CN107656001B - Micro liter amount of gas single molecular compound stable isotope composition analysis device and use thereof - Google Patents
Micro liter amount of gas single molecular compound stable isotope composition analysis device and use thereof Download PDFInfo
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- CN107656001B CN107656001B CN201610591927.6A CN201610591927A CN107656001B CN 107656001 B CN107656001 B CN 107656001B CN 201610591927 A CN201610591927 A CN 201610591927A CN 107656001 B CN107656001 B CN 107656001B
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- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 150000001875 compounds Chemical class 0.000 title claims abstract description 29
- 238000004458 analytical method Methods 0.000 title claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 159
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011435 rock Substances 0.000 claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000007872 degassing Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012159 carrier gas Substances 0.000 claims abstract description 9
- 238000002347 injection Methods 0.000 claims description 22
- 239000007924 injection Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000005086 pumping Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 25
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- -1 etc.) Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/8868—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample elemental analysis, e.g. isotope dilution analysis
Abstract
The invention relates to a micro liter quantity gas single molecular compound stable isotope composition analysis device which comprises a gas chromatography-continuous flow stable isotope mass spectrometer, a high vacuum system, a rock sample sectionalized heating and degassing device, a rock sample high vacuum electromagnetic crushing and degassing device, a water removing device and an active carbon cold finger. The rock sample sectional heating degasser is connected with the rock sample high-vacuum electromagnetic crushing degasser through a pipeline I, and high-vacuum valves II and III are arranged on the pipeline I; a pipeline II with the tail ends connected with pipelines III and IV is arranged on the pipeline I between the high vacuum valves II and III; the pipeline III is connected with a water removing device, an active carbon cold finger and a high-vacuum six-way valve, and the tail end of the pipeline III is connected with the pipeline IV; the pipeline IV is connected with a high vacuum system; the high-vacuum six-way valve is connected with a carrier gas input pipe, a sample ring and a gas chromatograph-continuous flow stable isotope mass spectrometer; and a film vacuum gauge is arranged at the joint of the pipeline II, the pipeline III and the pipeline IV. The invention also discloses a using method of the device. The invention has high sensitivity and good separation effect.
Description
Technical Field
The invention relates to the technical field of gas geochemistry, in particular to a micro-liter gas single-molecule compound stable isotope composition analysis device and application thereof.
Background
Gas geochemistry research involves numerous fields of geoscience: gas transport in the global mass circulation, gas action in volcanic seismic activity, petroleum and gas resources, interactions of gases inside the earth with rocks, mantle degassing, geological storage of gases, and the like. Main study: gas samples (e.g. atmosphere, natural gas, etc.), dissolved gases in liquid samples (e.g. groundwater, hot spring water, seawater, etc.), gases present in solid samples (e.g. shale, natural gas source rock or reservoir, mineral rock, etc.), these gases (H 2 、N 2 、O 2 、CO、CO 2 、H 2 S、CH 4 、C 2 H 2n+2 He, ne, ar, kr and Xe, etc.) and their stable isotopic composition characteristics to investigate the origin, source, geochemical characteristics, coupling coexistence mechanisms, and their reflected geodynamic environment and evolution of these gases.
Common gas samples such as natural gas, which are usually in large amounts, have become conventional analytical methods for the detection of single molecule compound stable carbon/hydrogen isotope compositions. Some experimental devices individually degas rock samples, collect sufficient gas volume, and analyze their single molecule compound stable carbon/hydrogen isotope composition according to conventional gas sample detection methods. This method is only suitable for the case that the rock sample is easy to obtain or the gas content of the rock sample is high. When rock samples are not readily available or gas content is low, an in-line method should be used. In the past, the method for analyzing the carbon/hydrogen isotope composition of the rock sample on-line by degassing adopts carrier gas driving to enrich gas into a sample ring of a six-way valve, and analyzes the carbon/hydrogen isotope composition of the single molecule by using a gas chromatograph-continuous flow stable isotope mass spectrometer. The method does not determine the total amount of gas, and the amount of gas entering a gas chromatograph-continuous flow stable isotope mass spectrometer is difficult to control; filling and treatment of fillers (such as molecular sieves and activated carbon) in the sample ring require high skill, otherwise, the gas path is blocked or the adsorption and desorption effects are poor; the carrier gas in the gas path does not directly pass through part of the gas sample, and is difficult to collect.
Therefore, it is necessary to provide a novel rock sample degasification microliter amount of gas single molecule compound carbon/hydrogen isotope composition analysis device.
Disclosure of Invention
The invention aims to solve the technical problem of providing a stable isotope composition analysis device for a microliter amount of gas single-molecule compound, which has high sensitivity, good linearity and good separation effect.
Another technical problem to be solved by the present invention is to provide a method for using the stable isotope composition analysis device for micro liter amount of gas single molecule compound.
In order to solve the above problems, the stable isotope composition analysis device for micro liter amount of gas single molecular compound of the present invention is characterized in that: the device comprises a gas chromatograph-continuous flow stable isotope mass spectrometer, a high vacuum system, a rock sample sectionalized heating and degassing device, a rock sample high vacuum electromagnetic crushing and degassing device, a water removing device and an active carbon cold finger; the rock sample sectional heating degasser is connected with the rock sample high-vacuum electromagnetic crushing degasser through a pipeline I, and a high-vacuum valve II and a high-vacuum valve III are respectively arranged on the pipeline I; a pipeline II with one end connected with a gas injection port is arranged on the pipeline I between the high vacuum valve II and the high vacuum valve III, and the tail end of the pipeline II is respectively connected with a pipeline III and a pipeline IV; the pipeline III is sequentially connected with the water removal device, the active carbon cold finger and the high-vacuum six-way valve, and the tail end of the pipeline III is connected with the pipeline IV; the pipeline IV is connected with the high vacuum system; the high-vacuum six-way valve is respectively connected with a carrier gas input pipe, a sample ring and the gas chromatography-continuous flow stable isotope mass spectrometer; and a film vacuum gauge is arranged at the joint of the pipeline II and the pipeline III and the pipeline IV.
And a high vacuum valve I is arranged on the pipeline II close to the gas sample inlet.
And a high vacuum valve IV is arranged near the joint of the pipeline II and the pipeline III and the pipeline IV.
And a high vacuum valve V is arranged on the pipeline IV between the film vacuum gauge and the high vacuum system.
And a high vacuum valve VI is arranged on the pipeline III between the film vacuum gauge and the water removing device.
And a high vacuum valve IX and a high vacuum valve X are sequentially arranged on the pipeline III between the water removing device and the active carbon cold finger.
And a high-vacuum valve VII is arranged on the pipeline III between the active carbon cold finger and the high-vacuum six-way valve.
And a high-vacuum valve VIII is arranged on the pipeline III between the high-vacuum six-way valve and the high-vacuum system.
The method for using the stable isotope composition analysis device for the microliter amount of the gas single-molecule compound comprises the following steps:
placing a rock sample to be tested into a rock sample sectional heating degasser;
all high vacuum valves are opened, high vacuum is pumped to a vacuum pipeline, and the background pressure P of the film vacuum gauge is recorded 0 ；
Third, the high vacuum valve III, the high vacuum valve V and the high vacuum valve IX are closed, and the volume L is injected from the gas injection port under the standard state 0 Then closing the high vacuum valve I and the high vacuum valve II, and recording the pressure P of the film vacuum gauge 1 ；
Fourth, the high vacuum valve II, the high vacuum valve V and the high vacuum valve IX are opened, and high vacuum is pumped to a vacuum pipeline;
fifthly, closing the high vacuum valve II, heating the rock sample to a given temperature and keeping the temperature for a given time;
closing the high vacuum valve V and the high vacuum valve IX, opening the high vacuum valve II, waiting for 20s, then closing the high vacuum valve II, and recording the pressure P of the film vacuum gauge 2 ；
Calculating the amount of gas released by the rock sample when heated at a given temperature for a given time, the volume of the rock sample being L in a standard state 1 Wherein L is 1 = L 0 ×(P 2 -P 0 )/(P 1 -P 0 )；
Closing a high vacuum valve VI and a high vacuum valve X, closing a high vacuum valve VII, setting the temperature of the activated carbon cold finger to be 77K, and enriching part of gas into the activated carbon cold finger by a sectional sample injection method;
is equal to or larger than 373K, a high vacuum valve VIII is closed, the high vacuum valve VII is opened for 20 seconds, the high vacuum valve VII is closed, and the volume in a standard state is L 2 Is introduced into the sample loop;
the gas in the sample ring is led into a gas chromatograph-continuous flow stable isotope mass spectrometer to analyze the single molecular hydrogen isotope composition of the gas;
switching the gas path of the high-vacuum six-way valve, opening the high-vacuum valve VIII, and pumping high vacuum to the sample ring;
is to close the high vacuum valve VIII, open the high vacuum valve VII, wait for 20s, close the high vacuum valve VII, and make the volume L in the standard state 3 Is introduced into the sample loop;
and (3) switching the gas paths of the high-vacuum six-way valve, introducing the gas in the sample ring into the gas chromatograph-continuous flow stable isotope mass spectrometer, and analyzing the single-molecule carbon isotope composition of the gas.
The method for using the stable isotope composition analysis device for the microliter amount of the gas single-molecule compound comprises the following steps:
placing a rock sample to be tested into a rock sample high-vacuum electromagnetic crushing and degassing device;
all high vacuum valves are opened, high vacuum is pumped to a vacuum pipeline, and the background pressure P of the film vacuum gauge is recorded 0 ；
Third, the high vacuum valve II, the high vacuum valve V and the high vacuum valve IX are closed, and the volume L is injected from the gas injection port under the standard state 0 Then closing the high vacuum valve I and the high vacuum valve III, and recording the pressure P of the film vacuum gauge 1 ；
Fourth, the high vacuum valve III, the high vacuum valve V and the high vacuum valve IX are opened, and high vacuum is pumped to a vacuum pipeline;
fifthly, closing the high vacuum valve III, and performing electromagnetic crushing and degassing on the rock sample;
closing the high vacuum valve V and the high vacuum valve IX, opening the high vacuum valve III, waiting for 20s, then closing the high vacuum valve III, and recording the pressure P of the film vacuum gauge 2 ；
Calculating the gas quantity released by high-vacuum electromagnetic breaking of rock sample, and the volume is L under standard state 1 Wherein L is 1 = L 0 ×(P 2 -P 0 )/(P 1 -P 0 )；
Closing a high vacuum valve VI and a high vacuum valve X, closing a high vacuum valve VII, setting the temperature of the activated carbon cold finger to be 77K, and enriching part of gas into the activated carbon cold finger by a sectional sample injection method;
is equal to or larger than 373K, a high vacuum valve VIII is closed, the high vacuum valve VII is opened for 20 seconds, the high vacuum valve VII is closed, and the volume in a standard state is L 2 Is introduced into the sample loop;
and (3) switching the gas paths of the high-vacuum six-way valve, introducing the gas in the sample ring into a gas chromatograph-continuous flow stable isotope mass spectrometer, and analyzing the single-molecule carbon isotope composition of the gas.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts a high vacuum degassing mode, gas is enriched into the cold finger by differential pressure driving, and the problem that partial gas sample is difficult to collect because the carrier gas in the gas path does not directly pass through when the carrier gas is driven is avoided.
2. The invention adopts the film vacuum gauge to measure the pressure intensity of the gas, and the total gas quantity can be directly measured.
3. According to the invention, a sectional sample injection method is adopted, and the gas to be tested is enriched into the cold finger in a sectional manner according to the total gas quantity, so that the gas sample quantity entering the gas chromatograph-continuous flow stable isotope mass spectrometer can be controlled in a better linear range, and the success rate of single test is improved.
4. The cold finger enrichment is adopted, and the method is different from most enrichment devices which adopt U-shaped pipes, so that the pipe cannot be blocked, and gas flow and rapid vacuumizing are facilitated.
5. The sample ring of the invention has no filler, can not block a pipeline, and has good chromatographic peak shape.
6. The invention adopts a sectional sample injection method, and when the total gas amount is more, gas samples can be introduced into the sample ring in batches. When the gas chromatograph-continuous flow stable isotope mass spectrometer has the function of detecting the isotope composition of the multi-element single-molecule compound, after measuring the hydrogen isotope composition of the single-molecule compound, the carbon isotope composition of the single-molecule compound, even the nitrogen isotope composition of the molecular compound of nitrogen, and the like can be measured.
7. The invention has the characteristics of high sensitivity, good linearity, good separation effect and one-time degassing of various stable isotope composition analysis.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
Fig. 1 is a schematic structural view of the present invention.
In the figure: 1-gas chromatography-continuous flow stable isotope mass spectrometer; 2-a high vacuum system; 3-a rock sample sectional heating degasser; 4, a gas sample inlet; 5-a high-vacuum electromagnetic crushing and degassing device for rock samples; 6-a film vacuum gauge; 7, a water removing device; 8-activated carbon cold finger; 9-a high vacuum six-way valve; 10-sample loop; 11-a carrier gas input tube; 12-line I; 13-a high vacuum valve II; 14-a high vacuum valve III; 15-line ii; 16-a high vacuum valve I; 17-line iii; 18-line IV; 19-a high vacuum valve IV; 20-a high vacuum valve v; 21-a high vacuum valve vi; 22-a high vacuum valve IX; 23-high vacuum valve x; 24-a high vacuum valve VII; 25-high vacuum valve VIII.
Detailed Description
As shown in fig. 1, the device for analyzing the stable isotope composition of the micro-liter quantity gas single-molecule compound comprises a gas chromatography-continuous flow stable isotope mass spectrometer 1, a high vacuum system 2, a rock sample sectioning heating and degassing device 3, a rock sample high vacuum electromagnetic breaking and degassing device 5, a water removing device 7 and an activated carbon cold finger 8.
The rock sample sectional heating degasser 3 is connected with the rock sample high-vacuum electromagnetic crushing degasser 5 through a pipeline I12, and the pipeline I12 is respectively provided with a high-vacuum valve II 13 and a high-vacuum valve III 14; a pipeline II 15 with one end connected with the gas injection port 4 is arranged on a pipeline I12 between the high vacuum valve II 13 and the high vacuum valve III 14, and the tail end of the pipeline II 15 is respectively connected with a pipeline III 17 and a pipeline IV 18; the pipeline III 17 is sequentially connected with a water removing device 7, an activated carbon cold finger 8 and a high-vacuum six-way valve 9, and the tail end of the pipeline III is connected with a pipeline IV 18; the pipeline IV 18 is connected with a high vacuum system 2; the high-vacuum six-way valve 9 is respectively connected with a carrier gas input pipe 11, a sample ring 10 and a gas chromatograph-continuous flow stable isotope mass spectrometer 1; a thin film vacuum gauge 6 is arranged at the joint of the pipeline II 15 and the pipeline III 17 as well as the pipeline IV 18.
A high vacuum valve I16 is arranged on a pipeline II 15 near the gas injection port 4.
A high vacuum valve IV 19 is arranged near the joint of the pipeline II 15 and the pipeline III 17 and the pipeline IV 18.
A high vacuum valve V20 is arranged on a pipeline IV 18 between the film vacuum gauge 6 and the high vacuum system 2.
A high vacuum valve VI 21 is arranged on a pipeline III 17 between the film vacuum gauge 6 and the water removing device 7.
A high vacuum valve IX 22 and a high vacuum valve X23 are sequentially arranged on a pipeline III 17 between the water removing device 7 and the active carbon cold finger 8.
A high-vacuum valve VII 24 is arranged on a pipeline III 17 between the active carbon cold finger 8 and the high-vacuum six-way valve 9.
A high vacuum valve VIII 25 is arranged on a pipeline III 17 between the high vacuum six-way valve 9 and the high vacuum system 2.
The method for using the micro liter quantity gas single molecular compound stable isotope composition analysis device comprises the following steps:
placing a rock sample to be tested into a rock sample sectional heating degasser 3;
all high vacuum valves are opened, high vacuum is pumped to a vacuum pipeline, and the background pressure P of the film vacuum gauge 6 is recorded 0 ；
Third, the high vacuum valve III 14, the high vacuum valve V20 and the high vacuum valve IX 22 are closed, and the volume L is injected from the gas injection port 4 under the standard state 0 Then closing the high vacuum valve I16 and the high vacuum valve II 13, and recording the pressure P of the film vacuum gauge 6 1 ；
Fourth, a high vacuum valve II 13, a high vacuum valve V20 and a high vacuum valve IX 22 are opened, and high vacuum is pumped to a vacuum pipeline;
fifthly, closing the high vacuum valve II 13, heating the rock sample to a given temperature and keeping the temperature for a given time;
sixth, closing a high vacuum valve V20 and a high vacuum valve IX 22, opening a high vacuum valve II 13, waiting for 20 seconds, then closing the high vacuum valve II 13, and recording the pressure P of the film vacuum gauge 6 2 ；
Calculating the amount of gas released by the rock sample when heated at a given temperature for a given time, the volume of the rock sample being L in a standard state 1 Wherein L is 1 = L 0 ×(P 2 -P 0 )/(P 1 -P 0 )；
Closing a high vacuum valve VI 21 and a high vacuum valve X23, closing a high vacuum valve VII 24, setting the temperature of the activated carbon cold finger 8 to be 77K, and enriching part of gas into the activated carbon cold finger 8 by a sectional sample injection method;
is equal to or greater than 373K, closes the high vacuum valve VIII 25, opens the high vacuum valve VII 24, waits for 20s, closes the high vacuum valve VII 24, and takes the volume L in the standard state 2 Is introduced into the sample ring 10; description of the embodiments: volume of gas L 2 The size of the (C) should meet the requirement of the single-molecule hydrogen isotope composition test, and the optimal air inflow of the single-molecule hydrogen isotope composition test should be achieved when possible. ' s of
The gas path of the high-vacuum six-way valve 9 is switched, the gas in the sample ring 10 is led into the gas chromatograph-continuous flow stable isotope mass spectrometer 1, and the single molecular hydrogen isotope composition of the gas is analyzed;
switching the gas path of the high-vacuum six-way valve 9, opening the high-vacuum valve VIII 25, and pumping high vacuum to the sample ring 10;
is to close the high vacuum valve VIII 25, open the high vacuum valve VII 24, wait 20s,closing the high vacuum valve VII 24 to obtain the volume L in the standard state 3 Is introduced into the sample ring 10;
the gas path of the high-vacuum six-way valve 9 is switched, the gas in the sample ring 10 is led into the gas chromatograph-continuous flow stable isotope mass spectrometer 1, and the single-molecule carbon isotope composition of the gas is analyzed. Description of the embodiments: volume of gas L 3 The size of the valve (C) should meet the requirement of the single-molecule carbon isotope composition test, and the optimal air inflow of the single-molecule carbon isotope composition test should be achieved when possible. ' s of
Or (b)
The method for using the micro liter quantity gas single molecular compound stable isotope composition analysis device comprises the following steps:
placing a rock sample to be tested into a rock sample high-vacuum electromagnetic crushing and degassing device 5;
all high vacuum valves are opened, high vacuum is pumped to a vacuum pipeline, and the background pressure P of the film vacuum gauge 6 is recorded 0 ；
Third, the high vacuum valve II 13, the high vacuum valve V20 and the high vacuum valve IX 22 are closed, and the standard state is injected from the gas injection port 4, wherein the volume is L 0 Then the high vacuum valve I16 and the high vacuum valve III 14 are closed, and the pressure P of the film vacuum gauge 6 is recorded 1 ；
Fourth, the high vacuum valve III 14, the high vacuum valve V20 and the high vacuum valve IX 22 are opened, and high vacuum is pumped to the vacuum pipeline;
fifthly, closing the high vacuum valve III 14, and performing electromagnetic crushing and degassing on the rock sample;
sixth, closing a high vacuum valve V20 and a high vacuum valve IX 22, opening a high vacuum valve III 14, waiting for 20 seconds, then closing the high vacuum valve III 14, and recording the pressure P of the film vacuum gauge 6 2 ；
Calculating the gas quantity released by high-vacuum electromagnetic breaking of rock sample, and the volume is L under standard state 1 Wherein L is 1 = L 0 ×(P 2 -P 0 )/(P 1 -P 0 )；
Closing a high vacuum valve VI 21 and a high vacuum valve X23, closing a high vacuum valve VII 24, setting the temperature of the activated carbon cold finger 8 to be 77K, and enriching part of gas into the activated carbon cold finger 8 by a sectional sample injection method;
is equal to or greater than 373K, closes the high vacuum valve VIII 25, opens the high vacuum valve VII 24, waits for 20s, closes the high vacuum valve VII 24, and takes the volume L in the standard state 2 Is introduced into the sample ring 10; description of the embodiments: volume of gas L 2 The size of the valve (C) should meet the requirement of the single-molecule carbon isotope composition test, and the optimal air inflow of the single-molecule carbon isotope composition test should be achieved when possible. ' s of
The gas path of the high-vacuum six-way valve 9 is switched, the gas in the sample ring 10 is led into the gas chromatograph-continuous flow stable isotope mass spectrometer 1, and the single-molecule carbon isotope composition of the gas is analyzed.
Example 1 a rock sample sectional heating degassing single molecule hydrocarbon isotope composition test is taken as an example to illustrate the use of the microliter amount gas single molecule compound stable isotope composition analysis apparatus, which comprises the following steps:
the method comprises the steps of placing a rock sample 1g to be tested into a rock sample sectional heating degasser 3.
All high vacuum valves are opened, high vacuum is pumped to a vacuum pipeline, and the background pressure P of the film vacuum gauge 6 is recorded 0 。
Third, high vacuum valve III 14, high vacuum valve V20 and high vacuum valve IX 22 are closed, 100 μl of dry air under standard state is injected from gas inlet 4, then high vacuum valve I16 and high vacuum valve II 13 are closed, and pressure P of film vacuum gauge 6 is recorded 1 。
And fourthly, opening the high vacuum valve II 13, the high vacuum valve V20 and the high vacuum valve IX 22, and vacuumizing the vacuum pipeline.
And fifthly, closing the high vacuum valve II 13, heating the rock sample to 500 ℃ and keeping the temperature for 30min.
Sixth, closing a high vacuum valve V20 and a high vacuum valve IX 22, opening a high vacuum valve II 13, waiting for 20 seconds, then closing the high vacuum valve II 13, and recording the pressure P of the film vacuum gauge 6 2 。
The amount of gas released by heating 1g of the rock sample at 500 ℃ for 30min was calculated to be x μl in the standard state, where x=100× (P 2 -P 0 )/(P 1 -P 0 )。
And closing the high vacuum valve VI 21 and the high vacuum valve X23, closing the high vacuum valve VII 24, setting the temperature of the activated carbon cold finger 8 to be 77K, and enriching 60 mu l of gas in a standard state into the activated carbon cold finger 8 by a sectional sample injection method.
Is used for heating activated carbon cold fingers 8 to 373K, closing a high vacuum valve VIII 25, opening a high vacuum valve VII 24, waiting for 20 seconds, closing the high vacuum valve VII 24, and allowing 30 mu l of gas in a standard state to enter the sample ring 10.
The gas path of the high-vacuum six-way valve 9 is switched, the gas in the sample ring 10 is led into the gas chromatograph-continuous flow stable isotope mass spectrometer 1, and the single molecular hydrogen isotope composition of the gas is analyzed.
And (3) switching the gas path of the high-vacuum six-way valve 9, opening the high-vacuum valve VIII 25, and pumping high vacuum to the sample ring 10.
Is to close the high vacuum valve VIII 25, open the high vacuum valve VII 24, wait 20s, close the high vacuum valve VII 24, and enter the sample loop 10 at 15. Mu.l of standard conditions.
The gas path of the high-vacuum six-way valve 9 is switched, the gas in the sample ring 10 is led into the gas chromatograph-continuous flow stable isotope mass spectrometer 1, and the single-molecule carbon isotope composition of the gas is analyzed.
Example 2 a rock sample high vacuum electromagnetic fragmentation degasified single molecule carbon isotope composition test is exemplified, and the method of using the microliter amount of gas single molecule compound stable isotope composition analysis apparatus comprises the following steps:
the method comprises the steps of placing 5g of rock sample to be tested into a rock sample high-vacuum electromagnetic crushing and degassing device 5.
All high vacuum valves are opened, high vacuum is pumped to a vacuum pipeline, and the background pressure P of the film vacuum gauge 6 is recorded 0 。
Third, the high vacuum valve II 13, the high vacuum valve V20 and the high vacuum valve IX 22 are closed, 100 μl of dry air under standard state is injected from the gas injection port 4, then the high vacuum valve I16 and the high vacuum valve III 14 are closed, and the pressure P of the film vacuum gauge 6 is recorded 1 。
And fourthly, opening the high vacuum valve III 14, the high vacuum valve V20 and the high vacuum valve IX 22, and vacuumizing the vacuum pipeline.
And fifthly, closing the high vacuum valve III 14, and performing electromagnetic crushing and degassing on the rock sample.
Sixth, closing a high vacuum valve V20 and a high vacuum valve IX 22, opening a high vacuum valve III 14, waiting for 20 seconds, then closing the high vacuum valve III 14, and recording the pressure P of the film vacuum gauge 6 2 。
The amount of gas released by high vacuum electromagnetic breaking of a 5g rock sample was calculated to be x μl in the standard state, where x=100× (P 2 -P 0 )/(P 1 -P 0 )。
And closing the high vacuum valve VI 21 and the high vacuum valve X23, closing the high vacuum valve VII 24, setting the temperature of the activated carbon cold finger 8 to be 77K, and enriching 30 mu l of gas in a standard state into the activated carbon cold finger 8 by a sectional sample injection method.
Is used for heating activated carbon cold fingers 8 to 373K, closing a high vacuum valve VIII 25, opening a high vacuum valve VII 24, waiting for 20 seconds, closing the high vacuum valve VII 24, and introducing 15 mu l of gas in a standard state into the sample ring 10.
The gas path of the high-vacuum six-way valve 9 is switched, the gas in the sample ring 10 is led into the gas chromatograph-continuous flow stable isotope mass spectrometer 1, and the single-molecule carbon isotope composition of the gas is analyzed.
Claims (8)
1. The stable isotope composition analysis device for the micro-liter amount of the gas single-molecule compound is characterized in that: the device comprises a gas chromatograph-continuous flow stable isotope mass spectrometer (1), a high vacuum system (2), a rock sample sectional heating and degassing device (3), a rock sample high vacuum electromagnetic crushing and degassing device (5), a water removing device (7) and an active carbon cold finger (8); the rock sample sectional heating degasser (3) is connected with the rock sample high-vacuum electromagnetic crushing degasser (5) through a pipeline I (12), and a high-vacuum valve II (13) and a high-vacuum valve III (14) are respectively arranged on the pipeline I (12); a pipeline II (15) with one end connected with a gas injection port (4) is arranged on the pipeline I (12) between the high vacuum valve II (13) and the high vacuum valve III (14), and the tail end of the pipeline II (15) is respectively connected with a pipeline III (17) and a pipeline IV (18); the pipeline III (17) is sequentially connected with the water removal device (7), the activated carbon cold finger (8) and the high-vacuum six-way valve (9), and the tail end of the pipeline III is connected with the pipeline IV (18); the pipeline IV (18) is connected with the high vacuum system (2); the high-vacuum six-way valve (9) is respectively connected with a carrier gas input pipe (11), a sample ring (10) and the gas chromatography-continuous flow stable isotope mass spectrometer (1); a film vacuum gauge (6) is arranged at the joint of the pipeline II (15) and the pipeline III (17) and the pipeline IV (18);
a high vacuum valve IX (22) and a high vacuum valve X (23) are sequentially arranged on the pipeline III (17) between the water removing device (7) and the active carbon cold finger (8);
and a high-vacuum valve VII (24) is arranged on the pipeline III (17) between the active carbon cold finger (8) and the high-vacuum six-way valve (9).
2. A microliter amount of gas single molecule compound stable isotope composition analysis apparatus in accordance with claim 1 wherein: and a high vacuum valve I (16) is arranged on the pipeline II (15) close to the gas injection port (4).
3. A microliter amount of gas single molecule compound stable isotope composition analysis apparatus in accordance with claim 1 wherein: a high vacuum valve IV (19) is arranged near the joint of the pipeline II (15) and the pipeline III (17) and the pipeline IV (18).
4. A microliter amount of gas single molecule compound stable isotope composition analysis apparatus in accordance with claim 1 wherein: and a high vacuum valve V (20) is arranged on the pipeline IV (18) between the film vacuum gauge (6) and the high vacuum system (2).
5. A microliter amount of gas single molecule compound stable isotope composition analysis apparatus in accordance with claim 1 wherein: and a high vacuum valve VI (21) is arranged on the pipeline III (17) between the film vacuum gauge (6) and the water removing device (7).
6. A microliter amount of gas single molecule compound stable isotope composition analysis apparatus in accordance with claim 1 wherein: and a high-vacuum valve VIII (25) is arranged on the pipeline III (17) between the high-vacuum six-way valve (9) and the high-vacuum system (2).
7. A method of using a microliter amount of gas single molecule compound stable isotope composition analysis apparatus in accordance with claim 1 comprising the steps of:
placing a rock sample to be tested into a rock sample sectional heating degasser (3);
secondly, all high vacuum valves are opened, high vacuum is pumped to a vacuum pipeline, and the background pressure P0 of a film vacuum gauge (6) is recorded;
closing a high vacuum valve III (14), a high vacuum valve V (20) and a high vacuum valve IX (22), injecting dry air with the volume L0 in a standard state from a gas injection port (4), closing a high vacuum valve I (16) and a high vacuum valve II (13), and recording the pressure P1 of the film vacuum gauge (6);
fourth, the high vacuum valve II (13), the high vacuum valve V (20) and the high vacuum valve IX (22) are opened, and high vacuum is pumped to a vacuum pipeline;
fifthly, closing the high vacuum valve II (13), heating the rock sample to a given temperature and keeping the temperature constant for a given time;
closing the high vacuum valve V (20) and the high vacuum valve IX (22), opening the high vacuum valve II (13), waiting for 20s, then closing the high vacuum valve II (13), and recording the pressure P2 of the film vacuum gauge (6);
and (d) calculating the amount of gas released by heating the rock sample at a given temperature for a given time, the volume being L1 in a standard state, wherein l1=l0× (p2—p0)/(p1—p0);
closing a high vacuum valve VI (21) and a high vacuum valve X (23), closing a high vacuum valve VII (24), setting the temperature of the activated carbon cold finger (8) to be 77K, and enriching part of gas into the activated carbon cold finger (8) by a sectional sample injection method;
the active carbon cold finger (8) is larger than 373K, a high vacuum valve VIII (25) is closed, the high vacuum valve VII (24) is opened, the high vacuum valve VII (24) is closed after 20 seconds, and the gas with the volume L2 in the standard state is introduced into the sample ring (10);
the gas path of the high-vacuum six-way valve (9) is switched, the gas in the sample ring (10) is led into a gas chromatograph-continuous flow stable isotope mass spectrometer (1), and the single molecular hydrogen isotope composition of the gas is analyzed;
switching the gas path of the high-vacuum six-way valve (9), opening the high-vacuum valve VIII (25), and pumping high vacuum to the sample ring (10);
is provided, wherein the high vacuum valve VIII (25) is closed, the high vacuum valve VII (24) is opened, the high vacuum valve VII (24) is closed after 20 seconds, and the gas with the volume L3 in the standard state is introduced into the sample ring (10);
and (3) switching the gas path of the high-vacuum six-way valve (9), introducing the gas in the sample ring (10) into the gas chromatography-continuous flow stable isotope mass spectrometer (1), and analyzing the single-molecule carbon isotope composition of the gas.
8. A method of using a microliter amount of gas single molecule compound stable isotope composition analysis apparatus in accordance with claim 1 comprising the steps of:
placing a rock sample to be tested into a rock sample high-vacuum electromagnetic crushing and degassing device (5);
closing a high vacuum valve II (13), a high vacuum valve V (20) and a high vacuum valve IX (22), injecting dry air with the volume L0 in a standard state from a gas injection port (4), closing a high vacuum valve I (16) and a high vacuum valve III (14), and recording the pressure P1 of the film vacuum gauge (6);
fourth, opening the high vacuum valve III (14), the high vacuum valve V (20) and the high vacuum valve IX (22) to pump high vacuum to a vacuum pipeline;
closing the high vacuum valve III (14), and carrying out electromagnetic crushing and degassing on the rock sample;
closing the high vacuum valve V (20) and the high vacuum valve IX (22), opening the high vacuum valve III (14), waiting for 20s, then closing the high vacuum valve III (14), and recording the pressure P2 of the film vacuum gauge (6);
and (d) calculating the amount of gas released by high vacuum electromagnetic breaking of the rock sample, the volume being L1 in the standard state, wherein l1=l0× (p2—p0)/(p1—p0);
closing a high vacuum valve VI (21) and a high vacuum valve X (23), closing a high vacuum valve VII (24), setting the temperature of the activated carbon cold finger (8) to be 77K, and enriching part of gas into the activated carbon cold finger (8) by a sectional sample injection method;
the active carbon cold finger (8) is larger than 373K, a high vacuum valve VIII (25) is closed, the high vacuum valve VII (24) is opened, the high vacuum valve VII (24) is closed after 20 seconds, and the gas with the volume L2 in the standard state is introduced into the sample ring (10);
the gas path of the high-vacuum six-way valve (9) is switched, the gas in the sample ring (10) is led into the gas chromatograph-continuous flow stable isotope mass spectrometer (1), and the single molecular carbon isotope composition of the gas is analyzed.
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