CN112362721B - Device and method for detecting sulfur isotopes in gas in continuous flow mode - Google Patents
Device and method for detecting sulfur isotopes in gas in continuous flow mode Download PDFInfo
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- CN112362721B CN112362721B CN201910682615.XA CN201910682615A CN112362721B CN 112362721 B CN112362721 B CN 112362721B CN 201910682615 A CN201910682615 A CN 201910682615A CN 112362721 B CN112362721 B CN 112362721B
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 50
- 239000011593 sulfur Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims description 29
- 239000007789 gas Substances 0.000 claims abstract description 135
- 239000001307 helium Substances 0.000 claims abstract description 36
- 229910052734 helium Inorganic materials 0.000 claims abstract description 36
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 29
- 238000002485 combustion reaction Methods 0.000 claims abstract description 27
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004891 communication Methods 0.000 claims abstract description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 36
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- 239000011491 glass wool Substances 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims 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 8
- 238000004949 mass spectrometry Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 2
- 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
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 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
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000002253 acid Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000022 continuous-flow isotope ratio mass spectrometry 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
- 239000003365 glass fiber Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 150000004763 sulfides Chemical class 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
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
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 comprises: a gas holder for storing a gas sample, a cold trap, an elemental device, an isotope mass spectrometer, a first helium gas delivery line, a second helium gas delivery line, a first gas inlet line, a vent line, an oxygen gas delivery line, and a second gas inlet line; the elemental instrument includes: a solid autosampler, a combustion furnace and a reduction furnace; the first helium gas conveying pipeline, the gas storage tank, the cold trap, the first air inlet pipeline, the combustion furnace, the reduction furnace, the second air inlet pipeline and the isotope mass spectrometer are sequentially communicated; the cold trap is communicated with the emptying pipeline; the second helium gas conveying pipeline is communicated with the air inlet end of the cold trap; the oxygen delivery line is in communication with the burner. The device does not need to carry out pretreatment on the gas sample, and can calibrate the sulfur isotope in the gas sample by utilizing 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 element analyzer and the isotope ratio mass spectrometer are connected through a continuous flow interface to realize the on-line analysis of stable isotopes. The continuous flow mass spectrum directly collects target gas into a mass spectrum ion source under the carrying of helium flow, and the sample is continuously processed and measured on line, so that the loss of the sample in the analysis process can be reduced, and the analysis speed and sensitivity are improved.
Continuous flow mass spectrometry detectionThe analysis method of sulfur isotope is based on the principle of 'dynamic instant combustion', a sample is wrapped by a tin cup, an automatic sampler is sent into a high-temperature combustion tube of an element analyzer, the sample is combusted into sulfur oxide through 'oxygen blowing technology' under the protection of He gas, and SO is further generated through the reduction of Cu 2 And (3) entering isotope mass spectrometry along with helium gas flow. The method can realize rapid and batched test of sulfur isotopes in samples such as rock, soil, plants, kerogen and the like.
Currently, chemical methods are adopted for determining sulfur isotopes in gases to convert the gases into solid sulfides, for example, sulfur dioxide gas can be fixed into sulfate radicals by glass fibers treated by potassium carbonate and then converted into silver sulfide or barium sulfate; the sulfur isotope in the hydrogen sulfide gas can fix the hydrogen sulfide gas into CdS through cadmium acetate, and then Ag is added + Converting it to silver sulfide; and then the sulfide is converted into sulfur dioxide in a room, and the sulfur isotope composition of the sulfur dioxide is analyzed by a stable isotope mass spectrometer, or the sulfide is converted into sulfur hexafluoride, so that the sulfur isotope composition of the sulfur dioxide can be analyzed. These methods all involve two or more chemical reactions, which must be complete to prevent isotope fractionation, and therefore require very strict operation and have a large number of factors that produce errors in response. Meanwhile, sulfur-containing chemical pretreatment is more harmful. And in the isotope mass spectrometry process, SO is adopted 2 As a working reference gas, due to SO 2 Belongs to sulfur-containing acid gas with high toxicity, is not easy to preserve, has strong viscosity in a pipeline, is easy to cause corrosion to the pipeline and causes pollution to the environment.
Disclosure of Invention
The invention aims to provide a device and a method for detecting sulfur isotopes in gas, which are low in pipeline corrosion degree.
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 comprises: a gas holder for storing a gas sample, a cold trap, an elemental device, an isotope mass spectrometer, a first helium gas delivery line, a second helium gas delivery line, a first gas inlet line, a vent line, an oxygen gas delivery line, and a second gas inlet line;
the elemental instrument includes: a solid autosampler, a combustion furnace and a reduction furnace;
the first helium gas conveying pipeline, the gas storage tank, the cold trap, the first air inlet pipeline, the combustion furnace, the reduction furnace, the second air inlet pipeline and the isotope mass spectrometer are sequentially communicated;
the cold trap is communicated with the emptying pipeline;
the second helium gas conveying pipeline is communicated with the air inlet end of the cold trap;
the oxygen delivery line is in communication with the burner.
Preferably, the device further comprises a six-way valve, six interfaces of the six-way valve are respectively communicated with the air storage tank, the air inlet end and the air outlet end of the cold trap, the air inlet end and the air 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 air outlet end of the second helium gas conveying pipeline with the combustion furnace and simultaneously communicating the oxygen gas conveying pipeline with the combustion furnace.
In one embodiment of the present invention, the cold trap includes: 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 gas conveying pipeline; glass wool is filled in the U-shaped tube; the U-shaped tube is a glass tube; the inner diameter of the U-shaped pipe is 2-3 mm.
In one embodiment of the present invention, the isotope mass spectrometer comprises: a chromatographic column, an interface and an isotope mass spectrometer which are communicated in sequence;
the chromatographic column is communicated with the reduction furnace.
Preferably, the chromatographic column is a Teflon chromatographic column; the pipelines in the elemental instrument are all Teflon tubes.
In a second aspect, the invention provides a method for detecting a sulfur isotope in a gas in a continuous flow mode. The method is carried out in an apparatus according to the first aspect, said method comprising the steps of:
s1, carrying a gas sample released by the gas storage tank through a first helium conveying pipeline to enter the cold trap for cooling and adsorption, and discharging the gas which is not cooled and adsorbed in the gas sample from the emptying pipeline to the device;
s2, placing a solid standard substance in the solid automatic sampler, entering the combustion furnace through the solid automatic sampler, conveying oxygen into the combustion furnace through the oxygen conveying pipeline, fully burning 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 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 so that the cold trap releases cooling adsorption gas, enabling helium in a second helium conveying pipeline to carry the released cooling adsorption gas into the combustion furnace, conveying oxygen into the combustion furnace through the oxygen conveying pipeline, fully combusting the released cooling adsorption gas to generate gas containing sulfur dioxide and sulfur trioxide, and then sending the gas into a reduction furnace to reduce the sulfur trioxide in the gas into sulfur dioxide;
s5, sending 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, so as to obtain 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 make the outlet end of the second helium gas delivery line communicate with the inlet end of the cold trap.
Preferably, the temperature at which the cold trap is heated is from 100 ℃ to 150 ℃.
More preferably, the temperature at which the cold trap is heated is 150 ℃.
Preferably, the solid standard substance is Ag 2 S or merle.
Preferably Ag 2 S is GBW04414 and/or GBW04415.
The device for detecting sulfur isotopes in gas in continuous flow mode provided by the invention uses the sulfur dioxide gas processed by a combustion furnace and a reduction furnace as working reference gas to calibrate a solid standard substance in sequence through a solid automatic sampler, avoids directly using sulfur dioxide which is not easy to preserve as the reference gas, reduces the detention of sulfur disulfide in a pipeline and the corrosion to the pipeline, simultaneously does not need pretreatment of a gas sample, utilizes a cold trap to cool and adsorb sulfide gas in the gas sample, and can not be cooled and adsorbed by non-sulfide gas such as N 2 、O 2 CH (CH) 4 And (3) discharging the gas from the device through a vent line, conveying the purified gas to an elemental instrument to be fully combusted and reduced together with a solid standard substance in sequence, and detecting the gas through an isotope mass spectrometer to obtain the composition of sulfur isotopes in a gas sample.
The device for detecting the sulfur isotopes in the gas in the continuous flow mode provided by the invention realizes switching between pipelines through the six-way valve and the four-way valve, and is convenient and quick to operate.
The pipeline in the device for detecting the sulfur isotopes in the gas in the continuous flow mode provided by the invention has strong corrosion resistance.
The method for detecting the sulfur isotopes in the gas in the continuous flow mode reduces the retention of the sulfur disulfide in the pipeline and the corrosion to the pipeline, and meanwhile, the gas sample does not need pretreatment.
According to the method for detecting the sulfur isotopes in the gas in the continuous flow mode, GBW04414 and GBW04415 are used as reference substances for calibration, and the composition of the sulfur isotopes in the gas sample can be more accurately determined.
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 shows a schematic diagram of an apparatus for detecting sulfur isotopes in a gas in a continuous flow mode provided by the invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.
Example 1
The embodiment provides a device for detecting sulfur isotopes in a gas in a continuous flow mode. Referring to fig. 1, 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. As shown in fig. 1, the apparatus includes: a gas tank 1 for storing a gas sample, a cold trap 2, an elemental instrument 3, an isotope mass spectrometer 4, a six-way valve F1, a four-way valve F2, a first helium gas delivery line a, a second helium gas delivery line B, a first intake line C, a vent line D, an oxygen gas delivery line E, and a second intake line F; the elemental instrument includes: a solid autosampler 301, a combustion furnace 302, and a reduction furnace 303; the first helium gas conveying pipeline A, the gas storage tank 1, the cold trap 2, the first air inlet pipeline C, the combustion furnace 302, the reduction furnace 303, the second air inlet pipeline F and the isotope mass spectrometer 4 are sequentially communicated; the cold trap 2 is communicated with the emptying pipeline D; the second helium gas conveying pipeline B is communicated with the air inlet end of the cold trap 2; the oxygen transfer line E communicates with the burner 302; six interfaces of the six-way valve F1 are respectively communicated with the air storage tank 1, the air inlet end and the air outlet end of the cold trap 2, the air inlet end and the air outlet end of the second helium gas conveying pipeline B and the emptying pipeline D; the four-way valve F2 is used for communicating the air outlet end of the second helium gas conveying pipeline B with the combustion furnace 302 and simultaneously 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 in sequential communication; the chromatographic column 401 is in communication 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 is carried out in the apparatus mentioned in example 1, said process comprising the steps of:
s1, carrying a gas sample released by the gas storage tank 1 through a first helium conveying pipeline A to enter the cold trap 2 for cooling and adsorption, and discharging the gas which is not cooled and adsorbed in the gas sample from the emptying pipeline D.
S2, placing a solid standard substance in the solid automatic sampler 301, entering the combustion furnace 302 through the solid automatic sampler 301, simultaneously conveying oxygen into the combustion furnace 302 through the oxygen conveying pipeline E, fully burning 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.
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 so that the cold trap 2 releases cooling adsorption gas, enabling helium in a second helium conveying pipeline B to carry the released cooling adsorption gas into the combustion furnace 302, conveying oxygen into the combustion furnace 302 through an oxygen conveying pipeline E, fully combusting the released cooling adsorption gas to generate gas containing sulfur dioxide and sulfur trioxide, and then sending the gas into a reduction furnace 303 to reduce the sulfur trioxide in the gas into sulfur dioxide.
S5, sending the reduced gas into the isotope mass spectrometer 4 to detect the 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, so as to obtain the composition of the sulfur isotope in the gas sample.
Example 3
H in Natural gas Using the method provided in example 2 2 Sulfur isotopes of S were measured.
Natural gas is collected by a high-pressure aluminum alloy steel cylinder, and is frozen by liquid nitrogen through a cold trap 2 (shown in figure 1), wherein H in the natural gas 2 S is frozen and enriched in the cold trap 2, he and N 2 And CH 4 The gas which is not frozen and adsorbed is exhausted, and the solid standard substance is sent into an elemental instrument-isotope mass spectrometry system through a solid sampler 301, and signals of m/e=36 and m/e=34 are measured.
Switching the six-way valve F1 to heat the cold trap 2 so as to enrich H 2 S and other gases are carried into the elemental instrument-isotope mass spectrometry by He, 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 a solid standard substance, and H in the natural gas is calculated according to the existing isotope composition definition formula 2 Sulfur isotope composition of S.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or 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 various embodiments described.
Claims (9)
1. A method for detecting sulfur isotopes in a gas in a continuous flow mode, the method comprising: a gas holder (1) for storing a gas sample, a cold trap (2), an elemental instrument (3), an isotope mass spectrometer (4), a first helium gas delivery line (a), a second helium gas delivery line (B), a first gas inlet line (C), a vent line (D), an oxygen gas delivery line (E), and a second gas inlet line (F);
the elemental instrument (3) includes: a solid autosampler (301), a combustion furnace (302), and a reduction furnace (303);
the first helium gas conveying pipeline (A), the gas storage tank (1), the cold trap (2), the first air inlet pipeline (C), the combustion furnace (302), the reduction furnace (303), the second air inlet pipeline (F) and the isotope mass spectrometer (4) are sequentially communicated;
the cold trap (2) is communicated with the emptying pipeline (D);
the second helium gas conveying pipeline (B) is communicated with the air inlet end of the cold trap (2);
the oxygen transfer line (E) is in communication with the burner (302);
the method comprises the following steps:
s1, carrying a gas sample released by the gas storage tank (1) through a first helium conveying pipeline (A) to enter the cold trap (2) for cooling and adsorption, and discharging the gas which is not cooled and adsorbed in the gas sample from the emptying pipeline (D) to the device;
s2, placing a solid standard substance in the solid automatic sampler (301), entering the combustion furnace (302) through the solid automatic sampler (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;
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) so that the cold trap (2) releases cooling adsorption gas, enabling helium in a second helium conveying pipeline (B) to carry the released cooling adsorption gas into the combustion furnace (302), conveying oxygen into the combustion furnace (302) through the oxygen conveying pipeline (E), fully combusting the released cooling adsorption 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, sending 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, so as to obtain the composition of the sulfur isotope in the gas sample.
2. The method according to claim 1, characterized in that the device further comprises a six-way valve (F1), the six interfaces of the six-way valve (F1) being in communication with the air reservoir (1), the inlet and outlet ends of the cold trap (2), respectively, the inlet and outlet ends of the second helium gas transfer line (B), and the vent line (D).
3. The method of claim 1, wherein the apparatus further comprises a four-way valve (F2), the four-way valve (F2) being adapted to communicate the outlet end of the second helium gas delivery line (B) with the burner (302) and simultaneously being adapted to communicate the oxygen gas delivery line (E) with the burner (302).
4. The method according to claim 1, characterized in that the cold trap (2) 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 gas conveying pipeline (B); glass wool is filled in the U-shaped tube; the U-shaped tube is a glass tube; the inner diameter of the U-shaped pipe is 2-3 mm.
5. The method according to claim 1, wherein 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 in communication with the reduction furnace (303).
6. The method according to claim 5, wherein the chromatography column (401) is a Teflon chromatography column; the pipelines in the elemental instrument are all Teflon tubes.
7. The method according to claim 1, characterized in that the temperature at which the cold trap (2) is heated is 100-150 ℃.
8. The method according to claim 1, wherein the solid standard substance is Ag 2 S or merle.
9. The method according to claim 8, wherein Ag 2 S is GBW04414 and/or GBW04415.
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