium (Rh), platinum (Pt), palladium (Pd), silver (Ag), the iridium (Ir); And wherein the weight content of rhodium (Rh) is 10-100%.
When selectivity acetylene fuel cell of the present invention uses separately; When promptly not having said electro-catalysis filtering layer; Cross sensitivity summation to other interference gas has about 5%; Though be deposited on the electrode on the Nafion with respect to pure Au, its cross sensitivity has had tangible improvement, when using separately, still can not satisfy the requirement of on-line monitoring fully.The present invention adopts selectivity electro-catalysis filtering layer to reduce the relative concentration of interference gas in the mixed gas; The efficient that filtering layer consumes interference gas reaches more than 80%; Therefore on the whole, the cross sensitivity summation of interference gas has really realized the selectivity of acetylene gas is detected less than 1%.
Therefore; The present invention passes through said gas-oil separation film; The optimization of selectivity acetylene fuel cell and selectivity electro-catalysis filtering layer cooperates, and has prepared the all-in-one micro fuel cell acetylene gas sensor that possesses high selectivity, said various environmental pressures of all-in-one micro fuel cell acetylene gas sensor ability and temperature variation; Can in the interference gas environment of high concentration accurately stably detect low concentration acetylene gas content.
Description of drawings
Fig. 1 is the decomposition texture synoptic diagram of the gas sensor in a preferred embodiment of the invention;
Fig. 2 is the response curve of acetylene gas sensor shown in Figure 1 to acetylene, hydrogen, carbon monoxide and ethene.
Among Fig. 1, the 1st, combined type gas-oil separation film, the 2nd, electro-catalysis filtering layer, the 20th, integrated casing, the 201st, outer cover fixing threaded hole, the 21st, the screw, the 22nd of integrated casing upper end, rubber seal, the 23rd, fixing metal circle, the 24th, fixed screw, 25 anodes, the 251st, anode metal lead-in wire, the 26th, whole fuel cell, the 27th, negative electrode, the 271st, cathodic metal lead-in wire, the 29th, battery cover, the 33rd, casing cover, the 331st, Signal connector, the 332nd, ventilated membrane, the 333rd, capillary equalizing port, the 34th, casing cover screw, the 35th, bolt, the 36th, screw, 37 are second O-ring seals.
Embodiment
One, the structure of gas sensor
The structure of the acetylene gas sensor in a preferred embodiment of the invention is as shown in Figure 1.Wherein, be provided with external thread, can be directly connected in the internal thread on transformer valve or the valve flanges dish (not drawing in the drawings) in the lower end of integrated casing 20.Also be provided with fixing threaded hole 201 on the disk of integrated casing 20, this fixing threaded hole 201 is used for fixing signal processing unit and the outer cover (do not mark) supporting with sensor.Signal processing unit and outer cover had both guaranteed that sensor signal do not have distance and transmit, and had guaranteed that also sensor avoids environment and climate effect, thereby had guaranteed that the electric signal that sensor produces is interference-free.
As can be seen from Figure 1, the sealing between the inner chamber of combined type gas-oil separation film 1 and shell 20 is accomplished with oil resistant viton seal ring (i.e. first O-ring seal) 22, fixing metal circle 23 and fixed screw 24.
Used combined type gas-oil separation film 1 is that the cementing agent bonding of highly-breathable forms through having very between macromolecule body membrane and the porous metals sintered sheets in the present embodiment, and its manufacturing process has detailed description on Chinese patent CN200310111953
7 prospectus.This combined type gas-oil separation film allows gas molecule (comprising acetylene) to see through, but does not allow insulating oil to see through.The outstanding feature of combined type gas-oil separation film is to have the opposing malleation, the ability of negative pressure and varying environment temperature.Said macromolecule body membrane can be polytetrafluoroethylene (PTFE), gathered one or more the combination in PVF (PVDF), teflon/hexafluoropropylene copolymer (PFEP), teflon/perfluor third vinyl ether copolymers (PFA), tygon/TFE copolymer (PETFE), silicon rubber (SR) or the silicon fluoride rubber (FSR).Preferably adopt the mode of lamination (Lamination) combination.
Macromolecule body membrane surface in the gas-oil separation film should be towards the oil stream of transformer; Thereby the failure gas that is dissolved in the oil can be spread and desorption through absorption, dissolving on the body membrane surface; Arrive the another side of gas-oil separation film, and the air-sensitive parts of gas sensor (being micro fuel cell) are just installed this one side of porous metals sintered sheets of gas-oil separation film.
During installation, the distance between gas-oil separation film surface and the air-sensitive parts should preferably less than 2mm, thereby can shorten the sensor's response time less than 5mm, improves the analytical performance of monitoring device.
In the present embodiment, fuel cell 26 is made up of anode 25, anode metal lead-in wire 251, electrolyte (not marking), negative electrode 27 and cathodic metal lead-in wire 271 etc.And be fixed on the fixing metal circle 23 through battery cover 29 and screw 36, in the shell 20 of finally packing into.Wherein, anode in the fuel cell and negative electrode are preferably same porous gas diffusive electrode, and active component wherein is two or more the combination in gold (Au), ruthenium (Ru), rhodium (Rh), platinum (Pt), palladium (Pd), silver (Ag), the iridium (Ir); And wherein the weight content of gold (Au) is 10-99%.On Chinese patent CN200410028129.X prospectus, detailed description is arranged about the eelctro-catalyst of fuel cell use and the preparation method of porous gas diffusive electrode.
After failure gas in the transformer oil (containing acetylene) is separated from porous metals sintered sheets one side of gas-oil separation film 1; Arrive electro-catalysis filtering layer 2; Most of H2 and CO oxidation on said electro-catalysis filtering layer 2 that sees through gas-oil separation film 1, most acetylene gas then continue toward fuel cell 26 diffusions.One side of electro-catalysis filtering layer 2 is near said gas-oil separation film, and opposite side is near fuel cell; The electro-catalysis filtering layer adopts carbon as carrier, and its active component comprises two or more the combination in gold (Au), ruthenium (Ru), rhodium (Rh), platinum (Pt), palladium (Pd), silver (Ag), the iridium (Ir); And wherein the weight content of rhodium (Rh) is 10-100%.About the eelctro-catalyst that uses in the electro-catalysis filtering layer and the preparation method of porous gas diffusive electrode, on Chinese patent CN200410028129.X prospectus, detailed description is arranged.
Gas arrives the anode 25 of fuel cell 26, and oxidation discharges electronics on anode 25, and concrete reaction equation is following
Anode: C
2H
2+ 4H
2O → 2CO
2+ 10H
++ 10e
-
Negative electrode: 4H
++ O
2+ 4e
-→ 2H
2O
Overall reaction: 2C
2H
2+ 5O
2=4CO
2+ 2H
2O
The electric signal that above-mentioned reaction produced is through passing to external signal receiving trap (not drawing in the drawings) with the anode 25 tight metal lead wires 251 (platinum filament or spun gold) that contact through electric signal joint 331.Proton after anodic oxidation (H+) can arrive the negative electrode 27 of fuel cell through electrolyte, and is combined into water with oxygen atom in cathodic reduction.The electric signal of negative electrode 27 is through passing to the external signal receiving trap with metal lead wire 271 (platinum filament or spun gold) that negative electrode closely contacts; And through external element and metal lead wire 251 composition closed-loop paths (not drawing in the drawings), current in loop intensity is directly proportional with acetylene gas concentration.
As can be seen from Figure 1, ventilated membrane 332 is housed on casing cover 33, this ventilated membrane 332 has two effects, and first protection fuel cell avoids outside foul, dust or water droplet to get into; It two is to be used for seeing through oxygen, and prolongs the life-span of fuel cell.In the present embodiment; Ventilated membrane 332 optional usefulness possess the polymeric membrane of the ventilative ratio of higher oxygen gas/water vapour, and the ventilative ratio of its oxygen steam generally is higher than 0.03, like teflon, tygon, polypropylene screen; Preferably use poly tetrafluoroethylene, its thickness is between 5 to 100 μ m.
A capillary equalizing port 333 also is housed on the casing cover 33 in Fig. 1, and the effect of this equalizing port is the pressure differential that balance sensor inner chamber and outside cause owing to temperature variation, and the aperture of said capillary equalizing port 333 is smaller or equal to 0.1mm, and height is more than or equal to 2mm.
After packing into above-mentioned each parts in the shell 20, through inserting the bolt 35 of screw 21,34, can casing cover 33 be fixed on the upper end of shell 20 again.Casing cover 33 passes through the sealing between 37 realizations of second O-ring seal and the shell 20, thereby the inside of whole sensor and extraneous seal (but permeable oxygen and balance external and internal pressure).
The structure that it is emphasized that the above integrated gas sensor is not only applicable to the sensing acetylene gas, and the insider is perfectly clear, and it is equally applicable to other gas sensor, comprises the feulcell prototype gas sensor that is used to detect other gas.
Two, the performance test of gas sensing
Adopt the described structure of Fig. 1, combine the embodiment 2 of back again, process the selective gas sensor that contains the electro-catalysis filtering layer, and be used for the gas sensing experiment.
Test condition is: at ambient temperature, import cleaned air earlier, import the H that contains 50 μ L/L more successively respectively
2, the CO of 500 μ L/L, the C of 100 μ L/L
2H
4, and the C of 15 μ L/L
2H
2Gas appearance (the gas concentration here has been converted into oil dissolved gas concentration).The pull-up resistor of sensor is 2k ohm.Test findings is as shown in Figure 2:
When importing common cleaned air, the signal of sensor approaches zero;
In the time of the 10th minute, import the H of 50 μ L/L
2(A point), this moment, the signal changing value of sensor approached zero;
In the time of the 30th minute, append the CO (B point) of 500 μ L/L, this moment, the signal changing value of sensor approached zero;
In the time of the 50th minute, append the C of 100 μ L/L again
2H
4(C point), this moment, the signal changing value of sensor approached zero;
In the time of the 70th minute, append the C of 15 μ L/L again
2H
2(D point), this moment, the signal of sensor increased sharply, and within about 50 minutes, rose to summit (E point), and its changing value is about 16 μ v;
In the time of the 135th minute, import normal air (E point) again, the signal of sensor is reduced to rapidly and approaches zero and settle out;
In the time of the 210th, 230 and 250 minute, import the H of 50 μ L/L once more
2The C of the CO of (A ' point), 500 μ L/L (B ' point) and 100 μ L/L
2H
4(C ' point), the signal changing value of sensor approaches zero;
In the time of the 270th minute, append the C of 15 μ L/L again
2H
2(D ' point), this moment, the signal of sensor increased sharply, and was raised to 16 μ v to E ' point.
So repeat, sensor has good response as shown in Figure 2 and repeatability.
In below the Comparative Examples and embodiment, probe temperature is a room temperature, and the gained electrode is cut into the electrode that diameter is 11mm, and makes the feulcell prototype acetylene gas sensor; Fuel cell in the Comparative Examples in 1 and 2 with the proton film as electrolyte, other feulcell prototype acetylene gas sensor with sulfogel as electrolyte.Asymmetric electrode is meant that the anode of electrolyte both sides uses different eelctro-catalysts with negative electrode, and symmetry electrode is meant that the anode of electrolyte both sides and negative electrode use identical eelctro-catalyst.
Three, the asymmetric electrode of Nafion deposition Au/Pt--Comparative Examples 1
With Takenaka-Torikai (T-T) method (specifically can be referring to Raymond Liu, Wei-Hwa Herand Peter S.Fedkiw, J.Electrochem.Soc.; 1992, Vol.139, No.1; Pp15-23) deposit crystallite Au and Pt eelctro-catalyst respectively on Nafion117 proton film (du pont company production) two sides; Obtain asymmetric electrode, wherein, at the about 6mg/cm of anode surface deposition
2Au, at the about 8mg/cm of cathode plane deposition
2Pt, the asymmetric electrode that obtains is processed the feulcell prototype acetylene gas sensor again, and test is to the response of acetylene and other gases, the result sees table 1.
Table 1
Can find out, report in the relative sensitivity of ethene and the document 14% very near (referring to PeterC.Hauser, Amperometric Gas Sensors of High Sensitivity, Electroanalysis, 1999,11, No10-11, pp782-787).
Four, the asymmetric electrode-Comparative Examples 2 of Nafion deposition Au/Nafion/Pt that contains the electro-catalysis filtering layer
Add in the anode front of the feulcell prototype acetylene gas sensor described in the Comparative Examples 1 and to put the electro-catalysis filtering layer (Rh:Ru=20:80, wherein the carrying capacity of Rh is 0.2mg/cm
2), make gas before being diffused into anode earlier through said electro-catalysis filtering layer, and under the condition identical, test response to acetylene and other gases with Comparative Examples 1, the result sees table 2.
Table 2
Can find out by above-mentioned Comparative Examples 1 and 2; When the electro-catalysis filtering layer; The cross sensitivity of CO and H2 descends to some extent, but the cross sensitivity of C2H4 does not change basically, therefore still can't realize under the high interference gas concentration environment C2H2 being carried out the detection of high selectivity.
Five, the pure Au symmetry electrode of carbon back--Comparative Examples 3
Because the activity of pure Au electrode pair oxygen is very little, so (wherein the carrying capacity of Au is 5mg/cm with the pure Au symmetry electrode of carbon back
2) though the fuel cell anode that obtains has enough activity to acetylene, because the restriction of negative electrode can't obtain enough detection sensitivities, test result is seen table 3.
Table 3
Six, carbon back Au:Ru alloy symmetry electrode--embodiment 1
(Au:Ru=20:80, wherein the carrying capacity of Au is 0.2mg/cm with the pure Au in the carbon back Au:Ru alloy replacement Comparative Examples 3
2) symmetry electrode, processing the feulcell prototype acetylene gas sensor, and test response acetylene and other gases, the result sees table 4.
Table 4
Relatively Comparative Examples 1 can be found out with enforcement 1; The sensor that the asymmetric electrode of Au/Nafion/Pt that the sensor of being processed by carbon back Au:Ru alloy symmetry electrode deposits than Nafion is processed has higher accuracy when detecting acetylene; Just Au:Ru alloy symmetry electrode has obviously reduced the cross sensitivity of other gases, especially the cross sensitivity of ethene is almost reduced to 0.However, the cross sensitivity of H2 and CO still can not be ignored.
Seven, contain the electro-catalysis filtering layer Au:Ru alloy symmetry electrode--embodiment 2
Add in the anode front of the feulcell prototype acetylene gas sensor described in the embodiment 1 and to put the electro-catalysis filtering layer (Rh:Ru=20:80, wherein the carrying capacity of Rh is 0.2mg/cm
2), make gas before being diffused into anode earlier through said electro-catalysis filtering layer, and under the condition identical, test response to acetylene and other gases with embodiment 1, the result sees table 5.
Table 5
Can find out when containing the electro-catalysis filtering layer; Sensor has high accuracy when detecting acetylene; The cross sensitivity sum of other interference gas of electrode pair is less than 1%, can be implemented in fully in the environment of high interference gas and optionally detects trace acetylene.
Eight, electro-catalysis filtering layer efficient
Can find out that from the comparing result of embodiment 1 and embodiment 2 the electro-catalysis filtering layer reaches 90% to the filter effect of H2, the filter effect of CO is reached 86%, all surpass 80%.But then, in Comparative Examples 1 and the Comparative Examples 2, same electro-catalysis filtering layer is to H
2Have only 37% and 50% with the filter effect of CO, well below 80%.Therefore fuel cell has play a part suitable to the catalytic activity of interference gas.For this reason; Difference electricity consumption oxidation catalyst filter layer; Carbon back Au:Ru alloy symmetry electrode (embodiment 1) and the Nafion deposition asymmetric electrode of Au/Pt (Comparative Examples 1) are processed the fuel cell gas sensor, and test its sensitivity to interference gas (activity), and test condition is identical with Comparative Examples and embodiment.The electro-catalysis filtering layer is as active benchmark (equaling 1), and its relative sensitivity (specific activity) result sees table 6.
Table 6
In fact, the oxidation reaction of gas on electro-catalysis filtering layer or fuel cell is a process of vying each other, so the relative activity of catalyzer has determined the efficient of filtering layer.At first, the electro-catalysis filtering layer must be greater than the activity (as shown in table 1) of fuel cell to interference gas to the activity of interference gas, and secondly, carbon back Au:Ru alloy symmetry electrode (embodiment 1) is to H
2Has only the electro-catalysis filtering layer respectively to H with the activity of CO
2With 1/20 and 1/45 of the activity of CO, also much smaller than the asymmetric electrode pair H of Nafion deposition Au/Pt
2Activity with CO.
Therefore when selectivity electro-catalysis filtering layer and fuel cell be: H to the specific activity of interference gas
2More than or equal to 20, CO was more than or equal to 45 o'clock, and its filtration efficiency can surpass 80%.
Claims (8)
1. gas sensor that is used for monitoring the insulating oil gas content comprises and combined type gas-oil separation film is housed the integrated casing of hollow structure and is used for the air-sensitive parts of sensing gas with the output corresponding electric signal in said shell;
It is characterized in that, the selectivity electro-catalysis filtering layer that is used for filtering interfering gas also is housed between said combined type gas-oil separation film and air-sensitive parts;
First end of said shell is used for being connected with oil-filled electrical equipment; The body membrane one side of said combined type gas-oil separation film is towards said first end; Said air-sensitive parts then are contained in the porous metals sintered sheets one side of said gas-oil separation film, and outwards export electric signal through metal lead wire.
2. the gas sensor that is used for monitoring the insulating oil gas content according to claim 1 is characterized in that,
Said combined type gas-oil separation film is to be formed by macromolecule body membrane and porous metals sintered sheets high temperature sintering;
Said macromolecule body membrane is polytetrafluoroethylene (PTFE), gathered one or more the combination in PVF (PVDF), teflon/hexafluoropropylene copolymer (PFEP), teflon/perfluor third vinyl ether copolymers (PFA), tygon/TFE copolymer (PETFE), silicon rubber (SR) or the silicon fluoride rubber (FSR).
3. the gas sensor that is used for monitoring the insulating oil gas content according to claim 1 is characterized in that,
Said air-sensitive parts are the miniature acetylene fuel cells of selectivity, comprise anode, anode metal lead-in wire, electrolyte, negative electrode and cathodic metal lead-in wire;
Said anode and negative electrode are same porous gas diffusive electrode, and active component wherein is two or more the combination in gold (Au), ruthenium (Ru), rhodium (Rh), platinum (Pt), palladium (Pd), silver (Ag), the iridium (Ir); And wherein the weight content of gold (Au) is 10-99%.
4. the gas sensor that is used for monitoring the insulating oil gas content according to claim 3 is characterized in that, a side of said selectivity electro-catalysis filtering layer is near said gas-oil separation film, and opposite side is near said fuel cell;
Said electro-catalysis filtering layer adopts porous gas diffusive electrode, and its active component comprises two or more the combination in gold (Au), ruthenium (Ru), rhodium (Rh), platinum (Pt), palladium (Pd), silver (Ag), the iridium (Ir); And wherein the weight content of rhodium (Rh) is 10-100%.
5. the gas sensor that is used for monitoring the insulating oil gas content according to claim 4; It is characterized in that said selectivity electro-catalysis filtering layer is higher than the activity of selectivity acetylene fuel cell to interference gas itself to the activity of other interference gas outside the acetylene.
6. the gas sensor that is used for monitoring the insulating oil gas content according to claim 5; It is characterized in that; Said selectivity electro-catalysis filtering layer reaches more than 80% the filtration efficiency of other interference gas outside the acetylene; Wherein selectivity electro-catalysis filtering layer and fuel cell to the specific activity of interference gas are: H2 is more than or equal to 20, and CO is more than or equal to 45.
7. according to each described gas sensor that is used for monitoring the insulating oil gas content among the claim 1-6, it is characterized in that,
The inner chamber of said shell is provided with step; The body membrane one side of said combined type gas-oil separation film is contained on the said step through first O-ring seal; Said gas-oil separation film is fixed on the said step by a fixing metal circle, and oil infiltrates and contacts with said air-sensitive parts from said first end when preventing to use;
Said fuel cell and electro-catalysis filtering layer are passed through screw retention to said fixing metal circle by the battery cover of a central openings;
Second end at said shell is provided with a casing cover; The sealed electrical Signal connector that is connected with the external signal receiving device is equipped with in the central authorities of said shell; Near the capillary equalizing port that there is a ventilated membrane at sealed electrical Signal connector place and is used for said inner chamber of balance and external pressure difference, realize sealing through second O-ring seal between said casing cover and the said shell;
Said anode metal lead-in wire and cathodic metal lead-in wire are connected respectively to the relevant position of said electric signal joint;
Said ventilated membrane is processed by the polymeric membrane that possesses the ventilative ratio of higher oxygen/water vapour, and the ventilative ratio of its oxygen steam is higher than 0.03, and its thickness is between 5-100 μ m, and said polymeric membrane can be teflon, tygon or polypropylene screen;
The aperture of said capillary pressure equalizing port is smaller or equal to 0.1mm, and height is more than or equal to 2mm.
8. the gas sensor that is used for monitoring the insulating oil gas content according to claim 7; It is characterized in that; First end of said shell is provided with and is used for the external thread that is connected with oil-filled electrical equipment; Be provided with an annulus on said externally threaded top, on said annulus, be provided with the fixed screw holes that is used to install signal processing unit and outer cover.
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| CN2007100755957A CN101363813B (en) | 2007-08-10 | 2007-08-10 | Gas sensor for monitoring gas content in insulating oil |
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| CN2007100755957A CN101363813B (en) | 2007-08-10 | 2007-08-10 | Gas sensor for monitoring gas content in insulating oil |
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| CN101363813A CN101363813A (en) | 2009-02-11 |
| CN101363813B true CN101363813B (en) | 2012-05-30 |
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| FR2978828B1 (en) * | 2011-08-02 | 2013-09-06 | Snecma | MULTI-ELECTRODE SENSOR FOR DETERMINING THE GAS CONTENT IN A DIPHASIC FLOW |
| DE102012205398A1 (en) * | 2012-04-03 | 2013-10-10 | Robert Bosch Gmbh | A sensor device and method for analyzing a component of a fluid |
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| CN109459560A (en) * | 2018-12-27 | 2019-03-12 | 日新电机（无锡）有限公司 | A kind of high-voltage parallel capacitor device and power equipment |
| CN110455988B (en) * | 2019-07-15 | 2022-02-08 | 山东五岳电器有限公司 | Sensor array calculation method and system based on gas content in transformer insulating oil, monitor and monitoring method |
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| CN113933357A (en) * | 2021-11-18 | 2022-01-14 | 北京化工大学 | Application of polytetrafluoroethylene film in gas sensor, metal pipe cap for gas sensor and nitrogen dioxide sensor |
| CN114509472B (en) * | 2022-04-19 | 2022-07-19 | 佛山速敏智能仪器科技有限公司 | Gas detection system, detection method and gas detection device in transformer oil |
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