Chromatograph-mass spectrometer and mixed gas discharge decomposition product detection method

Abstract

The embodiment of the invention discloses a chromatograph-mass spectrometer and a mixed gas discharge decomposition product detection method, a sample quantification assembly is used for quantitatively controlling a sample gas, dividing the sample gas into two paths, and respectively feeding the two paths into a first chromatographic column and a first channel and a second chromatographic column and a second channel; wherein the first channel is a BID channel, and the BID channel is used for detecting substances before the appearance time of sample gas SF6, and mainly comprises N2, O2, NF3, CF4, CH4 and H2; wherein the first channel is an MSD channel, the second channel is an MSD channel, the MSD channel is used for detecting substances after the appearance time of sample gas SF6, and the substances mainly comprise SO2F2, SOF2, COS, SO2, N2O, C2F6 and C3F8; according to the invention, the existing standard gas can be calibrated, and no interference peak or impurity exists when an unknown sample is detected; the method has important help to detection of SF6 / N2 mixed gas decomposition products, and lays a foundation for providing equipment defect diagnosis through characteristic decomposition products.

Description

Technical Field

[0001] The embodiments of the present application relate to the technical field of gas purification and treatment, and in particular to a chromatography-mass spectrometry instrument and a method for detecting discharge decomposition products of mixed gases. Background Art

[0002] SF6 gas is widely used in the power industry due to its good insulation and arc extinguishing properties. N2 has the advantages of low environmental pollution, low price, and stable chemical properties. In recent years, N2 and SF6 mixed gas has been widely used as a gas insulation medium in the power industry. Accurate detection of the decomposition products of SF6 / N2 mixed gas under different discharge conditions is of great significance for finding characteristic decomposition products, proposing defect diagnosis methods, and improving the stability of power grid operation. At present, the use of chromatography-mass spectrometry can be used to comprehensively detect the decomposition products. The chromatography-mass spectrometry has both the advantages of mass spectrometry quantitative and chromatography qualitative. Its working principle is: chromatographic separation of the product to be tested, separation of different components in the mixture through a chromatographic column according to different physical and chemical properties; ionization of the components separated by chromatography through a mass spectrometer, and accurate characterization of their chemical composition based on their mass-charge ratio.

[0003] Traditional chromatography-mass spectrometry detection uses a single-channel injection method, and only one chromatographic column is used to separate the mixture. Since the physical and chemical properties of the SF6 / N2 mixed gas discharge decomposition products are similar, it is difficult to effectively distinguish all the products using one chromatographic column, which easily leads to fewer peaks in the test results spectrum, and often large peaks contain small peaks, resulting in the inability to accurately identify all the products. In addition, due to the high nitrogen content in the SF6 / N2 mixed gas, the products with similar properties to nitrogen (CH4, NF3, CF4, O2, etc.) cannot be seen as obvious peaks, which in turn affects the detection effect. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art or related art.

[0005] To this end, a first aspect of the present invention provides a chromatography-mass spectrometer.

[0006] A second aspect of the present invention provides a method for detecting mixed gas discharge decomposition products.

[0007] In view of this, according to a first aspect of an embodiment of the present application, a chromatography-mass spectrometry instrument is proposed, comprising: A sample quantitative component, which is used to quantitatively control the sample gas and divide the sample gas into two paths; A first chromatographic column, wherein the first chromatographic column is connected to a sample quantification component; A first channel, the first channel is connected to the first chromatographic column, the first channel is a dielectric barrier discharge plasma detector channel, and the first channel is used to detect substances before the peak time of the sample gas SF6; a second chromatographic column, the second chromatographic column being connected to the sample quantification component; The second channel is connected to the second chromatographic column, the second channel is a mass spectrometer detector channel, and the second channel is used to detect substances after the peak time of the sample gas SF6.

[0008] In a feasible embodiment, the sample quantification component includes: A ten-way valve, wherein the ten-way valve has a first state and a second state, and the ten-way valve is connected to the first chromatographic column and the second chromatographic column; A sample air inlet pipeline, wherein the sample air inlet pipeline is connected to the ten-way valve; A sample exhaust pipeline, wherein the sample exhaust pipeline is connected to the ten-way valve; a first quantitative ring, wherein the first quantitative ring is connected to the ten-way valve; a second quantitative ring, the second quantitative ring being connected to the ten-way valve; A first carrier gas inlet is connected to the ten-way valve.

[0009] In a feasible implementation manner, when the ten-way valve is in the first state, valve No. 2 inside the ten-way valve is connected to valve No. 3, valve No. 4 is connected to valve No. 5, valve No. 6 is connected to valve No. 7, valve No. 8 is connected to valve No. 9, and valve No. 10 is connected to valve No. 1; When the ten-way valve is in the second state, valve No. 1 in the ten-way valve is connected to valve No. 2, valve No. 3 is connected to valve No. 4, valve No. 5 is connected to valve No. 6, valve No. 7 is connected to valve No. 8, and valve No. 9 is connected to valve No. 10; The sample air inlet pipeline is connected to the No. 2 valve of the ten-way valve; The sample exhaust pipeline is connected to valve No. 1 of the ten-way valve; One end of the first quantitative ring is connected to the seventh valve of the ten-way valve, and the other end of the first quantitative ring is connected to the tenth valve of the ten-way valve; One end of the second quantitative ring is connected to the No. 3 valve of the ten-way valve, and the other end of the second quantitative ring is connected to the No. 6 valve of the ten-way valve; The first chromatographic column is connected to valve No. 8 of the ten-way valve, and the second chromatographic column is connected to valve No. 4 of the ten-way valve; The first carrier gas inlet is connected to the ninth valve of the ten-way valve; The second carrier gas inlet is connected to valve No. 5 of the ten-way valve.

[0010] In a feasible implementation, it also includes: The shunt component is arranged between the first chromatographic column and the first channel. Before the SF6 in the sample gas reaches the peak time, the shunt component introduces the sample gas into the first channel. After the SF6 in the sample gas reaches the peak time, the shunt component discharges the sample gas.

[0011] In a feasible implementation manner, the flow diversion component includes: A six-way valve having a first state and a second state; When the six-way valve is in the first state, valve No. 2 inside the six-way valve is connected to valve No. 3, valve No. 4 is connected to valve No. 5, and valve No. 6 is connected to valve No. 1; When the six-way valve is in the second state, valve No. 1 inside the six-way valve is connected to valve No. 2, valve No. 3 is connected to valve No. 4, and valve No. 6 is connected to valve No. 1; The sixth valve of the six-way valve is connected to the first chromatographic column, and the first valve of the six-way valve is connected to the first channel; a third chromatographic column, the third chromatographic column being connected to valve No. 1 of the six-way valve, and the third chromatographic column being connected to the second channel; An exhaust port, wherein the exhaust port is connected to valve No. 5 of the six-way valve.

[0012] In a feasible embodiment, the sample quantification component further includes: A shunt flow path is provided between the sample quantification component and the second chromatographic column.

[0013] In a feasible implementation manner, the flow diversion component further includes: A carrier gas circuit, one end of which is connected to valve No. 2 of the six-way valve, and the other end of which is connected to valve No. 4 of the six-way valve; A third carrier gas inlet is connected to valve No. 3 of the six-way valve.

[0014] In a feasible implementation manner, the chromatographic column selected for the first chromatographic column is a Q column; The chromatographic columns selected for the second chromatographic column are Q column and CPCIL5 column; The chromatographic column selected for the third chromatographic column is 5A molecular sieve.

[0015] According to a second aspect of an embodiment of the present application, a method for detecting mixed gas discharge decomposition products is provided, which is applied to any of the above-mentioned chromatograph-mass spectrometers, comprising: When the discharge decomposition product of the SF6 / N2 mixed gas is introduced into the sample quantitative component and no detection signal is sent to the sample quantitative component, the ten-way valve in the sample quantitative component is in the first state, and the SF6 / N2 mixed gas is directly discharged after being introduced into the sample quantitative component; Sending a detection signal to the sample quantification component, the ten-way valve in the sample quantification component switches from a first state to a second state; The sample quantitative component introduces the discharge decomposition products of the SF6 / N2 mixed gas into the first chromatographic column and the second chromatographic column; The discharge decomposition products of the SF6 / N2 mixed gas enter the first channel through the first chromatographic column, and the first channel detects the substances before the SF6 peak time in the mixed gas; The discharge decomposition products of the SF6 / N2 mixed gas enter the second channel through the second chromatographic column, and the second channel detects substances after the SF6 peak time in the mixed gas.

[0016] In a feasible implementation, it also includes: A flow splitter assembly is provided between the first chromatographic column and the first channel, and the flow splitter assembly is used to introduce the sample gas into the first channel or discharge the chromatograph-mass spectrometer; When SF6 in the sample gas has not reached the peak position, the flow splitting component introduces the sample gas into the first channel; After SF6 in the sample gas reaches the peak position, an electrical signal is sent to the diversion component, and the diversion component discharges the sample gas out of the chromatography-mass spectrometry instrument.

[0017] Compared with the prior art, the present invention has at least the following beneficial effects: the present invention realizes dual-channel detection. Compared with the existing single-channel detection combined instrument, the present invention solves the problem that the peak time of the above-mentioned substance is not obvious and is included in the peak of other substances.

[0018] The present invention increases the injection channel by modifying the chromatography-mass spectrometry instrument. Currently, dual-channel injection of the first channel BID channel and the second channel MSD channel can be realized, and the first chromatographic column and the second chromatographic column are used to separate the samples, thereby avoiding the situation that the existing samples cannot be completely separated when detected by the existing single-channel coupling instrument.

[0019] At present, the present invention can realize the calibration of existing standard gas, and there are no interference peaks and impurities when detecting unknown samples. It is of great help to the detection of decomposition products of SF6 / N2 mixed gas, and lays the foundation for realizing the diagnosis of equipment defects through characteristic decomposition products. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Various other advantages and benefits will become apparent to those of ordinary skill in the art by reading the detailed description of the preferred embodiments below. The accompanying drawings are only for the purpose of illustrating the preferred embodiments and are not to be considered as limiting the present application. Also, the same reference symbols are used throughout the accompanying drawings to represent the same components. In the accompanying drawings: Figure 1 A flow chart of a chromatogram-mass spectrometer according to an embodiment of the present application; Figure 2 A schematic flow chart of a method for detecting mixed gas discharge decomposition products according to an embodiment of the present application; Figure 3 This is a detection effect diagram of an existing single-channel detector; Figure 4 This is another detection effect diagram of the existing single-channel detector; Figure 5 A chromatogram detected by a BID channel of a chromatogram-mass spectrometer according to an embodiment of the present application; Figure 6 A BID channel detection table of a chromatographic mass spectrometer according to an embodiment of the present application; Figure 7 A chromatogram of standard gas 1 of a chromatogram-mass spectrometer according to an embodiment of the present application; Figure 8 A chromatogram of standard gas 2 of a chromatogram-mass spectrometer according to an embodiment of the present application; Fig. 9 This is a chromatogram of standard gas 3 of a chromatography-mass spectrometer according to an embodiment of the present application.

[0021] in, Figure 1 The corresponding relationship between the reference numerals and the component names is as follows: 100, sample quantification component; 200, first chromatographic column; 300, first channel; 400, second chromatographic column; 500, second channel; 600, flow splitting component; 110, ten-way valve; 120, sample air inlet pipeline; 130, sample air exhaust pipeline; 140, first quantitative loop; 150, second quantitative loop; 160, first carrier gas inlet; 170, second carrier gas inlet; 180, diversion flow path; 610, six-way valve; 620, third chromatographic column; 630, exhaust port; 640, carrier gas loop; 650, third carrier gas inlet. DETAILED DESCRIPTION

[0022] In order to better understand the above-mentioned technical scheme, the technical scheme of the embodiments of the present application is described in detail below through the accompanying drawings and specific embodiments. It should be understood that the embodiments of the present application and the specific features in the embodiments are detailed descriptions of the technical scheme of the embodiments of the present application, rather than limitations on the technical scheme of the present application. In the absence of conflict, the embodiments of the present application and the technical features in the embodiments may be combined with each other.

[0023] like Figure 1 As shown, according to the first aspect of an embodiment of the present application, a chromatography-mass spectrometry instrument is proposed, comprising: a sample quantification component 100, wherein the sample quantification component 100 is used to quantitatively control the sample gas and divide the sample gas into two paths; a first chromatographic column 200, wherein the first chromatographic column 200 is connected to the sample quantification component 100; a first channel 300, wherein the first channel 300 is connected to the first chromatographic column 200, wherein the first channel 300 is a dielectric barrier discharge plasma detector channel, and wherein the first channel 300 is used to detect substances before the peak time of the sample gas SF6; a second chromatographic column 400, wherein the second chromatographic column 400 is connected to the sample quantification component 100; and a second channel 500, wherein the second channel 500 is connected to the second chromatographic column 400, wherein the second channel 500 is a mass spectrometer detector channel, and wherein the second channel 500 is used to detect substances after the peak time of the sample gas SF6.

[0024] In this embodiment, the sample gas detected by the chromatography-mass spectrometry instrument is the discharge decomposition product of the SF6 / N2 mixed gas.

[0025] The chromatography-mass spectrometry instrument provided in the embodiment of the present application includes a sample quantification component 100 , a first chromatographic column 200 , a first channel 300 , a second chromatographic column 400 , and a second channel 500 .

[0026] During use, the sample quantitative component 100 is used to quantitatively control the sample gas and divide the sample gas into two paths, which are respectively sent to the first chromatographic column 200, the first channel 300 and the second chromatographic column 400, the second channel 500.

[0027] Among them, the first channel 300 is a dielectric barrier discharge plasma detector channel (hereinafter referred to as BID channel), which is used to detect substances before the peak time of the sample gas SF6, mainly including N2, O2, NF3, CF4, CH4, and H2.

[0028] Among them, the second channel 500 is a mass spectrometer detector channel (hereinafter referred to as MSD channel), which is used to detect substances after the peak time of the sample gas SF6, mainly including SO2F2, SOF2, COS, SO2, N2O, C2F6, and C3F8.

[0029] Furthermore, the present invention realizes dual-channel detection. Compared with the existing single-channel detection combined instrument, the present invention solves the problem that the peak time of the above-mentioned substance is not obvious and is included in the peak of other substances.

[0030] The present invention increases the injection channel by modifying the chromatography-mass spectrometry instrument. Currently, dual-channel injection of the first channel 300BID channel and the second channel 500MSD channel can be realized, and the first chromatographic column 200 and the second chromatographic column 400 are used to separate the samples, avoiding the situation that the existing samples cannot be completely separated when detected by the existing single-channel coupling instrument.

[0031] At present, the present invention can realize the calibration of existing standard gas, and there are no interference peaks and impurities when detecting unknown samples. It is of great help to the detection of decomposition products of SF6 / N2 mixed gas, and lays the foundation for realizing the diagnosis of equipment defects through characteristic decomposition products.

[0032] like Figure 1 As shown, the sample quantification component 100 includes: a ten-way valve 110, the ten-way valve 110 has a first state and a second state, and the ten-way valve 110 is connected to the first chromatographic column 200 and the second chromatographic column 400; a sample air inlet pipeline 120, the sample air inlet pipeline 120 is connected to the ten-way valve 110; a sample exhaust pipeline 130, the sample exhaust pipeline 130 is connected to the ten-way valve 110; a first quantitative ring 140, the first quantitative ring 140 is connected to the ten-way valve 110; a second quantitative ring 150, the second quantitative ring 150 is connected to the ten-way valve 110; a first carrier gas inlet 160, the first carrier gas inlet 160 is connected to the ten-way valve 110.

[0033] like Figure 1As shown, when the ten-way valve 110 is in the first state, valve No. 2 inside the ten-way valve 110 is connected to valve No. 3, valve No. 4 is connected to valve No. 5, valve No. 6 is connected to valve No. 7, valve No. 8 is connected to valve No. 9, and valve No. 10 is connected to valve No. 1; when the ten-way valve 110 is in the second state, valve No. 1 inside the ten-way valve 110 is connected to valve No. 2, valve No. 3 is connected to valve No. 4, valve No. 5 is connected to valve No. 6, valve No. 7 is connected to valve No. 8, and valve No. 9 is connected to valve No. 10; the sample air inlet pipeline 120 is connected to valve No. 2 of the ten-way valve 110; the sample exhaust pipeline 130 is connected to valve No. 1 of the ten-way valve 110; the first quantitative ring 140 is connected to the One end is connected to valve No. 7 of the ten-way valve 110, and the other end of the first quantitative ring 140 is connected to valve No. 10 of the ten-way valve 110; one end of the second quantitative ring 150 is connected to valve No. 3 of the ten-way valve 110, and the other end of the second quantitative ring 150 is connected to valve No. 6 of the ten-way valve 110; the first chromatographic column 200 is connected to valve No. 8 of the ten-way valve 110, and the second chromatographic column 400 is connected to valve No. 4 of the ten-way valve 110; the first carrier gas inlet 160 is connected to valve No. 9 of the ten-way valve 110; the second carrier gas inlet 170 is connected to valve No. 5 of the ten-way valve 110.

[0034] In this technical solution, the sample quantification component 100 includes a ten-way valve 110 , a sample air inlet pipe 120 , a sample air exhaust pipe 130 , a first quantification ring 140 , a second quantification ring 150 and a first carrier gas inlet 160 .

[0035] Among them, the ten-way valve 110 has ten valve ports, which are named valve No. 1, valve No. 2, valve No. 3, valve No. 4, valve No. 5, valve No. 6, valve No. 7, valve No. 8, valve No. 9 and valve No. 10 of the ten-way valve 110 in sequence in the present invention.

[0036] like Figure 1 As shown, in the ten-way valve 110 in the figure, the valve port marked 1 is valve No. 1 of the ten-way valve 110, the valve port marked 2 is valve No. 2 of the ten-way valve 110, the valve port marked 3 is valve No. 3 of the ten-way valve 110, the valve port marked 4 is valve No. 4 of the ten-way valve 110, the valve port marked 5 is valve No. 5 of the ten-way valve 110, the valve port marked 6 is valve No. 6 of the ten-way valve 110, the valve port marked 7 is valve No. 7 of the ten-way valve 110, the valve port marked 8 is valve No. 8 of the ten-way valve 110, the valve port marked 9 is valve No. 9 of the ten-way valve 110, and the valve port marked 10 is valve No. 10 of the ten-way valve 110.

[0037] The sample air inlet pipeline 120 is connected to the No. 2 valve of the ten-way valve 110 , and the sample air outlet pipeline 130 is connected to the No. 1 valve of the ten-way valve 110 .

[0038] The first quantitative ring 140 is connected to the seventh valve and the tenth valve of the ten-way valve 110 , and the second quantitative ring 150 is connected to the third valve and the sixth valve of the ten-way valve 110 .

[0039] Among them, the ten-way valve 110 has a first state and a second state. When the ten-way valve 110 is in the first state, valve No. 2 of the ten-way valve 110 is connected to valve No. 3, valve No. 4 is connected to valve No. 5, valve No. 6 is connected to valve No. 7, valve No. 8 is connected to valve No. 9, and valve No. 10 is connected to valve No. 1; when the ten-way valve 110 is in the second state, valve No. 1 of the ten-way valve 110 is connected to valve No. 2, valve No. 3 is connected to valve No. 4, valve No. 5 is connected to valve No. 6, valve No. 7 is connected to valve No. 8, and valve No. 9 is connected to valve No. 10.

[0040] The first carrier gas inlet 160 is connected to the fifth valve of the ten-way valve 110 .

[0041] During use, when no detection signal is sent to the ten-way valve 110, the ten-way valve 110 is in the first state. When the ten-way valve 110 is in the first state, the gas flow path of the sample quantitative component 100 is that the sample air inlet pipe 120 supplies the sample gas to valve No. 2 of the ten-way valve 110, the sample gas enters valve No. 3 from valve No. 2, enters valve No. 6 from valve No. 3 through the second quantitative ring 150, enters valve No. 7 from valve No. 6, enters valve No. 10 from valve No. 7 through the first quantitative ring 140, and the sample gas is discharged from valve No. 10 from the sample exhaust pipe 130.

[0042] After the detection signal is sent to the ten-way valve 110 , the ten-way valve 110 switches from the first state to the second state.

[0043] At this time, the sample gas inlet pipeline 120 delivers the sample gas into valve No. 2 of the ten-way valve, the sample gas flows from valve No. 2 into valve No. 1, and is discharged from the sample gas exhaust pipeline 130 .

[0044] The first carrier gas inlet 160 delivers carrier gas into the ten-way valve 110 through valve No. 9 of the ten-way valve 110. The carrier gas is delivered from valve No. 9 to valve No. 10, and the carrier gas enters the first quantitative ring 140 from valve No. 10. The carrier gas pushes the sample gas in the first quantitative ring 140 from the first quantitative ring 140 to valve No. 7, from valve No. 7 to valve No. 8, and from valve No. 8 to the first chromatographic column 200, thereby delivering a quantitative amount of sample gas into the first chromatographic column 200 and the first channel 300.

[0045] The second carrier gas inlet 170 delivers carrier gas into the ten-way valve 110 through valve No. 5 of the ten-way valve 110. The carrier gas flows from valve No. 5 into valve No. 6 and enters the second quantitative ring 150 from valve No. 6. The carrier gas pushes the sample gas in the second quantitative ring 150 into valve No. 3, and delivers the sample gas into the second chromatographic column 400 and the second channel 500 through valve No. 3.

[0046] Through the above-mentioned air flow path, during detection, the sample gas in the first quantitative ring 140 is sent to the first chromatographic column 200 and the first channel 300, and the sample gas in the second quantitative ring 150 is sent to the second chromatographic column 400 and the second channel 500, thereby realizing dual-channel detection.

[0047] like Figure 1 As shown, the chromatography-mass spectrometry instrument also includes: a diversion component 600, which is arranged between the first chromatographic column 200 and the first channel 300. Before the SF6 in the sample gas reaches the peak time, the diversion component 600 introduces the sample gas into the first channel 300. When the SF6 in the sample gas reaches the peak time, the diversion component 600 discharges the sample gas.

[0048] In this technical solution, the chromatographic mass spectrometer also includes a flow splitter assembly 600. The chromatographic column in the existing single-channel detector usually adopts a 5A molecular sieve chromatographic column. Since the decomposition products of SF6 contain highly corrosive products, the 5A molecular sieve chromatographic column will be corroded, resulting in poor separation effect of the chromatographic column after multiple injections and inaccurate detection results. To solve this problem, a flow splitter assembly 600 is arranged between the first chromatographic column 200 and the first channel 300. Before the SF6 in the sample gas reaches the peak position, the flow splitter assembly 600 introduces the sample gas into the first channel 300, so that the first channel 300 can detect the sample gas. After the SF6 in the sample gas reaches the peak position, the flow splitter assembly 600 can discharge the sample gas from the circuit of the coupled instrument, thereby preventing the decomposition products of SF6 from corroding the chromatographic column in the flow splitter assembly 600.

[0049] like Figure 1 As shown, the diversion component 600 includes: a six-way valve 610, the six-way valve 610 has a first state and a second state; when the six-way valve 610 is in the first state, valve No. 2 inside the six-way valve 610 is connected to valve No. 3, valve No. 4 is connected to valve No. 5, and valve No. 6 is connected to valve No. 1; when the six-way valve 610 is in the second state, valve No. 1 inside the six-way valve 610 is connected to valve No. 2, valve No. 3 is connected to valve No. 4, and valve No. 6 is connected to valve No. 1; a third chromatographic column 620, the third chromatographic column 620 is connected to valve No. 1 of the six-way valve 610, and the third chromatographic column 620 is connected to the second channel 500; an exhaust port 630, the exhaust port 630 is connected to the valve No. 5.

[0050] like Figure 1As shown, in the six-way valve 610 in the figure, the valve port marked 1 is valve No. 1 of the six-way valve 610, the valve port marked 2 is valve No. 2 of the six-way valve 610, the valve port marked 3 is valve No. 3 of the six-way valve 610, the valve port marked 4 is valve No. 4 of the six-way valve 610, the valve port marked 5 is valve No. 5 of the six-way valve 610, and the valve port marked 6 is valve No. 6 of the six-way valve 610.

[0051] In this technical solution, the flow splitting component 600 includes a six-way valve 610 , a third chromatographic column 620 and an exhaust port 630 .

[0052] The six-way valve 610 has six valve ports, which are respectively named valve No. 1, valve No. 2, valve No. 3, valve No. 4, valve No. 5 and valve No. 6 of the six-way valve 610 .

[0053] Among them, the six-way valve 610 has a first state and a second state. When the sample gas is before the peak time of SF6, the six-way valve 610 is in the first state through an electrical signal. When the six-way valve 610 is in the first state, valve No. 2 inside the six-way valve is connected to valve No. 3, valve No. 4 is connected to valve No. 5, and valve No. 6 is connected to valve No. 1.

[0054] In this state, the sample gas flows from the first chromatographic column 200 to the sixth valve of the six-way valve 610 , flows from the sixth valve to the first valve, and flows from the first valve to the first channel 300 .

[0055] The flow splitting component 600 further includes a third chromatographic column 620 , which is disposed between the first channel 300 and valve No. 1 of the six-way valve 610 .

[0056] When the sample gas reaches the peak time of SF6, the six-way valve 610 is switched from the first state to the second state through an electrical signal. When the six-way valve 610 is in the second state, valve No. 1 in the six-way valve 610 is connected to valve No. 2, valve No. 3 is connected to valve No. 4, and valve No. 5 is connected to valve No. 6.

[0057] In this state, the sample gas flows from the first chromatographic column 200 to the sixth valve of the six-way valve 610 , flows from the sixth valve to the fifth valve, and is exhausted from the exhaust port 630 connected to the fifth valve.

[0058] The present invention uses the above structure to deliver the sample gas into the first channel 300 through the third chromatographic column 620 before the sample gas SF6 reaches the peak time, and discharge the sample gas after the sample gas SF6 reaches the peak time, thereby effectively preventing the decomposition products of SF6 from corroding the third chromatographic column 620.

[0059] like Figure 1As shown, the sample quantification component 100 further includes: a diversion flow path 180 , and the diversion flow path 180 is arranged between the sample quantification component 100 and the second chromatographic column 400 .

[0060] In this technical solution, a bypass flow path 180 is set between the sample quantification component 100 and the second chromatographic column 400. The bypass flow path 180 is used to control the concentration of the sample entering the instrument. When the sample gas concentration is high, the bypass flow path 180 adopts a bypass injection method to reduce the concentration of the sample gas entering the instrument.

[0061] This arrangement can avoid saturation caused by the sample having too high a concentration and directly entering the second chromatographic column 400 and the second channel 500, thereby improving the stability of the present invention.

[0062] like Figure 1 As shown, the diversion component 600 also includes: a carrier gas circuit 640, one end of which is connected to valve No. 2 of the six-way valve 610, and the other end of which is connected to valve No. 4 of the six-way valve 610; a third carrier gas inlet 650, which is connected to valve No. 3 of the six-way valve 610.

[0063] In this technical solution, the diversion component 600 also includes a carrier gas circuit 640 and a third carrier gas inlet 650, wherein the carrier gas circuit 640 is connected to valve No. 2 and valve No. 4 of the six-way valve 610, and the third carrier gas inlet 650 is connected to valve No. 3 of the six-way valve 610.

[0064] During use, when the six-way valve 610 is in the first state, the carrier gas enters valve No. 3 of the six-way valve 610 from the third carrier gas inlet 650, enters valve No. 2 from valve No. 3 of the six-way valve 610, enters the carrier gas loop 640 from valve No. 2, enters valve No. 4 from the carrier gas loop 640, enters valve No. 5 from valve No. 4, and finally discharges the loop from the exhaust port 630 connected to valve No. 5.

[0065] When the six-way valve 610 is in the second state, the carrier gas enters valve No. 3 of the six-way valve 610 from the third carrier gas inlet 650, enters valve No. 4 from valve No. 3, enters the carrier gas loop 640 from valve No. 4, enters valve No. 2 from the carrier gas loop 640, enters valve No. 1 from valve No. 2, and enters the third chromatographic column 620 and the first channel 300 from valve No. 1, thereby pushing the sample gas after the SF6 peak out of the third chromatographic column 620 to the first channel 300 to avoid residue, and further avoid corrosion of the chromatographic column by the decomposition products of SF6.

[0066] like Figure 1As shown, the chromatographic column selected for the first chromatographic column 200 is a Q column; the chromatographic column selected for the second chromatographic column 400 is a Q column and a CPCIL5 column; and the chromatographic column selected for the third chromatographic column 620 is a 5A molecular sieve.

[0067] In this technical solution, the first chromatographic column 200 uses a Q column, the second chromatographic column 400 uses a Q column and a CPCIL5 column, and the third chromatographic column 620 uses a 5A molecular sieve.

[0068] Previously, the chromatographic column used in single-channel detection was a 5A molecular sieve, which has a better detection effect on the discharge decomposition products of the SF6 / N2 mixed gas before the SF6 peak, but is easily corroded by the SF6 decomposition products. When the 5A molecular sieve is corroded, the detection effect will be reduced. Therefore, the present invention limits the three types of chromatographic columns in the chromatographic mass spectrometer, among which the Q column and the CPCIL5 column can resist high corrosion. Therefore, the first chromatographic column 200 adopts the Q column, which is used to separate the discharge decomposition products of the mixed gas before the SF6 peak. At the same time, the SF6 peak The mixed gas discharge decomposition products after the SF6 peak still pass through the first chromatographic column 200. The second chromatographic column 400 uses a Q column and a CPCIL5 column, which are mainly used to separate the mixed gas discharge decomposition products after the SF6 peak. The third chromatographic column 620 still uses a 5A molecular sieve, which is mainly used to further separate the mixed gas discharge decomposition products before the SF6 peak. At the same time, the mixed gas discharge decomposition products after the SF6 peak do not pass through the third chromatographic column 620, and the shunt component 600 is used to prevent the SF6 decomposition products from corroding the third chromatographic column 620.

[0069] This setting further avoids the corrosion of the chromatographic column by the sample gas, thereby improving the accuracy of the detection results.

[0070] like Figure 2 As shown, according to the second aspect of the embodiment of the present application, a method for detecting mixed gas discharge decomposition products is proposed, which is applied to any one of the above-mentioned chromatograph-mass spectrometers, comprising: Step 101: introducing discharge decomposition products of SF6 / N2 mixed gas into the sample quantitative component 100. When no detection signal is sent to the sample quantitative component 100, the ten-way valve 110 in the sample quantitative component 100 is in the first state, and the discharge decomposition products of SF6 / N2 mixed gas are directly discharged after being introduced into the sample quantitative component 100; Step 102: sending a detection signal to the sample quantification component 100, and the ten-way valve 110 in the sample quantification component 100 switches from the first state to the second state; Step 103: The sample quantification component 100 introduces the discharge decomposition products of the SF6 / N2 mixed gas into the first chromatographic column 200 and the second chromatographic column 400; Step 104: the discharge decomposition products of the SF6 / N2 mixed gas enter the first channel 300 through the first chromatographic column 200, and the first channel 300 detects the substances before the SF6 peak time in the mixed gas; Step 105: the discharge decomposition products of the SF6 / N2 mixed gas enter the second channel 500 through the second chromatographic column 400, and the second channel 500 detects substances after the SF6 peak time in the mixed gas.

[0071] In this technical solution, the present invention proposes for the first time to use a dual-channel injection method to transform the chromatography-mass spectrometry instrument. The dual-channel injection method can allow sulfides and inorganic substances to enter different channels through the separation of chromatographic columns. The detection results are respectively reflected on the first channel 300BID channel and the second channel 500MSD channel, avoiding the situation in which nitrogen, oxygen, methane and other peaks are all included in nitrogen in the previous single-channel detection. Multiple chromatographic columns are used to separate the samples, and the detection results will not have peak crossing, overlapping, etc., and the detection efficiency is higher.

[0072] like Figure 3-Figure 9 As shown, the modified chromatograph-mass spectrometer is used, and the adaptation setting method is applied to perform qualitative and calibration processing on the existing standard gas, to verify whether the instrument can produce obvious peaks for the measured samples after modification, and whether there is non-overlapping phenomenon, and whether the samples can be accurately qualitatively measured. The gases contained in the standard gas measured by the present invention include standard gas 1: oxygen (O2), nitrogen (N2), hydrogen (H2), methane (CH4), carbon tetrafluoride (CF4), carbon monoxide (CO), carbon dioxide (CO2), hexafluoroethane (C2F6), nitrous oxide (N2O), octafluoropropane (C3F8), nitrogen trifluoride (NF3). Standard gas 2: hydrogen sulfide (H2S), sulfuryl fluoride (SO2F2), carbon disulfide (CS2), thionyl fluoride (SOF2), carbonyl sulfide (COS). Standard gas 3: hexafluoropropylene (C3F6), octafluorocyclobutane (C4F8), trifluoromethane (CHF3), pentafluoroethane (C2HF5), heptafluoropropane (C3HF7), trifluoroethane (C2H3F3), tetrafluoroethane (C2H2F4), tetrafluoroethylene (C2F4), hexafluoroethane (C2F6). The test results of the above standard gases using the modified instrument are as above. Figure 3-Figure 9 shown.

[0073] According to the above-mentioned benchmark gas detection results, it can be seen that the modified chromatography-mass spectrometry instrument can separate the benchmark gas, and the peaks are obvious. There is no peak overlap or crossover before the modification, and all components have obvious peaks. The modified instrument can accurately identify and quantify the decomposition products of the SF6 / N2 mixed gas after discharge decomposition. The research results are helpful for on-site equipment operation, maintenance and diagnosis.

[0074] The mixed gas discharge decomposition product detection method also includes: setting a shunt component between the first chromatographic column and the first channel, the shunt component is used to introduce the sample gas into the first channel or discharge it from the chromatogram-mass spectrometer; when SF6 in the sample gas has not reached the peak position, the shunt component introduces the sample gas into the first channel; after SF6 in the sample gas reaches the peak position, an electrical signal is sent to the shunt component, and the shunt component discharges the sample gas from the chromatogram-mass spectrometer.

[0075] In this technical solution, a flow splitter assembly is added between the first chromatographic column and the first channel, and a valve cut operation is performed to prevent the highly corrosive decomposition products of SF6 from corroding the third chromatographic column.

[0076] In the present invention, the terms "first", "second", and "third" are used for descriptive purposes only and should not be understood as indicating or implying relative importance; the term "plurality" refers to two or more, unless otherwise clearly defined. The terms "installed", "connected", "connected", "fixed", etc. should be understood in a broad sense. For example, "connected" can be a fixed connection, a detachable connection, or an integral connection; "connected" can be a direct connection or an indirect connection through an intermediate medium. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0077] In the description of the present invention, it is necessary to understand that the directions or positional relationships indicated by terms such as “upper”, “lower”, “left”, “right”, “front” and “back” are based on the directions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or unit referred to must have a specific direction, be constructed and operated in a specific orientation, and therefore, cannot be understood as a limitation on the present invention.

[0078] In the description of this specification, the description of the terms "one embodiment", "some embodiments", "specific embodiments", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0079] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A chromatography-mass spectrometry instrument, characterized in that: include: A sample quantitative component, which is used to quantitatively control the sample gas and divide the sample gas into two paths; a first chromatographic column, the first chromatographic column being connected to the sample quantification component; A first channel, the first channel is connected to the first chromatographic column, the first channel is a dielectric barrier discharge plasma detector channel, and the first channel is used to detect substances before the peak time of the sample gas SF6; a second chromatographic column, the second chromatographic column being connected to the sample quantification component; The second channel is connected to the second chromatographic column, the second channel is a mass spectrometer detector channel, and the second channel is used to detect substances after the peak time of the sample gas SF6.

2. The chromatography-mass spectrometry instrument according to claim 1, characterized in that: The sample quantification component comprises: A ten-way valve, the ten-way valve having a first state and a second state, the ten-way valve being connected to the first chromatographic column and the second chromatographic column; A sample air inlet pipeline, wherein the sample air inlet pipeline is connected to the ten-way valve; A sample exhaust pipeline, wherein the sample exhaust pipeline is connected to the ten-way valve; a first quantitative ring, wherein the first quantitative ring is connected to the ten-way valve; a second quantitative ring, the second quantitative ring being connected to the ten-way valve; a first carrier gas inlet, the first carrier gas inlet being connected to the ten-way valve; A second carrier gas inlet is connected to the ten-way valve.

3. The chromatography-mass spectrometry instrument according to claim 2, characterized in that: When the ten-way valve is in the first state, valve No. 2 inside the ten-way valve is connected to valve No. 3, valve No. 4 is connected to valve No. 5, valve No. 6 is connected to valve No. 7, valve No. 8 is connected to valve No. 9, and valve No. 10 is connected to valve No. 1; When the ten-way valve is in the second state, valve No. 1 in the ten-way valve is connected to valve No. 2, valve No. 3 is connected to valve No. 4, valve No. 5 is connected to valve No. 6, valve No. 7 is connected to valve No. 8, and valve No. 9 is connected to valve No. 10; The sample air inlet pipeline is connected to the No. 2 valve of the ten-way valve; The sample exhaust pipeline is connected to valve No. 1 of the ten-way valve; One end of the first quantitative ring is connected to the seventh valve of the ten-way valve, and the other end of the first quantitative ring is connected to the tenth valve of the ten-way valve; One end of the second quantitative ring is connected to the No. 3 valve of the ten-way valve, and the other end of the second quantitative ring is connected to the No. 6 valve of the ten-way valve; The first chromatographic column is connected to valve No. 8 of the ten-way valve, and the second chromatographic column is connected to valve No. 4 of the ten-way valve; The first carrier gas inlet is connected to the ninth valve of the ten-way valve; The second carrier gas inlet is connected to valve No. 5 of the ten-way valve.

4. The chromatography-mass spectrometry instrument according to claim 1, characterized in that: Also includes: The shunt component is arranged between the first chromatographic column and the first channel. Before the SF6 in the sample gas reaches the peak time, the shunt component introduces the sample gas into the first channel. After the SF6 in the sample gas reaches the peak time, the shunt component discharges the sample gas.

5. The chromatography-mass spectrometry instrument according to claim 4, characterized in that: The diversion component comprises: A six-way valve having a first state and a second state; When the six-way valve is in the first state, valve No. 2 inside the six-way valve is connected to valve No. 3, valve No. 4 is connected to valve No. 5, and valve No. 6 is connected to valve No. 1; When the six-way valve is in the second state, valve No. 1 inside the six-way valve is connected to valve No. 2, valve No. 3 is connected to valve No. 4, and valve No. 6 is connected to valve No. 1; The sixth valve of the six-way valve is connected to the first chromatographic column, and the first valve of the six-way valve is connected to the first channel; a third chromatographic column, the third chromatographic column being connected to valve No. 1 of the six-way valve, and the third chromatographic column being connected to the second channel; An exhaust port, wherein the exhaust port is connected to valve No. 5 of the six-way valve.

6. The chromatography-mass spectrometry instrument according to claim 2, characterized in that: The sample quantification component also includes: A shunt flow path is provided between the sample quantification component and the second chromatographic column.

7. The chromatography-mass spectrometry instrument according to claim 5, characterized in that: The diversion component also includes: A carrier gas circuit, one end of which is connected to valve No. 2 of the six-way valve, and the other end of which is connected to valve No. 4 of the six-way valve; A third carrier gas inlet is connected to valve No. 3 of the six-way valve.

8. The chromatography-mass spectrometry instrument according to claim 5, characterized in that: The chromatographic column selected for the first chromatographic column is a Q column; The chromatographic columns selected for the second chromatographic column are Q column and CPCIL5 column; The chromatographic column selected for the third chromatographic column is 5A molecular sieve.

9. A method for detecting mixed gas discharge decomposition products, characterized in that: The chromatographic mass spectrometer used in any one of claims 1 to 8 comprises: When the discharge decomposition products of the SF6 / N2 mixed gas are introduced into the sample quantitative component and no detection signal is sent to the sample quantitative component, the ten-way valve in the sample quantitative component is in the first state, and the discharge decomposition products of the SF6 / N2 mixed gas are directly discharged after being introduced into the sample quantitative component; Sending a detection signal to the sample quantification component, the ten-way valve in the sample quantification component switches from a first state to a second state; The sample quantification component introduces discharge decomposition products of the SF6 / N2 mixed gas into the first chromatographic column and the second chromatographic column; The discharge decomposition products of the SF6 / N2 mixed gas enter the first channel through the first chromatographic column, and the first channel detects the substances before the SF6 peak time in the decomposition products; The discharge decomposition products of the SF6 / N2 mixed gas enter the second channel through the second chromatographic column, and the second channel detects substances after the SF6 peak time in the decomposition products.

10. The method for detecting mixed gas discharge decomposition products according to claim 9, characterized in that: Also includes: A flow splitter assembly is provided between the first chromatographic column and the first channel, and the flow splitter assembly is used to introduce the sample gas into the first channel or discharge the chromatograph-mass spectrometer; When SF6 in the decomposition products has not reached the peak position, the flow splitting component introduces the sample gas into the first channel; After SF6 in the decomposition product reaches the peak position, an electrical signal is sent to the diversion component, and the diversion component discharges the sample gas out of the chromatography-mass spectrometry instrument.

Images