CN112362721A - Device and method for detecting sulfur isotope in gas in continuous flow mode - Google Patents
Device and method for detecting sulfur isotope in gas in continuous flow mode Download PDFInfo
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- CN112362721A CN112362721A CN201910682615.XA CN201910682615A CN112362721A CN 112362721 A CN112362721 A CN 112362721A CN 201910682615 A CN201910682615 A CN 201910682615A CN 112362721 A CN112362721 A CN 112362721A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 51
- 239000011593 sulfur Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims description 23
- 239000007789 gas Substances 0.000 claims abstract description 142
- 239000001307 helium Substances 0.000 claims abstract description 39
- 229910052734 helium Inorganic materials 0.000 claims abstract description 39
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 32
- 238000002485 combustion reaction Methods 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 21
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 238000004891 communication Methods 0.000 claims abstract description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 33
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052946 acanthite Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 4
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical group [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- 239000011491 glass wool Substances 0.000 claims description 2
- RTKIYNMVFMVABJ-UHFFFAOYSA-L thimerosal Chemical compound [Na+].CC[Hg]SC1=CC=CC=C1C([O-])=O RTKIYNMVFMVABJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 6
- 238000001514 detection method Methods 0.000 abstract description 2
- 101100204059 Caenorhabditis elegans trap-2 gene Proteins 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 2
- 229940056910 silver sulfide Drugs 0.000 description 2
- NVSDADJBGGUCLP-UHFFFAOYSA-N trisulfur Chemical compound S=S=S NVSDADJBGGUCLP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- -1 cadmium peracetic acid Chemical compound 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000022 continuous-flow isotope ratio mass spectrometry Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
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- General Health & Medical Sciences (AREA)
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Abstract
The invention belongs to the technical field of isotope analysis and detection, and relates to a device for detecting sulfur isotopes in gas in a continuous flow mode. The device includes: the system comprises a gas storage tank, a cold trap, an element instrument, an isotope mass spectrometer, a first helium conveying pipeline, a second helium conveying pipeline, a first gas inlet pipeline, a vent pipeline, an oxygen conveying pipeline and a second gas inlet pipeline, wherein the gas storage tank is used for storing a gas sample; the element appearance includes: a solid autosampler, a combustion furnace, and a reduction furnace; the first helium conveying pipeline, the gas storage tank, the cold trap, the first gas inlet pipeline, the combustion furnace, the reduction furnace, the second gas inlet pipeline and the isotope mass spectrometer are communicated in sequence; the cold trap is communicated with an emptying pipeline; the second helium conveying pipeline is communicated with the air inlet end of the cold trap; the oxygen delivery line is in communication with the furnace. The device of the invention does not need to pretreat the gas sample, and can calibrate the sulfur isotope in the gas sample by using the solid standard substance.
Description
Technical Field
The invention belongs to the technical field of isotope analysis detection, and particularly relates to a device and a method for detecting sulfur isotopes in gas in a continuous flow mode.
Background
Continuous flow mass spectrometry (CF-IRMS) is a new instrument developed on the basis of gas isotope mass spectrometry. The on-line analysis of stable isotopes is realized by connecting an element analyzer and an isotope ratio mass spectrometer through a continuous flow interface. The continuous flow mass spectrum directly collects target gas to enter a mass spectrum ion source under the carrying of helium flow, and because the sample is continuously processed and measured on line, the loss of the sample in the analysis process can be reduced, and the analysis speed and the sensitivity are improved.
The analysis method for detecting sulfur isotope by continuous flow mass spectrum is based on the principle of 'dynamic instantaneous combustion', a sample is wrapped by a tin cup, an automatic sample injector is fed into a high-temperature combustion tube of an element analyzer, the sample is combusted into sulfur oxide by 'oxygen blowing technology' under the protection of He gas, and SO is further generated by the reduction action of Cu2And enters isotope mass spectrometry with helium flow. The method can realize rapid and batch test on sulfur isotopes in samples such as rocks, soil, plants, kerogen and the like.
At present, the gas is mostly converted into solid sulfide by a chemical method for measuring sulfur isotopes in the gas, for example, sulfur dioxide gas can be fixed into sulfate radical by glass fiber treated by potassium carbonate and then converted into silver sulfide or barium sulfate; sulfur isotope in hydrogen sulfide gas can be introducedFixing hydrogen sulfide gas into CdS by cadmium peracetic acid, and adding Ag+Converting it into silver sulfide; and then converting the sulfide into sulfur dioxide indoors, analyzing the sulfur isotope composition by using a stable isotope mass spectrometer, and also converting the sulfide into sulfur hexafluoride to analyze the sulfur isotope composition. These methods all involve two or more chemical reactions, which must be completed to prevent isotope fractionation, and therefore, are very strict in operation and have many factors causing errors in response. Meanwhile, the harmfulness of the sulfur-containing chemical pretreatment is large. And SO is adopted in the isotope mass spectrometry process2As a working reference gas, due to SO2The sulfur-containing acidic gas is high in toxicity, is not easy to store, has strong viscosity in a pipeline, and is easy to corrode the pipeline and pollute the environment.
Disclosure of Invention
The invention aims to provide a device and a method for detecting sulfur isotopes in gas, wherein the device and the method have low pipeline corrosion degree.
In order to achieve the above object, a first aspect of the present invention provides an apparatus for detecting sulfur isotopes in a gas in a continuous flow mode. The device includes: the system comprises a gas storage tank, a cold trap, an element instrument, an isotope mass spectrometer, a first helium conveying pipeline, a second helium conveying pipeline, a first gas inlet pipeline, a vent pipeline, an oxygen conveying pipeline and a second gas inlet pipeline, wherein the gas storage tank is used for storing a gas sample;
the element appearance includes: a solid autosampler, a combustion furnace, and a reduction furnace;
the first helium gas delivery pipeline, the gas storage tank, the cold trap, the first gas inlet pipeline, the combustion furnace, the reduction furnace, the second gas inlet pipeline and the isotope mass spectrometer are communicated in sequence;
the cold trap is communicated with the emptying pipeline;
the second helium gas conveying pipeline is communicated with the gas inlet end of the cold trap;
the oxygen delivery line is in communication with the furnace.
Preferably, the device further comprises a six-way valve, wherein six interfaces of the six-way valve are respectively communicated with the gas storage tank, the gas inlet end and the gas outlet end of the cold trap, the gas inlet end and the gas outlet end of the second helium gas conveying pipeline and the emptying pipeline.
Preferably, the device further comprises a four-way valve, wherein the four-way valve is used for communicating the gas outlet end of the second helium gas conveying pipeline with the combustion furnace and is also used for communicating the oxygen conveying pipeline with the combustion furnace.
In one embodiment of the invention, the cold trap comprises: the device comprises a liquid nitrogen tank and a U-shaped pipe arranged in the liquid nitrogen tank;
the air inlet end of the U-shaped pipe is communicated with the air storage tank, and the air outlet end of the U-shaped pipe is communicated with the first air inlet pipeline and the second helium conveying pipeline; glass wool is filled in the U-shaped pipe; the U-shaped pipe is a glass pipe; the inner diameter of the U-shaped pipe is 2-3 mm.
In one embodiment of the invention, the isotope mass spectrometer comprises: the chromatographic column, the interface and the isotope mass spectrometer are communicated in sequence;
the chromatographic column is communicated with the reduction furnace.
Preferably, the chromatography column is a Teflon chromatography column; and pipelines in the element instrument are all Teflon pipes.
In a second aspect, the present invention provides a method for detecting sulfur isotopes in a gas in a continuous flow mode. The method is carried out in the apparatus according to the first aspect, and includes the steps of:
s1, helium carries a gas sample released by the gas storage tank through a first helium conveying pipeline, enters the cold trap for cooling adsorption, and gas which is not cooled and adsorbed in the gas sample is discharged out of the device through the emptying pipeline;
s2, placing a solid standard substance into the solid automatic sample injector, allowing the solid standard substance to enter the combustion furnace through the solid automatic sample injector, simultaneously conveying oxygen into the combustion furnace through the oxygen conveying pipeline, fully combusting the solid standard substance to generate gas containing sulfur dioxide and sulfur trioxide, and then conveying the gas into a reduction furnace to reduce the sulfur trioxide in the gas into the sulfur dioxide;
s3, inputting the reduced gas into the isotope mass spectrometer to detect a signal of a sulfur isotope, wherein the solid standard substance has a known sulfur isotope value;
s4, heating the cold trap to enable the cold trap to release the gas cooled and adsorbed by the cold trap, enabling helium in a second helium conveying pipeline to carry the released gas cooled and adsorbed to enter the combustion furnace, conveying oxygen to the combustion furnace through the oxygen conveying pipeline, fully combusting the released gas cooled and adsorbed to generate gas containing sulfur dioxide and sulfur trioxide, and then conveying the gas into a reduction furnace to reduce the sulfur trioxide in the gas into the sulfur dioxide;
s5, conveying the reduced gas into the isotope mass spectrometer to detect a signal of a sulfur isotope;
s6, comparing the signal of the sulfur isotope obtained in the step S5 with the signal of the sulfur isotope obtained in the step S3, thereby obtaining the composition of the sulfur isotope in the gas sample.
Preferably, step S4 further includes, before heating the cold trap, switching the state of the six-way valve to communicate the outlet end of the second helium gas delivery line with the inlet end of the cold trap.
Preferably, the temperature for heating the cold trap is 100 ℃ to 150 ℃.
More preferably, the temperature at which the cold trap is heated is 150 ℃.
Preferably, the solid standard substance is Ag2S or merthiolate.
Preferably, Ag2S is GBW04414 and/or GBW 04415.
According to the device for detecting the sulfur isotope in the gas in the continuous flow mode, the sulfur dioxide gas obtained by sequentially treating the solid standard substance through the combustion furnace and the reduction furnace is used as the working reference gas for calibration through the solid automatic sample injector, so that the sulfur dioxide which is not easy to store is prevented from being directly used as the reference gas, the retention of the sulfur disulfide in a pipeline and the corrosion to the pipeline are reduced, and meanwhile, a gas sample does not need to be subjected to the previous detectionTreatment of sulfide gases in adsorbed gas samples by cooling with cold traps, non-sulfide gases not adsorbed by cooling, e.g. N2、O2And CH4And (3) discharging the gas from the device through an emptying pipeline, conveying the purified gas to an element instrument to be fully combusted and reduced together with the solid standard substance in sequence, and detecting the gas by an isotope mass spectrometer to obtain the composition of the sulfur isotope in the gas sample.
The device for detecting the sulfur isotope in the gas in the continuous flow mode realizes the switching between pipelines through the six-way valve and the four-way valve, and is convenient and quick to operate.
The device for detecting the sulfur isotope in the gas in the continuous flow mode has strong corrosion resistance of pipelines.
The method for detecting the sulfur isotope in the gas in the continuous flow mode reduces the retention of sulfur disulfide in the pipeline and the corrosion to the pipeline, and meanwhile, the gas sample does not need to be pretreated.
The method for detecting the sulfur isotope in the gas in the continuous flow mode provided by the invention utilizes GBW04414 and GBW04415 as reference substances to calibrate, and can more accurately determine the composition of the sulfur isotope in the gas sample.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings.
Fig. 1 is a schematic diagram of an apparatus for detecting sulfur isotopes in a gas in a continuous flow mode according to the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Example 1
The embodiment provides a device for detecting sulfur isotopes in gas in a continuous flow mode. Referring to fig. 1, fig. 1 is a schematic diagram illustrating an apparatus for detecting sulfur isotopes in a gas in a continuous flow mode according to the present invention. As shown in fig. 1, the apparatus includes: the system comprises a gas storage tank 1 for storing gas samples, a cold trap 2, an element instrument 3, an isotope mass spectrometer 4, a six-way valve F1, a four-way valve F2, a first helium conveying pipeline A, a second helium conveying pipeline B, a first gas inlet pipeline C, a vent pipeline D, an oxygen conveying pipeline E and a second gas inlet pipeline F; the element appearance includes: a solid autosampler 301, a burner 302, and a reduction furnace 303; the first helium gas delivery pipeline A, the gas storage tank 1, the cold trap 2, the first gas inlet pipeline C, the combustion furnace 302, the reduction furnace 303, the second gas inlet pipeline F and the isotope mass spectrometer 4 are communicated in sequence; the cold trap 2 is communicated with the emptying pipeline D; the second helium conveying pipeline B is communicated with the air inlet end of the cold trap 2; the oxygen delivery line E is in communication with the furnace 302; six interfaces of the six-way valve F1 are respectively communicated with an air inlet end and an air outlet end of the air storage tank 1 and the cold trap 2, an air inlet end and an air outlet end of the second helium conveying pipeline B and the emptying pipeline D; the four-way valve F2 is used for communicating the outlet end of the second helium gas conveying pipeline B with the combustion furnace 302 and is also used for communicating the oxygen gas conveying pipeline E with the combustion furnace 302; the isotope mass spectrometer 4 includes: a chromatographic column 401, an interface 402, and an isotope mass spectrometer 403 which are communicated in sequence; the chromatographic column 401 is communicated with the reduction furnace.
Example 2
The present embodiment provides a method for detecting sulfur isotopes in a gas in a continuous flow mode. The process was carried out in the apparatus mentioned in example 1, comprising the following steps:
s1, helium carries a gas sample released by the gas storage tank 1 through a first helium conveying pipeline A, enters the cold trap 2 for cooling adsorption, and gas which is not cooled and adsorbed in the gas sample is discharged out of the device through the emptying pipeline D.
S2, placing the solid standard substance into the solid autosampler 301, feeding the solid standard substance into the combustion furnace 302 through the solid autosampler 301, simultaneously conveying oxygen into the combustion furnace 302 through the oxygen conveying pipeline E, fully combusting the solid standard substance to generate gas containing sulfur dioxide and sulfur trioxide, and then conveying the gas into the reduction furnace 303 to reduce the sulfur trioxide in the gas into sulfur dioxide.
And S3, inputting the reduced gas into the isotope mass spectrometer 4 to detect a signal of a sulfur isotope, wherein the solid standard substance has a known sulfur isotope value.
And S4, heating the cold trap 2 to enable the cold trap 2 to release the cooled and adsorbed gas, enabling the helium gas in the second helium gas conveying pipeline B to carry the released cooled and adsorbed gas to enter the combustion furnace 302, simultaneously conveying oxygen gas into the combustion furnace 302 through the oxygen gas conveying pipeline E, fully combusting the released cooled and adsorbed gas to generate gas containing sulfur dioxide and sulfur trioxide, and then conveying the gas into a reduction furnace 303 to reduce the sulfur trioxide in the gas into the sulfur dioxide.
And S5, conveying the reduced gas into the isotope mass spectrometer 4 to detect a signal of the sulfur isotope.
S6, comparing the signal of the sulfur isotope obtained in the step S5 with the signal of the sulfur isotope obtained in the step S3, thereby obtaining the composition of the sulfur isotope in the gas sample.
Example 3
Application of the method provided in example 2 to H in Natural gas2The sulfur isotope of S was measured.
Collecting natural gas with high pressure aluminum alloy steel cylinder, passing the natural gas through liquid nitrogen refrigerated cold trap 2 (shown in figure 1), and collecting H in the natural gas2S is frozen and enriched in the cold trap 2, He and N2And CH4The gas which is not adsorbed by freezing is discharged, and the solid standard substance is fed into the elemental analyzer-isotope mass spectrometry system through the solid sample injector 301, and the signals of m/e 36 and m/e 34 are measured.
Switching the six-way valve F1 to warm the cold trap 2 will result in enriched H2S, etc. gas quilt He is carried into an element instrument-isotope mass spectrum, and signals of m/e 36 and m/e 34 are measured; the signal of the sulfur isotope is compared with the signal of the sulfur isotope of the solid standard substance, and H in natural gas is calculated according to the existing isotope composition definition formula2Sulfur isotope composition of S.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. An apparatus for detecting sulfur isotopes in a gas in a continuous flow mode, the apparatus comprising: the device comprises a gas storage tank (1) for storing a gas sample, a cold trap (2), an element instrument (3), an isotope mass spectrometer (4), a first helium conveying pipeline (A), a second helium conveying pipeline (B), a first gas inlet pipeline (C), a vent pipeline (D), an oxygen conveying pipeline (E) and a second gas inlet pipeline (F);
the element meter (3) comprises: a solid autosampler (301), a combustion furnace (302), and a reduction furnace (303);
the first helium gas delivery pipeline (A), the gas storage tank (1), the cold trap (2), the first gas inlet pipeline (C), the combustion furnace (302), the reduction furnace (303), the second gas inlet pipeline (F) and the isotope mass spectrometer (4) are communicated in sequence;
the cold trap (2) is communicated with the emptying pipeline (D);
the second helium conveying pipeline (B) is communicated with the air inlet end of the cold trap (2);
the oxygen delivery line (E) is in communication with the furnace (302).
2. The apparatus according to claim 1, further comprising a six-way valve (F1), six ports of the six-way valve (F1) communicating with the gas storage tank (1), the inlet and outlet ends of the cold trap (2), the inlet and outlet ends of the second helium gas delivery line (B), and the vent line (D), respectively.
3. The apparatus of claim 1 further comprising a four-way valve (F2), said four-way valve (F2) being adapted to communicate the outlet of said second helium gas delivery line (B) to said furnace (302) and to communicate said oxygen delivery line (E) to said furnace (302).
4. The apparatus according to claim 1, characterized in that the cold trap (2) comprises: the device comprises a liquid nitrogen tank and a U-shaped pipe arranged in the liquid nitrogen tank;
the air inlet end of the U-shaped pipe is communicated with the air storage tank (1), and the air outlet end of the U-shaped pipe is communicated with the first air inlet pipeline (C) and the second helium conveying pipeline (B); glass wool is filled in the U-shaped pipe; the U-shaped pipe is a glass pipe; the inner diameter of the U-shaped pipe is 2-3 mm.
5. The apparatus according to claim 1, characterized in that the isotope mass spectrometer (4) comprises: a chromatographic column (401), an interface (402) and an isotope mass spectrometer (403) which are communicated in sequence;
the chromatographic column (401) is communicated with the reduction furnace (303).
6. The device according to claim 5, wherein the chromatography column (401) is a Teflon chromatography column; and pipelines in the element instrument are all Teflon pipes.
7. A method for detecting sulfur isotopes in a gas in a continuous flow mode, wherein the method is performed in the apparatus of any one of claims 1 to 6, and the method comprises the following steps:
s1, helium carries a gas sample released by the gas storage tank (1) through a first helium conveying pipeline (A) and enters the cold trap (2) for cooling and adsorption, and gas which is not cooled and adsorbed in the gas sample is discharged out of the device through the emptying pipeline (D);
s2, placing a solid standard substance into the solid automatic sample injector (301), feeding the solid standard substance into the combustion furnace (302) through the solid automatic sample injector (301), simultaneously conveying oxygen into the combustion furnace (302) through the oxygen conveying pipeline (E), fully combusting the solid standard substance to generate gas containing sulfur dioxide and sulfur trioxide, and then conveying the gas into the reduction furnace (303) to reduce the sulfur trioxide in the gas into the sulfur dioxide;
s3, inputting the reduced gas into the isotope mass spectrometer (4) to detect a signal of a sulfur isotope, wherein the solid standard substance has a known sulfur isotope value;
s4, heating the cold trap (2) to enable the cold trap (2) to release cooling adsorbed gas, enabling helium in a second helium conveying pipeline (B) to carry the released cooling adsorbed gas to enter the combustion furnace (302), simultaneously conveying oxygen to the combustion furnace (302) through an oxygen conveying pipeline (E), fully combusting the released cooling adsorbed gas to generate gas containing sulfur dioxide and sulfur trioxide, and then conveying the gas into a reduction furnace (303) to reduce the sulfur trioxide in the gas into sulfur dioxide;
s5, conveying the reduced gas into the isotope mass spectrometer (4) to detect a signal of a sulfur isotope;
s6, comparing the signal of the sulfur isotope obtained in the step S5 with the signal of the sulfur isotope obtained in the step S3, thereby obtaining the composition of the sulfur isotope in the gas sample.
8. The method according to claim 7, characterized in that the temperature at which the cold trap (2) is heated is between 100 ℃ and 150 ℃.
9. The method of claim 7, wherein the solid standard substance is Ag2S or merthiolate.
10. The method of claim 9, wherein Ag2S is GBW04414 and/or GBW 04415.
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| CN113624860A (en) * | 2021-07-07 | 2021-11-09 | 自然资源部第三海洋研究所 | Element analysis-mass spectrometry combined system and method for testing trace sulfur isotope |
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