CN103336070B - The pick-up unit of sulfur-bearing failure gas component and method in a kind of quantitative detection sulfur hexafluoride electrical equipment - Google Patents
The pick-up unit of sulfur-bearing failure gas component and method in a kind of quantitative detection sulfur hexafluoride electrical equipment Download PDFInfo
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- 229910018503 SF6 Inorganic materials 0.000 title claims abstract description 113
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229960000909 sulfur hexafluoride Drugs 0.000 title claims abstract description 104
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 86
- 239000011593 sulfur Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000001514 detection method Methods 0.000 title claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 23
- 238000012360 testing method Methods 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims description 143
- 239000001307 helium Substances 0.000 claims description 19
- 229910052734 helium Inorganic materials 0.000 claims description 19
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 238000004817 gas chromatography Methods 0.000 claims description 13
- 239000012159 carrier gas Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000002371 helium Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 13
- 239000012491 analyte Substances 0.000 abstract description 5
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000003822 preparative gas chromatography Methods 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000013459 approach Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
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- 230000008676 import Effects 0.000 description 1
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- 239000011810 insulating material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 230000000284 resting effect Effects 0.000 description 1
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- 150000004763 sulfides Chemical class 0.000 description 1
- -1 sulphur compound Chemical class 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a kind of pick-up unit of quantitative detection sulfur hexafluoride electrical equipment fault gas component, comprise separation chromatography post, thermal conductivity detector (TCD) and sulfur chemiluminescent detector, described separation chromatography post is connected with thermal conductivity detector (TCD), thermal conductivity detector (TCD) is connected with sulfur chemiluminescent detector by a six-way valve, the sample outlet end of described thermal conductivity detector (TCD) is connected with the port 2 of six-way valve, the test entrance point of described sulfur chemiluminescent detector is connected with six-way valve port 3, the switch controlling six-way valve makes the connection of its conducting thermal conductivity detector (TCD) and sulfur chemiluminescent detector when sample introduction, when being separated SF6, disconnect thermal conductivity detector (TCD) to be connected with sulfur chemiluminescent detector, discharge SF6.The present invention is the open method quantitatively detecting sulfur hexafluoride electrical equipment fault gas component also.SF6, before carrying out the detection of SF6 analyte, discharges by these apparatus and method, reduces SF6 to the impact of testing result, improves the detection sensitivity of SF6 analyte.
Description
Technical field
The present invention relates to a kind of pick-up unit of sulfur hexafluoride electrical equipment fault gas, particularly relate to the pick-up unit of sulfur-bearing failure gas component in a kind of quantitative detection sulfur hexafluoride electrical equipment.The invention still further relates to the method adopting this device quantitatively to detect sulfur-bearing failure gas component in sulfur hexafluoride electrical equipment.
Background technology
Sulfur hexafluoride (SF6) is used as the insulating material of high-voltage switch gear, large variable quantity and pressure device, high-tension cable and gas in electrical industry.When these device fails, can discharge, and sulfur hexafluoride gas can issue solution estranged in high-temperature electric arc effect, its analyte comprises sulfocompound and other compounds etc., and sulfocompound comprises vikane (SO
2f
2), cos (COS), sulfuretted hydrogen (H
2s), carbon disulphide (CS
2), sulphuric dioxide (SO
2) etc., so quantitatively these sulfur hexafluoride decomposition products of detection can be used for fault and the defect of diagnosing electrical equipment.
At present, the quantitative detecting method of sulfur hexafluoride decomposition product is also very immature, is mainly reflected in: sulfur hexafluoride decomposition product composition is complicated, and each component often concentration is very low, and sulfur hexafluoride background value is very high, to sulfur hexafluoride decomposition product as vikane (SO
2f
2), cos (COS), sulfuretted hydrogen (H
2s), carbon disulphide (CS
2), sulphuric dioxide (SO
2) etc. separation and qualitative, quantitative bring great difficulty.
Current, the analytical approach being applied to sulfur hexafluoride electrical equipment fault gas mainly contains vapor-phase chromatography, GC-MS(gas chromatography-mass spectrography), infra-red sepectrometry, electrochemical methods, detects tube method etc.
1. detect tube method
Detect tube method mainly for SO
2detect with HF, SO
2be all highly acid material with HF, they can react with NaOH, simultaneously SO
2indicator can be impelled to change color with iodine generation chemical reaction again, the length of variable color is directly proportional to corresponding material concentration, so its concentration value reads from the figure of detector tube or marker tape easily.Because HF adopts acid-base reaction, SO
2adopt redox reaction, both reaction mechanisms are different, so these two kinds of materials do not need to be separated.But this method is easily subject to temperature, humidity and the impact of resting period, and effect is not detected to other main decomposition gas, SF6 discharge decomposed gas component situation can not be reacted comprehensively.
2. gas sensor method
The method mainly utilizes chemical gas sensitive device to detect gas composition.Chemistry gas sensor utilizes to have to the shape of tested gas or molecular structure the function (receptacle function) that selectivity captures and the function (converter function) chemical quantity of capturing effectively being converted into electric signal carrys out work.When tested gas is adsorbed to gas sensory surface, its resistance value can change, thus obtains the content of this gas.Gas sensing method has that detection speed is fast, and efficiency is high, can with computing machine with the use of thus realize the outstanding advantages such as automatic on-line checkout and diagnosis, but also exist and detect the shortcomings such as gas composition is single.At present, the mainly more common gas of the gas that can detect by gas sensor method is both at home and abroad as SO
2, HF and H
2s, and to important gas composition SO
2f
2, SOF
2, SF
4, SOF
4and CF
4then helpless.In addition, there is interference problem between component as H in it
2sensor can to SO
2there is effect and the problem such as HF sensor serviceable life is short.
3. electrochemical process
Utilize electrochemical method, use electrode and electrolytic solution to detect gas, but only can measure hydrolyzable fluoride and acidity in cracked gas, cannot judge the type of analyte and concentration.And instrument exists zero point drift, poor stability, affects testing result.
4. infra-red sepectrometry
Infra-red sepectrometry is based on the detection method of gas to the absorption of infrared light.It is qualitative is according to material to the wave number of infrared Absorption and waveform, and its quantitative foundation is the degree of material to infrared Absorption.Except monoatomic molecules and homonuclear molecule, as O
2, N
2, outside Ne etc., nearly all chemical substance all has absorption in infrared light district.The method compared with vapor-phase chromatography and GC-MS(gas chromatography-mass spectrography), analysis speed soon, do not destroy sample gas, normal temperature can be realized under detect.But when the analysis of sulfur hexafluoride electrical equipment fault gas component, the infrared absorption peak of sulfur hexafluoride and its decomposition product, as SO
2, F
2, CF
4, SO
2infrared absorption peak exist overlapping, there is interference mutually, so quantivative approach is complicated, and detection limit is also in ppm level, generally can only reach 5 μ L/L ~ 10 μ L/L, detection sensitivity can not meet the testing requirement of sulfur-bearing failure gas component in sulfur hexafluoride electrical equipment.
5. GC-MS(gas chromatography-mass spectrography)
Mass spectrum is to one of the strongest method that pure material is identified.GC-MS(gas chromatography-mass spectrography) utilizes the sample gas of chromatographic process to complicated components to carry out separation also quantitatively, then carry out qualitative analysis by mass spectrum to each component.The method combines the advantage of gas chromatography on quantitatively and the mass spectrum advantage on qualitative.But because mass spectrometer system is mainly for the analysis of pure material, and its signal value is extremely unstable, need often correct, work comparatively loaded down with trivial details.
6. vapor-phase chromatography
Vapor-phase chromatography can analyze the multicomponent mixture with separate complex, and can with multiple analytical instrument coupling, being a kind of strong analysis means, having bright prospects, is also the popular method of sulfur-bearing failure gas component in present analysis sulfur hexafluoride electrical equipment.
The advantage analyzing sulfur hexafluoride electrical equipment fault gas component by vapor-phase chromatography is, it is a kind ofly first separated the method detected afterwards, effectively can avoid the cross jamming of various component.In addition, gas chromatography can with multiple analytical instrument coupling, as mass spectrometry (GC-MS), gas chromatography and FTIR spectrum coupling (GC-FTIR), can the advantage of comprehensive various analytical instrument comparatively comprehensively analyze.
Be applied to the vapor-phase chromatography that in sulfur hexafluoride electrical equipment, sulfur-bearing failure gas component detects, classify according to the kind of detecting device, mainly contain thermal conductance (TCD) method, helium ionization detector (PDD) method and thermal conductance-flame luminosity series connection (TCD-FPD) method etc.
1. thermal conductance (TCD) method: adopt thermal conductivity detector (TCD) (TCD) to detect the gas that gas chromatography is separated.Thermal conductivity detector (TCD) almost has response to all substances, and versatility is good, and the range of linearity is wide.Its quantitative principle has different thermal conductivity coefficients based on different material, and quantivative approach is simple, is mainly applicable to the detection of the new gas of sulfur hexafluoride.But this detection method sensitivity is lower, particularly to H
2s, SO
2, SO
2f
2more weak etc. gas detection signals.And according to current experience, the detection of this several gas all plays an important role for the fault of sulfur hexafluoride electrical equipment or the judgement of Hidden fault.
2. thermal conductance-flame luminosity series connection (TCD-FPD): namely series connection uses thermal conductivity detector (TCD) (TCD) and flame photometric detector (FPD) (FPD).Flame photometric detector (FPD) (FPD) is that one has high selectivity and highly sensitive mass flow rate sensitive detector to phosphorus, sulphur compound.TCD-FPD method introduces FPD, overcomes when using merely TCD H
2s, SO
2and SO
2f
2the shortcoming that sulfides sensitivity is not high, but for helium ionization detector and sulfur chemiluminescent detector, its sensitivity is still not high.And the response of FPD is nonlinear response, quantivative approach is comparatively complicated.
3. helium ionization detector (PDD) method: helium ionization detector (PDD) can to the substance responds of the overwhelming majority, and along with the response of increase to fixed gas of fixed current be front, versatility is good.Helium ionization detector has high sensitivity simultaneously, can test in the scope of low ppb level.When measuring the concentration of minimum detectable quantity 5 orders of magnitude, result is still linear, has the good range of linearity.But it is the SO of spirit at quantitative SF6
2f
2, COS and H
2during S, the peak shape of SF6 has a strong impact on the peak shape of this several material, and its quantitative result allows people suspect.
In sum, the sensitivity of vapor-phase chromatography thermal conductivity detector (TCD) is not high, flame photometric detector (FPD) nonlinearity, and sensitivity can not meet fault analyte testing requirement; Helium ionization detector cannot accurate quantitative analysis SF6 be the SO of spirit
2f
2, COS and H
2s gas.
Summary of the invention
An object of the present invention is the pick-up unit providing sulfur-bearing failure gas component in a kind of quantitative detection sulfur hexafluoride electrical equipment.This device has good separating effect to each sulfur-bearing failure gas component under sulfur hexafluoride (SF6) background, and before quantitatively detecting, can be discharged by SF6, reduces SF6 to sulfur-bearing failure gas component, i.e. COS, H
2s, SO
2f
2, CS
2, SO
2and the testing result impact of other sulfur component, improve the detection sensitivity of sulfur-bearing failure gas component.
Two of object of the present invention is to provide the method adopting said apparatus quantitatively to detect sulfur-bearing failure gas component in sulfur hexafluoride electrical equipment.COS, H in the method energy accurate quantitative analysis sulfur-bearing failure gas
2s, SO
2f
2, CS
2, SO
2and other sulfur component.
First object of the present invention is achieved through the following technical solutions: the pick-up unit of sulfur-bearing failure gas component in a kind of quantitative detection sulfur hexafluoride electrical equipment, it comprises separation chromatography post, thermal conductivity detector (TCD) and sulfur chemiluminescent detector, described separation chromatography post is connected with thermal conductivity detector (TCD), thermal conductivity detector (TCD) is connected with sulfur chemiluminescent detector by a six-way valve, the sample outlet end of described thermal conductivity detector (TCD) is connected with the port 2 of six-way valve, the test entrance point of described sulfur chemiluminescent detector is connected with six-way valve port 3, the switch controlling six-way valve makes its port 2 when sample introduction be communicated with port 3, the connection of conducting thermal conductivity detector (TCD) and sulfur chemiluminescent detector, disconnect thermal conductivity detector (TCD) when being separated SF6 to be connected with sulfur chemiluminescent detector, port 2, port 1, port 5 and port 6 are communicated with formation SF6 discharge-channel successively, discharge SF6.
To refer to during sample introduction of the present invention in sulfur hexafluoride electrical equipment fault gas sample introduction process and sulfur-bearing failure gas component to sulfur chemiluminescent detector sample introduction time.Refer to when needing SF6 to separate during described separation SF6, when namely discharging SF6.
The sulfur chemiluminescent detector (SCD) that the present invention uses in waiting mole linear response (corresponding to sulphur atom), not by the interference of most sample substrate, has higher sensitivity (<0.5 pg S/sec) and more than 1 × 10 to sulfide
4linearly.It comprises ozone generator, low pressure reaction pond, double plasma controller, double plasma firing chamber and gas chromatography detector, products of combustion is drawn into a low pressure reaction pond, add excessive ozone herein, the light that subsequent reactions sends is detected by optical filter by the quick photomultiplier of indigo plant and is amplified, and then shows or exports to data handling system.Its principle to react the chemiluminescence reaction occurred based on sulfur monoxide (SO) and ozone that sulfocompound burning produces:
The present invention also comprises carrier gas source, and for carrier gas supply, described carrier gas source is connected with the port 4 of six-way valve.
The present invention also comprises helium gas source, and this helium gas source is connected with separation chromatography post by six-way valve injector, and gas sample to be determined and helium enter separation chromatography post through six-way valve injector and carry out gas separaion.
Separation chromatography post of the present invention adopts the existing separation chromatography post that can be used for sulfur hexafluoride electrical equipment fault gas and be separated at present, comprises capillary column.As one embodiment of the present of invention, described separation chromatography post adopts chromatographic column to be bore 0.32 mm, and length is the gas-pro capillary column of 60 m, as J & W113-4362.
Second object of the present invention is achieved through the following technical solutions: a kind of method of sulfur-bearing failure gas component in quantitative detection sulfur hexafluoride electrical equipment, comprises the following steps:
(1)
divided gas flow component:sulfur hexafluoride electrical equipment fault gas to be measured is passed into separation chromatography post, take helium as mobile phase, gas chromatography separation is carried out to gas composition;
(2)
discharge sulfur hexafluoride:separated gas enters in thermal conductivity detector (TCD) and detects, with the appearance time of sulfur hexafluoride standard items and appearance time region for referencial use, when arrival or the appearance time close to sulfur hexafluoride, open six-way valve, port 2 and port 3 disconnect, port 2, port 1, port 5 are communicated with successively with port 6, discharge sulfur hexafluoride;
(3)
sulfur-bearing failure gas measured portions measures:when arrival or when going out the peak end time close to sulfur hexafluoride, close six-way valve, port 2 is communicated with port 3, the connection of conducting thermal conductivity detector (TCD) and sulfur chemiluminescent detector, residual gas in described thermal conductivity detector (TCD) passes in sulfur chemiluminescent detector and quantitatively detects, and then obtains the content of each sulfur-bearing failure gas component.
The sulfur hexafluoride electrical equipment fault gas taking SF6 as substrate is passed in separation chromatography post SF6, COS, H
2s, SO
2f
2, CS
2and SO
2gas chromatography separation is carried out etc. gas composition.And in component, the appearance time of SF6 the earliest, therefore can change the path of gas by switch six-way valve, release SF6 gas, then residual gas is passed in sulfur chemiluminescent detector (SCD) and detect.Due to before entering SCD, that SF6 gas is complete or major part is removed, make the impact of the background value of SF6 on the signal value of other gas compositions drop to relatively low level, ensure that the accuracy of sulfur chemiluminescent detector (SCD) to the quantitative testing result of each sulfur-bearing failure gas component.The impulse force produced when closing six-way valve makes separation of C OS, H
2s, SO
2f
2, CS
2, SO
2and the retention time of the sulfur-bearing failure gas component such as other sulfur component is delayed, and further ensures the background value of SF6 and being separated of each sulfur-bearing failure gas component peak shape, substantially increases the accuracy of the quantitative testing result of each sulfur-bearing failure gas component.
In step of the present invention (1), the chromatographic condition of gas chromatographic column adopts the existing chromatographic condition for separating of the gas composition in sulfur hexafluoride electrical equipment fault gas at present.For improving the separating effect of the gas composition of sulfur hexafluoride electrical equipment fault gas, as one embodiment of the present of invention, the chromatographic condition of described separation chromatography post is: injector temperature: 200 DEG C, pressure: 25 psi, total flow: 41.498 ml/min, dottle pin purge flow rate: 3 ml/min, shunt mode: shunting 10:1, chromatographic column: J & W113-4362:260 DEG C: 60 m × 320 μm × 0 μm, post case temperature: initial temperature is 60 DEG C, maintains 6 min; Rise to 150 DEG C with the speed of 10 DEG C/min, maintain 2 min.
In step of the present invention (2), the running parameter of thermal conductivity detector (TCD) adopts the running parameter of the gas composition in known detection sulfur hexafluoride electrical equipment fault gas.As one embodiment of the present of invention, the detected temperatures of described thermal conductivity detector (TCD) is 200 DEG C.
The running parameter of step of the present invention (3) sulfur chemiluminescent detector adopts the running parameter of the gas composition in known detection sulfur hexafluoride electrical equipment fault gas.As one embodiment of the present of invention, the detected temperatures of described sulfur chemiluminescent detector is 225 DEG C, SCD gas ions burner temperature 800 DEG C wherein, hydrogen 45 ml/min, air 63 ml/min.
The present invention also comprises the step measuring sulfur hexafluoride and each sulfur-bearing failure gas component appearance time region, concrete operations are: the standard items getting sulfur hexafluoride and each sulfur-bearing failure gas component are made into mixed gas, then gas chromatographic detection is carried out, thus obtain the appearance time region of sulfur hexafluoride and each sulfur-bearing failure gas component, as the reference of subsequent step.The chromatographic condition of gas chromatography is identical with described step (1) chromatographic condition in this step.
the present invention compared with prior art, has following beneficial effect:
(1) detection accuracy is high
Pick-up unit provided by the invention has good separating effect to each sulfur-bearing failure gas component under sulfur hexafluoride (SF6) background.And thermal conductivity detector (TCD) is connected with sulfur chemiluminescent detector by six-way valve in device, gas passage between the two can be changed.Due to SF6 gas occur time the earliest, can by change gas passage be discharged, reduce it to COS, H
2s, SO
2f
2, CS
2, SO
2and the impact of the peak shape of other sulfur component, greatly increase the accuracy of quantitative testing result.
(2) detection sensitivity is high
The present invention is after thermal conductivity detector (TCD), and adopt sulfur chemiluminescent detector to detect further, and the sensitivity of sulfur chemiluminescent detector is ppb rank, detection limit is minimum reaches 0.01 μ L/L.And before entering sulfur chemiluminescent detector, SF6 gas has been removed or major part is removed, and without the interference of SF6 gas, more can substantially increase detection sensitivity.
(3) linear response
The present invention adopts sulfur chemiluminescent detector and thermal conductivity detector (TCD) to be all linear responses, and the range of linearity is wide.
Accompanying drawing explanation
Fig. 1 is installation drawing of the present invention.
Fig. 2 is the opening schematic diagram of the valve of six-way valve 2.
Fig. 3 is the closed condition schematic diagram of the valve of six-way valve 2.
Fig. 4 is that the TCD of each gas composition in sulfur hexafluoride electrical equipment fault gas detects spectrogram.
Fig. 5 is that the SCD of each sulfur-bearing failure gas component detects spectrogram (after removing sulfur hexafluoride).
Embodiment
The present invention will be described to enumerate a part of instantiation below, be necessary to herein means out be following specific embodiment only for the invention will be further described, do not represent limiting the scope of the invention.Some nonessential amendments that other people make according to the present invention and adjustment still belong to protection scope of the present invention.
embodiment one: pick-up unit
In a kind of quantitative detection sulfur hexafluoride electrical equipment as shown in Figure 1, the pick-up unit of sulfur-bearing failure gas component is one embodiment of the present of invention, comprises six-way valve injector 13, separation chromatography post 18, six-way valve 16, thermal conductivity detector (TCD) 15 and sulfur chemiluminescent detector 14.The port 1 ' of six-way valve injector 13 is injection port, and port 2 ' waste gas outlet, port 5 ' are mobile phase import.Port 4 ' is connected with the sample introduction end of separation chromatography post 18, and port 5 ' is then connected with mobile phase transfer pipeline 19, and the air intake opening of mobile phase transfer pipeline 19 is used for being connected with helium gas source, and this pipeline is provided with electronic pressure controller 12.The sample outlet end of separation chromatography post 18 is connected with thermal conductivity detector (TCD) 15, and thermal conductivity detector (TCD) 15 is by six-way valve 16 and sulfur chemiluminescent detector 14.Wherein, the port 2 of six-way valve 16 is injection port, and port 3 is outlet, and port 4 is carrier gas inlet, and port 6 is gas discharge outlet.The sample outlet end of thermal conductivity detector (TCD) 15 is connected with port 2, and port 3 is connected with the sample introduction end of sulfur chemiluminescent detector 14, and port 4 is connected with gas-carrier pipeline 17, and gas-carrier pipeline 10 inlet end establishes the interface for being connected with carrier gas source.
As shown in Figure 2, when port 1 is communicated with port 6 respectively with port 2, port 3 and port 4 and port 5, port 2 and port 3 disconnect, six-way valve 16 is in opening, port 2, port 1, port 5 are communicated with successively with port 6, form SF6 discharge-channel, and gas-carrier pipeline 17 is communicated with sulfur chemiluminescent detector 14.As shown in Figure 3, port 2 is communicated with port 1 with port 5, port 6 respectively with port 3, port 4, and six-way valve 16 is in closed condition, and thermal conductivity detector (TCD) 15 is connected with sulfur chemiluminescent detector 14, port 4, port 5, port 1 are communicated with successively with port 6, form carrier gas discharge-channel.
In the present embodiment, separation chromatography post adopts chromatographic column to be bore 0.32 mm, and length is the gas-pro capillary column of 60 m, concrete J & W113-4362:260 DEG C: 60 m × 320 μm × 0 μm of adopting.
The present embodiment also can comprise carrier gas source, and carrier gas source is connected with the interface of gas-carrier pipeline 17.
The present embodiment also can comprise helium gas source, and helium gas source is then connected with mobile phase transfer pipeline 19 with port 5 '.
embodiment two: detection method
1. determine appearance time and the appearance time region of sulfur hexafluoride and each sulfur-bearing failure gas component
The standard items getting sulfur hexafluoride (SF6) and part sulfur-bearing failure gas component are mixed into mixed gas, and wherein part sulfur-bearing failure gas component comprises vikane (SO
2f
2), cos (COS), sulfuretted hydrogen (H
2s), carbon disulphide (CS
2) and sulphuric dioxide (SO
2), wherein SF6 is balanced gas, SO
2f
2: COS:H
2s:CS
2: SO
2=20:10; 9.65:3.78:10, then gets 0.1ml and detects, and obtains SF6, SO
2f
2, COS, H
2s, CS
2and SO
2appearance time and appearance time region.As seen from Figure 4, SF6 is the gas composition occurred the earliest, and its appearance time, at about 3.2min, goes out the peak end time at about 4min, appearance time region between 3.0 ~ 4.2min, SO
2f
2, COS, H
2s, CS
2and SO
2appearance time be respectively 4.598 min, 5.003 min, 5.087 min, 9.007 min and 10.675 min.
The chromatographic condition of gas chromatography is: injector temperature: 200 DEG C, pressure: 25 psi, total flow: 41.498 ml/min, dottle pin purge flow rate: 3 ml/min, shunt mode: shunting 10:1, chromatographic column: J & W113-4362:260 DEG C: 60 m × 320 μm × 0 μm, post case temperature: initial temperature is 60 DEG C, maintains 6 min; Rise to 150 DEG C with the speed of 10 DEG C/min, maintain 2 min.
The detected temperatures of thermal conductivity detector (TCD) 15 is 200 DEG C.
gas composition in sulfur hexafluoride electrical equipment fault gas to be measured quantitatively detects
(1)
divided gas flow component:sulfur hexafluoride electrical equipment fault gas to be measured is passed into separation chromatography post, take helium as mobile phase, carries out gas chromatography separation to sulfur hexafluoride and each sulfur-bearing failure gas component.
Port 5 ' through six-way valve injector 13 injects into helium, and as mobile phase, the port 1 ' through six-way valve injector 13 injects sulfur hexafluoride electrical equipment fault gas, and sample size is 0.1ml.
The chromatographic condition of gas chromatography is: injector temperature: 200 DEG C, pressure: 25 psi, total flow: 41.498 ml/min, dottle pin purge flow rate: 3 ml/min, shunt mode: shunting 10:1, chromatographic column: J & W113-4362:260 DEG C: 60 m × 320 μm × 0 μm, post case temperature: initial temperature is 60 DEG C, maintains 6 min; Rise to 150 DEG C with the speed of 10 DEG C/min, maintain 2 min.
(2)
discharge sulfur hexafluoride:separated gas enters in thermal conductivity detector (TCD) and detects, the detected temperatures of thermal conductivity detector (TCD) 15 is 200 DEG C, for referencial use with the appearance time region of sulfur hexafluoride standard items, when arrival or the appearance time close to sulfur hexafluoride, namely close to or arrive 3.0min time, open six-way valve, port 1 and port 2, port 3 is communicated with port 6 respectively with port 4 and port 5, port 2 and port 3 disconnect, port 2, port 1, port 5 and port 6 are communicated with formation SF6 discharge-channel successively, sample gas sequentially passes through separation chromatography post 18, thermal conductivity detector (TCD) 15, port 2, port 1, port 5, port 6 is discharged, finally by emptying, do not enter in sulfur chemiluminescent detector and detect.
(3)
sulfur-bearing failure gas measured portions measures:when arrival or when going out the peak end time close to sulfur hexafluoride, namely arrive or close to 4.2min time, close six-way valve, port 1 is communicated with port 5 respectively with port 6, port 2 and port 3 and port 3, port 2 is communicated with port 3, the connection of conducting thermal conductivity detector (TCD) and sulfur chemiluminescent detector, port 4, port 5, port 1 and port 6 are communicated with formation carrier gas discharge-channel successively.Now, the impulse force produced owing to closing six-way valve 16 makes separation of C OS, H
2s, SO
2f
2, CS2, SO
2the retention time of middle portion gas is delayed, and occurs COS, H appears in 5.003 min at 4.595 min
2there is SO in S, 5.067 min
2f
2, there is CS in 9.007 min
2sO is there is with 10.675 min
2.Sample gas is separated by chromatographic column, through thermal conductivity detector (TCD) 15, enters into sulfur chemiluminescent detector 14 and detects, testing conditions is: detector temperature 225 DEG C, double plasma chamber temperature 800 DEG C, hydrogen 45 ml/min, air 63 ml/min, result as shown in Figure 5.And the typical curve of the part SF6 decomposition components set up, its parameter is as shown in the table:
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention or principal character.The above embodiment of the present invention and test example all can only be thought explanation of the present invention instead of restriction, therefore every above embodiment is done according to substantial technological of the present invention any trickle amendment, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
Claims (4)
1. a simultaneous quantitative detects the method for sulfur-bearing failure gas component in sulfur hexafluoride electrical equipment, it is characterized in that, the pick-up unit that the method uses comprises separation chromatography post, thermal conductivity detector (TCD) and sulfur chemiluminescent detector, described separation chromatography post is connected with thermal conductivity detector (TCD), thermal conductivity detector (TCD) is connected with sulfur chemiluminescent detector by a six-way valve, the sample outlet end of described thermal conductivity detector (TCD) is connected with the port 2 of six-way valve, the test entrance point of described sulfur chemiluminescent detector is connected with six-way valve port 3, the switch controlling six-way valve makes its port 2 when sample introduction be communicated with port 3, the connection of conducting thermal conductivity detector (TCD) and sulfur chemiluminescent detector, when being separated SF6, disconnect thermal conductivity detector (TCD) to be connected with sulfur chemiluminescent detector, port 2, port 1, port 5 and port 6 are communicated with formation SF6 discharge-channel successively, discharge SF6,
Said method comprising the steps of:
(1)
divided gas flow component:sulfur hexafluoride electrical equipment fault gas to be measured is passed into separation chromatography post, take helium as mobile phase, gas chromatography separation is carried out to gas composition, chromatographic condition is: injector temperature: 200 DEG C, pressure: 25 psi, total flow: 41.498 ml/min, dottle pin purge flow rate: 3 ml/min, shunt mode: shunting 10:1, gas-pro capillary chromatographic column: J & W113-4362:260 DEG C: 60 m × 320 μm × 0 μm, post case temperature: initial temperature is 60 DEG C, maintains 6 min; Rise to 150 DEG C with the speed of 10 DEG C/min, maintain 2 min;
(2)
discharge sulfur hexafluoride:separated gas enters in thermal conductivity detector (TCD) and detects, the detected temperatures of thermal conductivity detector (TCD) is 200 DEG C, with the appearance time of sulfur hexafluoride standard items and appearance time region for referencial use, when arrival or the appearance time close to sulfur hexafluoride, open six-way valve, port 2 and port 3 disconnect, and port 2, port 1, port 5 are communicated with successively with port 6, discharge sulfur hexafluoride;
(3)
sulfur-bearing failure gas measured portions measures:when arrival or when going out the peak end time close to sulfur hexafluoride, close six-way valve, port 2 is communicated with port 3, the connection of conducting thermal conductivity detector (TCD) and sulfur chemiluminescent detector, the residual gas in described thermal conductivity detector (TCD) passes in sulfur chemiluminescent detector and quantitatively detects, and then obtains the content of each sulfur-bearing failure gas component, the detected temperatures of described sulfur chemiluminescent detector is 225 DEG C, gas ions burner temperature wherein 800 DEG C, hydrogen 45 ml/min, air 63 ml/min.
2. simultaneous quantitative detects the method for sulfur-bearing failure gas component in sulfur hexafluoride electrical equipment according to claim 1, and it is characterized in that, also comprise carrier gas source, for carrier gas supply, described carrier gas source is connected with flowing valve port 4.
3. simultaneous quantitative detects the method for sulfur-bearing failure gas component in sulfur hexafluoride electrical equipment according to claim 1, it is characterized in that, also comprise helium gas source, this helium gas source is connected with separation chromatography post by six-way valve injector, and sulfur hexafluoride electrical equipment fault gas to be measured and helium enter separation chromatography post through six-way valve injector and carry out gas separaion.
4. simultaneous quantitative according to claim 1 detects the method for sulfur-bearing failure gas component in sulfur hexafluoride electrical equipment, it is characterized in that, also comprise the step measuring sulfur hexafluoride and each sulfur-bearing failure gas component appearance time region, concrete operations are: the standard items getting sulfur hexafluoride and each sulfur-bearing failure gas component are made into mixed gas, then gas chromatographic detection is carried out, thus obtain the appearance time region of sulfur hexafluoride and each sulfur-bearing failure gas component, as the reference of subsequent step, the chromatographic condition of gas chromatography is identical with described step (1) chromatographic condition in this step.
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| CN103616468A (en) * | 2013-11-27 | 2014-03-05 | 深圳供电局有限公司 | SF (sulfur hexafluoride)6Gas chromatography detection system and method |
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| JP7036228B2 (en) * | 2018-12-12 | 2022-03-15 | 株式会社島津製作所 | Chemiluminescent sulfur detector |
| JP7099344B2 (en) * | 2019-02-01 | 2022-07-12 | 株式会社島津製作所 | Chemiluminescent sulfur detector |
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| CN111398484B (en) * | 2020-04-27 | 2022-04-08 | 深圳供电局有限公司 | Gas Chromatograph for Detecting SF6 in Transformer Oil Dissolved Gas |
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| CN116067876B (en) * | 2021-11-01 | 2026-03-24 | 中国石油化工股份有限公司 | A system and method for detecting trace impurities in hydrogen gas |
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Address after: 510080 Dongfeng East Road, Dongfeng, Guangdong, Guangzhou, Zhejiang Province, No. 8 Patentee after: ELECTRIC POWER RESEARCH INSTITUTE, GUANGDONG POWER GRID CO., LTD. Address before: Guangzhou City, Guangdong province Yuexiu District 510080 Dongfeng East Road, No. 8 building water Kong Guangdong Patentee before: Electrical Power Research Institute of Guangdong Power Grid Corporation |