CN104267132A - Chromatography method for detecting SF6 decomposition products - Google Patents

Chromatography method for detecting SF6 decomposition products Download PDF

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CN104267132A
CN104267132A CN201410425092.8A CN201410425092A CN104267132A CN 104267132 A CN104267132 A CN 104267132A CN 201410425092 A CN201410425092 A CN 201410425092A CN 104267132 A CN104267132 A CN 104267132A
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valve
post
takey
detecting device
porapak
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CN104267132B (en
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王宇
方华
周永言
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Electric Power Research Institute of Guangdong Power Grid Co Ltd
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Electric Power Research Institute of Guangdong Power Grid Co Ltd
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Abstract

The invention discloses a chromatography method for detecting the SF6 decomposition products. A sample is fed into a set of chromatographic columns to separate the components in the sample, a set of valves is adopted to cut the components and separately control the components, a first PDD detector and a second PDD detector are adopted to analyze and test the separated components individually; wherein the chromatographic column set at least comprises six chromatographic columns: a Takey A column, a Takey B column, a Takey C column, a first Porapak Q column, a second Porapak Q column, and a 13X molecule sieve column; the valve set comprises at least five multi-way valves: a first valve, a second valve, a third valve, a fourth valve, and a fifth valve. The provided method can overall and precisely carry out analysis on SF6 decomposition products, so that the inner operation situation of SF6 gas insulation equipment can be precisely determined so as to guarantee the safe operation of electrical equipment.

Description

Detect SF 6the chromatogram analysis method of decomposition product
Technical field
The present invention relates to analysis detection field, particularly relate to a kind of detection SF 6the chromatogram analysis method of decomposition product.
Background technology
Sulfur hexafluoride (SF 6) be at normal temperatures and pressures a kind of colourless, tasteless, nontoxic, do not fire, the forming gas of chemical property stabilizer pole.SF 6molecule be the symmetrical structure of single sulphur polyfluoro, there is extremely strong electronegativity, give its excellent electrical isolation and arc extinction performance.At present, SF 6as the insulating medium of a new generation, be widely used in high pressure, extra-high voltage electrical equipment.Fill SF 6electrical equipment floor area few, running noises is little, without fire hazard, drastically increases the safe reliability of electric equipment operation.
SF 6gas is under the effect of overheated, electric arc, electric spark and corona discharge, and can decompose, its decomposition product also can react with the micro-moisture in equipment, electrode and solid insulating material, and its product more complicated, has gaseous impurities, as carbon tetrafluoride (CF 4), fluoridize sulfonyl (SO 2f 2), fluoridize thionyl (SOF 2), sulphuric dioxide (SO 2) etc., also have some solid impurities, as aluminum fluoride (AlF 3), tungsten fluoride (WF 6) etc., concrete decomposition approach is as shown in Figure 9.
For operating electrical equipment, judging its device interior running status relative difficulty, detecting SF by analyzing 6the decomposition product of gas judges SF 6strong means of air insulating device internal operation situation.In recent years, Guangdong Province is by detecting SF 6cF in gas 4and SO 2content Deng decomposition product has successfully judged a lot of electrical equipment malfunction.According to research experience and real work in the past, pass through SF 6the decomposition product SO of gas 2f 2, SOF 2, CS 2, the decomposition product such as SCO effectively can judge SF 6air insulating device internal operation situation, meanwhile, passes through H 2, O 2, N 2, CO, CH 4, CO 2, C 2f 6content Deng impurity also effectively can judge SF6 air insulating device internal operation situation.
Traditional colour spectral analysis method adopts single-column to come SF 6decomposition product carries out being separated and testing, and utilizes TCD and FDP to contact detecting device to SF 6decomposition product is analyzed, but relies on single-column separation effectively can not analyze H 2, O 2, N 2, CO, CH 4, CO 2, COS, H 2s, SOF 2, CS 2deng compound, and the running status of these compounds to inside electric appliance judges between right and wrong often important; And the detecting device utilizing TCD-FPD to connect also has shortcoming, TCD sensitivity is low, detects limit for height, can not be used for detecting the decomposition product of low content; FPD detecting device is not linear detector due to it, easily causes error comparatively large, quantitatively inaccurate when quantitative.
The present inventor has invented one and utilized four valve four post combination analysis SF early stage 6the method (hereinafter referred to as invention in early stage) of decomposition product, it compares traditional chromatogram analysis method, separable go out the indissociable compound of multiple traditional colour spectral analysis method, and separating effect is better, but the retention time of partial target compound is comparatively close, still have the space of improvement.
Summary of the invention
Based on this, be necessary for the problems referred to above, provide a kind of and detect SF 6the chromatogram analysis method of decomposition product, it is to SF 6the separating effect of decomposition product is better, and quantitative and qualitative analysis is more accurate.
For realizing above technical purpose, concrete technical scheme is as follows:
A kind of detection SF 6the chromatogram analysis method of decomposition product, adopts the coupling of chromatographic column group to carry out Component seperation to sample, adopts valve group to carry out cutting of components and is separated and controls, and adopts a PDD detecting device and the 2nd PDD detecting device to carry out analytical test respectively to the sample after being separated; Wherein, described chromatographic column group at least comprises six roots of sensation chromatographic column, is respectively Takey A post, Takey B post, Takey C post, a Porapak Q post, the 2nd Porapak Q post and 13X molecular sieve column; Described valve group comprises at least five multiport valves, is respectively the first valve, the second valve, the 3rd valve, the 4th valve and the 5th valve.
The present invention, by Takey A post and the coupling of Takey B post, analyzes SO 2f 2, H 2s, C 3f 8, COS, SOF 2; CS is analyzed by Takey C post 2and SO 2; By a Porapak Q post and the coupling of 13X molecular sieve column, analyze H 2, O 2, N 2, CO, CH 4, CF 4; By a Porapak Q post and the 2nd Porapak Q post coupling, Analysis for CO 2and C 2f 6.Inventor, according to permanent experience accumulation and a large amount of experiments, optimizes above-mentioned chromatographic column, and wherein Takey A post and the coupling of Takey B post, can avoid SO 2conditions of streaking, meanwhile, can SO be made 2f 2, C 3f 8, H 2the separating effect of S is better, can also make SOF 2and SO 2separating effect better.
Wherein in some embodiments, also comprise and adopt sample intake passage to input described sample, described sample intake passage is connected by described first valve, described Takey C post and described 4th valve with described 2nd PDD detecting device and forms the first sense channel successively;
Described sample intake passage is connected by described first valve, described Takey A post, described 3rd valve, described Takey B post and described 4th valve with described 2nd PDD detecting device and forms the second sense channel successively;
Described sample intake passage to be connected with a described PDD detecting device by described first valve, described second valve, a described Porapak Q post, the 2nd Porapak Q post and described 5th valve successively and to form the 3rd sense channel;
Described sample intake passage to be connected with a described PDD detecting device by described first valve, described second valve, a described Porapak Q post and described 13X molecular sieve column successively and to form the 4th sense channel.
Wherein in some embodiments, also comprise and adopt carrier gas passage and the 6th valve control inputs carrier gas; Described carrier gas passage is connected with described first valve, described second valve and described 3rd valve respectively by described 6th valve.
The present invention carries out cutting of components by the switching of valve and is separated and controls, and wherein the first valve and the second valve are ten-way valve, and the 3rd valve and the 4th valve are six-way valve, and the 5th valve is solenoid valve, and the 6th valve is four-way valve, first, second, third and fourth, six valves are pneumatic valve.First, second, third and fourth, five valves are used for the switching that realizes between chromatographic column, and the 6th valve is mainly used to ensure, when shutting down, to keep He (being full of helium) state in chromatographic column and pipeline, avoids start next time, and stabilization time is long.
Wherein in some embodiments, the two ends of a described Porapak Q post are connected with described second valve respectively.
Wherein in some embodiments, also comprise employing first quantity tube, the second quantity tube and the 3rd quantity tube and control sample introduction;
Described first quantity tube is located on described first sense channel, and the two ends of described first quantity tube are connected with described first valve, and described first valve is communicated with described Takey C post by described first quantity tube;
Described second quantity tube is located on described second sense channel, and the two ends of described second quantity tube are connected with described first valve, and described first valve is communicated with described Takey A post by described second quantity tube;
The two ends of described 3rd quantity tube are connected with described second valve, and described second valve is communicated with a described Porapak Q post by described 3rd quantity tube.
The effect of above-mentioned three quantity tubes is all control sample introduction, and gaseous sample enters quantity tube in original state, after entering routine analyzer, then enters different chromatographic column respectively by three quantity tubes and analyzes.
Wherein in some embodiments, a described PDD detecting device is used for detecting H 2, O 2, N 2, CO, CH 4, CF 4, CO 2, C 2f 6; Described 2nd PDD detecting device is used for detecting SO 2f 2, H 2s, C 3f 8, COS, SOF 2, SO 2, CS 2.
Wherein in some embodiments, described valve group at the changeover program of analytic process is: the initial state of six valves is closedown, and wherein the first valve is: 0min, and the first valve is opened; 1min, the first valve cuts out; Second valve is: 0min, and the second valve is opened; 1.5min, the second valve cuts out; 3rd valve is: 0.0min, and the 3rd valve is opened; 0.8min, the 3rd valve cuts out; 1.2min, the 3rd valve is opened; 20.0min, the 3rd valve cuts out; 4th valve is: 5.8min, and the 4th valve is opened; 20.0min, the 4th valve cuts out; 5th valve is: 11.5min, and the 5th valve is opened; 16.0min, the 5th valve cuts out; 6th valve is switched to opening before analysis starts, and analyzes after terminating and is switched to closed condition.
Invention people avoids impurity for the interference of final analysis result and qualitative, quantitative, optimizes whole handoff procedure in detail, and has carried out best optimal design to the opening/closing time of valve, ensure that the accuracy of final analysis result.
Wherein in some embodiments, six roots of sensation chromatographic column in described chromatographic column group all adopts thermostatic control, wherein, described post Takey A post, Takey C column temperature are 118 ~ 120 DEG C, described Takey B column temperature is 58 ~ 62 DEG C, a described Porapak Q post and the 2nd Porapak Q column temperature are 48 ~ 52 DEG C, and described 13X molecular sieve column temperature is 68 ~ 72 DEG C.
Wherein in some embodiments, analyzing detected parameters is: carrier gas: helium, purity >=99.999%, and output pressure is 0.5 ~ 0.6Mpa; Drive gas: air/nitrogen, drive gas output pressure to be 0.3 ~ 0.4Mpa, sample introduction pressure: 0.17 ~ 0.19Mpa; The temperature of a described PDD detecting device and the 2nd PDD detecting device is 175 ~ 185 DEG C.
Wherein in some embodiments, described analysis detected parameters is: carrier gas: helium, purity >=99.9999%, and output pressure is 0.6Mpa; Drive gas: air/nitrogen, drive gas output pressure to be 0.4Mpa, sample introduction pressure: 0.18 Mpa; The temperature of a described PDD detecting device and the 2nd PDD detecting device is 180 DEG C.
The present invention compares the advantage of prior art and beneficial effect is:
The present invention is by multidigit inventor years of researches and a large amount of experiments, determine optimized parameter and the combination thereof of analytic process, and combined the separation that can realize between different component by six valve six posts, except accurately can detect the SF that traditional analysis can not accurately detect simultaneously 6decomposition product, as H 2, O 2, N 2, CO, CH 4, CO 2, COS, H 2s, SOF 2, CS 2deng compound, also solve SO 2f 2and H 2s and SOF 2and SO 2the problem that retention time is too close, considerably increases the accuracy of the judgement to final goal compound, and SO in gained chromatogram of the present invention 2peak shape without hangover, further increase SO 2the accuracy of quantitative and qualitative, the present invention is comprehensive and accurate to SF 6decomposition product is analyzed, thus accurately judges SF 6air insulating device internal operation situation, ensures electrical equipment safe operation.
Accompanying drawing explanation
Fig. 1 is that the present invention detects SF 6valve and chromatographic column connection layout (6 valves are closed condition) in the chromatogram analysis method of decomposition product; Description of reference numerals: 101:Takey A post; 102:Takey B post; 103:Takey C post; 104: the one Porapak Q posts; 105:13X molecular sieve column; 106: the two Porapak Q posts; 201: the first valves; 202: the second valves; 203: the three valves; 204: the four valves; 205: the five valves; 206: the six valves; 301: the one PDD detecting devices; 302: the two PDD detecting devices; 401: the first quantity tubes; 402: the second quantity tubes; 403: the three quantity tubes; 501: sample intake passage; 502: carrier gas passage; 601: gas circuit hole; 602: gas circuit;
Fig. 2 is that the present invention detects SF 6valve in the chromatogram analysis method of decomposition product and chromatographic column connection layout (6 valves are opening);
Fig. 3 is the chromatogram of a PDD detecting device gained in embodiment 1, from left to right, goes out peak material and is respectively H 2(1.85min), O 2(2.33min), N 2(2.48min), CO (3.06min), CH 4(3.50min), CF 4(4.07min), CO 2(4.51min), C 2f 6(5.79min);
Fig. 4 is the chromatogram of the 2nd PDD detecting device gained in embodiment 1, from left to right, goes out peak material and is respectively SO 2f 2(2.76min), H 2s (3.37min), C 3f 8(3.71min), COS (4.42min), SOF 2(5.34min), SO 2(9.61min), CS 2(14.32min);
Fig. 5 is for analyzing gained chromatogram (COS+H invention in early stage (four valve four post method for combined use) 2s+CS 2);
Fig. 6 is for analyzing gained chromatogram (SO invention in early stage (four valve four post method for combined use) 2f 2+ C 3f 8);
Fig. 7 is for analyzing gained chromatogram (SO invention in early stage (four valve four post method for combined use) 2);
Fig. 8 is traditional single-column separation chromatography methods analyst gained chromatogram;
Fig. 9 is SF 6the decomposition reaction schematic diagram of gas under the effect of overheated, electric arc, electric spark and corona discharge.
embodiment
Further illustrate the present invention below in conjunction with embodiment and accompanying drawing, but embodiment can not in order to limit the scope of the invention.
In following examples, the supplier of chromatographic column used (comprising Takey A post, Takey B post, Takey C post, a Porapak Q post, the 2nd Porapak Q post and 13X molecular sieve column) is: Shanghai Hua Ai chromatogram company limited.
Embodiment 1
A kind of detection SF 6the chromatogram analysis method of decomposition product, adopts the coupling of chromatographic column group to carry out Component seperation to sample, adopts valve group to carry out cutting of components and is separated and controls, and adopts a PDD detecting device 301 and the 2nd PDD detecting device 302 to carry out analytical test respectively to the sample after being separated, wherein, described chromatographic column group at least comprises six roots of sensation chromatographic column, be respectively Takey A post 101 (long 2m, the stainless-steel tube of internal diameter 3mm, in-built particle diameter is the high molecular polymer of 0.18mm ~ 0.25mm), Takey B post 102 (long 2m, the stainless-steel tube of internal diameter 3mm, in-built particle diameter is the high molecular polymer of 0.18mm ~ 0.25mm), Takey C post 103 (long 2m, the stainless-steel tube of internal diameter 3mm, in-built particle diameter is the high molecular polymer of 0.18mm ~ 0.25mm), one Porapak Q post 104 (long 4m, the stainless-steel tube of internal diameter 3mm, in-built particle diameter is the Porapak Q of 0.18mm ~ 0.25mm), 2nd Porapak Q post 106 (long 2m, the stainless-steel tube of internal diameter 3mm, in-built particle diameter is the Porapak Q of 0.18mm ~ 0.25mm) and 13X molecular sieve column 105 (long 4m, the stainless steel column of internal diameter 3mm, in-built particle diameter is the 13X molecular sieve column scribbling Plexol 201 of 0.30mm ~ 0.60mm), described valve group comprises at least five multiport valves, is respectively the first valve 201, second valve 202, the 3rd valve 203, the 4th valve 204, the 5th valve 205.
As shown in Figure 1, 2, the present invention also comprises and adopts sample intake passage 501 to input sample, and sample intake passage 501 to be connected with the 2nd PDD detecting device 302 by the first valve 201, Takey C post 103 and the 4th valve 204 successively and to form the first sense channel;
Sample intake passage 501 to be connected with the 2nd PDD detecting device 302 by the first valve 201, Takey A post the 101, the 3rd valve 203, Takey B post 102 and the 4th valve 204 successively and to form the second sense channel;
Sample intake passage 501 to be connected with a PDD detecting device 301 by the first valve 201, second valve 202, Porapak Q post the 104, a 2nd Porapak Q post 106 and the 5th valve 205 successively and to form the 3rd sense channel;
Sample intake passage 501 to be connected with a PDD detecting device 301 by the first valve 201, second valve 202, a Porapak Q post 104 and 13X molecular sieve column 105 successively and to form the 4th sense channel.
The present invention also comprises employing carrier gas passage 502 and the 6th valve 206 inputs carrier gas; Carrier gas passage 502 is connected with the first valve 201, second valve 202 and the 3rd valve 203 respectively by the 6th valve 206; Carrier gas passage 502 is connected with a PDD detecting device 301 and the 2nd PDD detecting device 302 respectively by the 6th valve 206.
The present invention also comprises employing first quantity tube 401, second quantity tube 402 and the 3rd quantity tube 403 and controls sample introduction (effect of three quantity tubes is all control sample introduction, gaseous sample enters quantity tube in original state, after entering routine analyzer, enter different chromatographic column respectively by three quantity tubes again to analyze), first quantity tube 401 is located on the first sense channel, the two ends of the first quantity tube 401 are connected with the first valve 201, and the first valve 201 is communicated with Takey C post 103 by the first quantity tube 401; Second quantity tube 402 is located on the second sense channel, and the two ends of the second quantity tube 402 are connected with the first valve 201, and the first valve 201 is communicated with Takey A post 101 by the second quantity tube 402; The two ends of the 3rd quantity tube 403 are connected with described second valve 202, and described second valve 202 is communicated with a Porapak Q post 104 by the 3rd quantity tube 403; The two ends of the one Porapak Q post 104 are connected with the second valve 202 respectively.
The present invention's two PDD detecting devices carry out detection to the sample after separation respectively and analyze, and wherein a PDD detecting device 301 is used for detecting H 2, O 2, N 2, CO, CH 4, CF 4, CO 2, C 2f 6; 2nd PDD detecting device 302 is used for detecting SO 2f 2, H 2s, C 3f 8, COS, SOF 2, SO 2, CS 2.
The present invention carries out cutting of components by the switching of valve and is separated control, wherein the first valve 201 and the second valve 202 are ten-way valve, and the 3rd valve 203 and the 4th valve 204 are six-way valve, and the 5th valve 205 is solenoid valve, 6th valve 206 is four-way valve, first, second, third and fourth, six valves are pneumatic valve.First, second, third and fourth, five valves are used for the switching that realizes between chromatographic column, and the 6th valve 206 is mainly used to ensure, when shutting down, to keep He (being full of helium) state in chromatographic column and pipeline, avoids start next time, and stabilization time is long.Each valve and chromatographic column are connected by gas circuit 602, each valve are provided with gas circuit hole 601 (ten-way valve has ten gas circuit holes, eight logical valves have eight gas circuit holes, four-way valve has four gas circuit holes) in order to connect gas circuit 602.
Figure 1 shows that the original state (being closed condition) of 6 valves, all valve events are once opening, opening refers to that the connecting line in valve is changed completely, originally becoming of connection or not, originally disconnectedly connection is become, outside gas circuit 602 constant (as shown in Figure 2), more namely action once replys the original state of Fig. 1, i.e. closed condition.All valves all can single action, and whether the action between each valve does not affect by other valve, and the changeover program of valve is in table 1:
The changeover program of table 1 valve (unit: minute)
On/Off First valve Second valve 3rd valve 4th valve 5th valve
Open 0.0 0.0 0.0 5.8 11.5
Close 1.0 1.5 0.8 20 16.0
Open - - 1.2 - -
Close - - 20.0 - -
As seen from the above table, the initial state of six valves is closedown, and wherein the first valve 201 is: 0min, and the first valve 201 is opened; 1min, the first valve 201 cuts out; Second valve 202 is: 0min, and the second valve 202 is opened; 1.5min, the second valve 202 cuts out; 3rd valve 203 is: 0.0min, and the 3rd valve 203 is opened; 0.8min, the 3rd valve 203 cuts out; 1.2min, the 3rd valve 203 is opened; 20.0min, the 3rd valve 203 cuts out; 4th valve 204 is: 5.8min, and the 4th valve 204 is opened; 20.0min, the 4th valve 204 cuts out; 5th valve 205 is: 11.5min, and the 5th valve 205 is opened; 16.0min, the 5th valve 205 cuts out; 6th valve 206 is opened before whole analyte detection process starts, and closes after whole analyte detection process terminates.Carrier gas enters the 6th valve 206 from carrier gas inlet 502, and is the direction of carrier gas transport by the 6th valve 206 direction of arrow be transported in the first valve 201, second valve 202, the 3rd valve 203, Fig. 1,2.
Testing conditions is: carrier gas: helium, purity >=99.9999%, and output pressure is 0.6Mpa; Drive gas: air/nitrogen, drive gas output pressure to be 0.4Mpa, sample introduction pressure: 0.18Mpa; The temperature of the one PDD detecting device 301 and the 2nd PDD detecting device 302 is 180 DEG C.
Six roots of sensation chromatographic column all adopts thermostatic control, wherein, Takey A post 101, Takey C post 103 temperature are 120 DEG C, and Takey B post 102 temperature is 60 DEG C, one Porapak Q post 104 and the 2nd Porapak Q post 106 temperature are 50 DEG C, and 13X molecular sieve column 105 temperature is 70 DEG C.
Concrete detecting step is as follows: as shown in Figure 1, 2, first valve 201, second valve 202 and the 5th valve 205 be used for control the one PDD detect gas circuit (comprising the 3rd sense channel, the 4th sense channel), coordinate the 3rd quantity tube 403, a Porapak Q post 104,13X molecular sieve column 105 and the 2nd Porapak Q post 106 use.
Original state is sample introduction (closedown) state, and gas to be measured enters the 3rd quantity tube 403 by sample intake passage 501, first valve 201, second valve 202; 0min, the second valve 202 is opened, and the sample in the 3rd quantity tube 403 is blown into a Porapak Q post 104 by carrier gas, after enter 13X molecular sieve column 105 and be separated, then enter a PDD detecting device 301 and analyze, the target compound measured now is H 2, O 2, N 2, CO, CH 4, CF 4; 1.5min, second valve 202 action again, now the second valve recovering state is for closing, now, carrier gas continues the material remained in a Porapak Q post 104 to be blown into the 2nd Porapak Q post 106, further separation, after enter a PDD detecting device 301 and detect, main target compound is CO 2and C 2f 6.The original state of the 5th valve 205 is closed condition, and in 11.5min action, open, effect makes a large amount of SF 6background emptying, 16min restores to the original state, i.e. closed condition.
First valve 201, 3rd valve 203, 4th valve 204 be used for control the 2nd PDD detect gas circuit (comprise the first sense channel, second sense channel), coordinate the first quantity tube 401, second quantity tube 402, Takey A post 101, Takey B post 102 and Takey C post 103 use, wherein, first valve 201 is mainly used to Quality control and whether enters the first quantity tube 401 and the second quantity tube 402, 3rd valve 203 be mainly used to control Takey A post 101 whether with Takey B post 102 UNICOM, 4th valve 204 is mainly used to control objectives compound and whether enters the 2nd PPD detecting device 302, or which road gas enters the 2nd PPD detecting device 302 and carries out analysiss detection.
Original state is sample introduction (closedown) state, and testing sample gas enters the first quantity tube 401 and the second quantity tube 402 from sample intake passage 501 by the first valve 201; 0min, the first valve 201 is opened, and the sample in the first quantity tube 401 is blown into Takey C post 103 by carrier gas and is separated, and the sample in the second quantity tube 402 is blown into TakeyA post 101 and is separated; 1min, the first valve 201 action again, recovers to close; 0min, the 3rd valve 203 is opened, and TakeyA post 101 is a pre-separation post (TakeyA post 101 and Takey B post 102 cooperatively interact, and TakeyA post 101 is first separated in advance), can realize SF 6background is separated with target compound, and the 3rd valve 203 is opened can make the SF going out peak at first 6during background is drained, do not enter the 2nd PDD detecting device 302, in order to avoid excessive SF 6gaseous contamination detecting device; 0.8min, the 3rd valve 203 cuts out, and now, the target compound residued in TakeyA post 101 is blown into TakeyB post 102 by carrier gas and is separated; 1.2min, the 3rd valve 203 is opened, and now, other compound in TakeyA post 101 is drained; 20min, the 3rd valve 203 action again, recovers closed condition.When 4th valve 204 is positioned at original state (cut out), the target compound in TakeyB post 102 enters the 2nd PDD detecting device 302 and carries out analysis detection, and now, the target compound be detected mainly contains SO 2f 2, H 2s, C 3f 8, COS, SOF 2; 5.8min, the 4th valve 204 is opened, and now, the target compound in TakeyC post 103 enters the 2nd PDD detecting device 302 and analyzes, and the target compound be detected mainly contains CS 2and SO 2; 20min, the 4th valve 204 cuts out, and restores to the original state.
Fig. 3 and Fig. 4 is the chromatogram of the present embodiment gained, the chromatogram that analysis that Fig. 3 obtains by the PDD detecting device 301, and as can be seen from the figure, can be separated H completely 2, O 2, N 2, CO, CH 4, CF 4, CO 2, C 2f 6, the retention time of each target compound is as shown in table 2.The chromatogram that analysis that Fig. 4 obtains by the 2nd PDD detecting device 302, can be separated SO completely 2f 2, H 2s, C 3f 8, COS, SOF 2, SO 2, CS 2, the retention time of each target compound is as shown in table 3.
Fig. 5-Fig. 7 is the chromatogram of inventor's invention in early stage gained, and as can be seen from the figure, the separating effect of part of compounds is not very good, as SO in Fig. 6 2f 2and C 3f 8retention time close, degree of separation is not high, the SO shown in Fig. 7 2peak type there is obvious conditions of streaking.
And Fig. 8 is the chromatogram adopting traditional single-column separation chromatography analytical approach, air, CF can be separated 4, CO 2, SF 6, SO 2f 2, SOF 2, H 2o and SO 2, wherein SF 6and SO 2f 2separating effect also not so good, and rely on single-column to be separated effectively can not to analyze H 2, O 2, N 2, CO, CH 4, CO 2, COS, H 2s, CS 2deng compound, effect of the present invention can not be realized.
Lower list 2 and table 3 are respectively 15 kinds of concrete retention times of decomposition product measured by embodiment 1 two PDD detecting devices, and adopt 15 kinds of concrete retention times of decomposition product measured by inventor's invention in early stage:
Table 2 retention time (a PDD detecting device)
Table 3 retention time (the 2nd PDD detecting device)
As can be seen from table 2,3, compare with invention in early stage, separating effect of the present invention is better, and table 2 and table 3 list the difference of two kinds of method retention times.As can be seen from table 2 and table 3, early stage, the method for invention had the retention time between partial target compound more close, as SO 2f 2and H 2the retention time of S is respectively 6.58 and 6.44 minutes (chromatogram can see Fig. 5 and Fig. 6), SO 2f 2and C 3f 8retention time be respectively 6.58 and 6.81 minutes (chromatogram can see Fig. 6), SOF 2and SO 2retention time be respectively 14.50 and 14.64 minutes, between different target compound, retention time is close, may cause erroneous judgement and the misjudgement of target compound, at SF 6in electrical device status diagnosis, SO 2f 2, H 2s, SOF 2and SO 2four kinds of material particular importances, utilize these four kinds of materials of method qualitative, quantitative of invention in early stage, and Water demand personnel very a twist of the wrist could accurately identify; The present invention then solves this problem, utilizes the present invention to analyze SF 6decomposition product, SO 2f 2and H 2the retention time of S is respectively 2.76 and 3.37 minutes, SO 2f 2and C 3f 8retention time be respectively 2.76 and 3.71 minutes, SOF 2and SO 2retention time be respectively 5.34 and 9.61 minutes, differ by more than 0.6 minute between the retention time of several material, misjudgement and the erroneous judgement of different target compound can not be caused.Meanwhile, comparison diagram 4 and Fig. 7, the invention in early stage before the present invention comparatively, SO 2conditions of streaking obtain effective solution, early stage invention in, mainly through Gaspro capillary tube column analysis SO 2component, SO analyzed by this post 2the phenomenon that peak can be caused to trail produces, and the present invention analyzes SO mainly through Takey C post 2component, can avoid SO 2the generation of peak conditions of streaking.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. one kind is detected SF 6the chromatogram analysis method of decomposition product, it is characterized in that, adopt the coupling of chromatographic column group to carry out Component seperation to sample, adopt valve group to carry out cutting of components and be separated and control, adopt a PDD detecting device and the 2nd PDD detecting device to carry out analytical test respectively to the sample after being separated; Wherein, described chromatographic column group at least comprises six roots of sensation chromatographic column, is respectively Takey A post, Takey B post, Takey C post, a Porapak Q post, the 2nd Porapak Q post and 13X molecular sieve column; Described valve group comprises at least five multiport valves, is respectively the first valve, the second valve, the 3rd valve, the 4th valve and the 5th valve.
2. detection SF according to claim 1 6the chromatogram analysis method of decomposition product, it is characterized in that, also comprise and adopt sample intake passage to input described sample, described sample intake passage is connected by described first valve, described Takey C post and described 4th valve with described 2nd PDD detecting device and forms the first sense channel successively;
Described sample intake passage is connected by described first valve, described Takey A post, described 3rd valve, described Takey B post and described 4th valve with described 2nd PDD detecting device and forms the second sense channel successively;
Described sample intake passage to be connected with a described PDD detecting device by described first valve, described second valve, a described Porapak Q post, the 2nd Porapak Q post and described 5th valve successively and to form the 3rd sense channel;
Described sample intake passage to be connected with a described PDD detecting device by described first valve, described second valve, a described Porapak Q post and described 13X molecular sieve column successively and to form the 4th sense channel.
3. detection SF according to claim 2 6the chromatogram analysis method of decomposition product, is characterized in that, also comprises and adopts carrier gas passage and the 6th valve control inputs carrier gas; Described carrier gas passage is connected with described first valve, described second valve and described 3rd valve respectively by described 6th valve.
4. the detection SF according to any one of claims 1 to 3 6the chromatogram analysis method of decomposition product, is characterized in that, the two ends of a described Porapak Q post are connected with described second valve respectively.
5. the detection SF according to any one of claims 1 to 3 6the chromatogram analysis method of decomposition product, is characterized in that, also comprises employing first quantity tube, the second quantity tube and the 3rd quantity tube and controls sample introduction;
Described first quantity tube is located on described first sense channel, and the two ends of described first quantity tube are connected with described first valve, and described first valve is communicated with described Takey C post by described first quantity tube;
Described second quantity tube is located on described second sense channel, and the two ends of described second quantity tube are connected with described first valve, and described first valve is communicated with described Takey A post by described second quantity tube;
The two ends of described 3rd quantity tube are connected with described second valve, and described second valve is communicated with a described Porapak Q post by described 3rd quantity tube.
6. the detection SF according to any one of claims 1 to 3 6the chromatogram analysis method of decomposition product, is characterized in that, a described PDD detecting device is used for detecting H 2, O 2, N 2, CO, CH 4, CF 4, CO 2, C 2f 6; Described 2nd PDD detecting device is used for detecting SO 2f 2, H 2s, C 3f 8, COS, SOF 2, SO 2, CS 2.
7. the detection SF according to any one of claims 1 to 3 6the chromatogram analysis method of decomposition product, is characterized in that, described valve group at the changeover program of analytic process is: the initial state of six valves is closedown, and wherein the first valve is: 0min, and the first valve is opened; 1min, the first valve cuts out; Second valve is: 0min, and the second valve is opened; 1.5min, the second valve cuts out; 3rd valve is: 0.0min, and the 3rd valve is opened; 0.8min, the 3rd valve cuts out; 1.2min, the 3rd valve is opened; 20.0min, the 3rd valve cuts out; 4th valve is: 5.8min, and the 4th valve is opened; 20.0min, the 4th valve cuts out; 5th valve is: 11.5min, and the 5th valve is opened; 16.0min, the 5th valve cuts out; 6th valve is switched to opening before analysis starts, and analyzes after terminating and is switched to closed condition.
8. the detection SF according to any one of claims 1 to 3 6the chromatogram analysis method of decomposition product, it is characterized in that, six roots of sensation chromatographic column in described chromatographic column group all adopts thermostatic control, wherein, described post Takey A post, Takey C column temperature are 118 ~ 120 DEG C, described Takey B column temperature is 58 ~ 62 DEG C, and a described Porapak Q post and the 2nd Porapak Q column temperature are 48 ~ 52 DEG C, and described 13X molecular sieve column temperature is 68 ~ 72 DEG C.
9. the detection SF according to any one of claims 1 to 3 6the chromatogram analysis method of decomposition product, is characterized in that, analyzes detected parameters to be: carrier gas: helium, purity>=99.999%, and output pressure is 0.5 ~ 0.6Mpa; Drive gas: air/nitrogen, drive gas output pressure to be 0.3 ~ 0.4Mpa, sample introduction pressure: 0.17 ~ 0.19Mpa; The temperature of a described PDD detecting device and the 2nd PDD detecting device is 175 ~ 185 DEG C.
10. detection SF according to claim 9 6the chromatogram analysis method of decomposition product, is characterized in that, described analysis detected parameters is: carrier gas: helium, purity>=99.9999%, and output pressure is 0.6Mpa; Drive gas: air/nitrogen, drive gas output pressure to be 0.4Mpa, sample introduction pressure: 0.18Mpa; The temperature of a described PDD detecting device and the 2nd PDD detecting device is 180 DEG C.
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CN109459511A (en) * 2018-11-14 2019-03-12 中国南方电网有限责任公司超高压输电公司检修试验中心 Helium ion detector and subject breaker decomposition product mixed gas separation method
CN110726794A (en) * 2019-10-23 2020-01-24 朗析仪器(上海)有限公司 Analysis system for full analysis of decomposition products in sulfur hexafluoride mixed gas
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CN106885864A (en) * 2015-12-15 2017-06-23 中国科学院大连化学物理研究所 The more bundles of capillaries post and flight time mass spectrum of sampling sample introduction integration are used in conjunction device
US10900940B2 (en) 2016-10-31 2021-01-26 Electric Power Research Institute Of Guangdong Power Gird Co., Ltd. Refilling-type online chromatographic detector for sulphur hexafluoride decomposition products
CN106370764A (en) * 2016-10-31 2017-02-01 广东电网有限责任公司电力科学研究院 Refilling type sulfur hexafluoride decomposition product chromatography online detector
CN106370764B (en) * 2016-10-31 2018-08-07 广东电网有限责任公司电力科学研究院 A kind of recharging type sulfur hexafluoride decomposition product chromatography on-line detector
CN110780015A (en) * 2018-07-31 2020-02-11 西安市宇驰检测技术有限公司 Detection device and detection method for non-methane total hydrocarbons
CN109085280A (en) * 2018-10-16 2018-12-25 广东电网有限责任公司 A kind of system of quantitative detection sulfur hexafluoride gas ingredient
CN109085280B (en) * 2018-10-16 2024-04-12 广东电网有限责任公司 System for quantitatively detecting sulfur hexafluoride gas component
CN109459511A (en) * 2018-11-14 2019-03-12 中国南方电网有限责任公司超高压输电公司检修试验中心 Helium ion detector and subject breaker decomposition product mixed gas separation method
CN110726794A (en) * 2019-10-23 2020-01-24 朗析仪器(上海)有限公司 Analysis system for full analysis of decomposition products in sulfur hexafluoride mixed gas
CN111398484A (en) * 2020-04-27 2020-07-10 深圳供电局有限公司 Used for detecting SF in transformer oil dissolved gas6Gas chromatograph
CN111398484B (en) * 2020-04-27 2022-04-08 深圳供电局有限公司 Used for detecting SF in transformer oil dissolved gas6Gas chromatograph
CN114019040A (en) * 2021-10-15 2022-02-08 广西电网有限责任公司电力科学研究院 System for detecting gas impurities in sulfur hexafluoride

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