CN112881593A - On-line extraction device and method for gaseous hydrocarbon isotopes in gas and mineral inclusion - Google Patents
On-line extraction device and method for gaseous hydrocarbon isotopes in gas and mineral inclusion Download PDFInfo
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- CN112881593A CN112881593A CN202011130012.8A CN202011130012A CN112881593A CN 112881593 A CN112881593 A CN 112881593A CN 202011130012 A CN202011130012 A CN 202011130012A CN 112881593 A CN112881593 A CN 112881593A
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- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000000605 extraction Methods 0.000 title claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 240
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 144
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 116
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- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000009834 vaporization Methods 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 239000001307 helium Substances 0.000 claims description 94
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 34
- 239000005751 Copper oxide Substances 0.000 claims description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 34
- 229910000431 copper oxide Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 238000002347 injection Methods 0.000 claims description 23
- 239000007924 injection Substances 0.000 claims description 23
- 238000007599 discharging Methods 0.000 claims description 21
- 238000010926 purge Methods 0.000 claims description 16
- 238000000859 sublimation Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000007710 freezing Methods 0.000 claims description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
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- 239000003054 catalyst Substances 0.000 claims 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0022—General constructional details of gas analysers, e.g. portable test equipment using a number of analysing channels
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
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- 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
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- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/004—CO or CO2
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- Engineering & Computer Science (AREA)
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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- Combustion & Propulsion (AREA)
- Food Science & Technology (AREA)
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention belongs to the technical field of hydrogen isotope determination, and particularly discloses an on-line extraction device and method for gaseous hydrocarbon isotope composition in a gas and mineral inclusion, wherein the device comprises a first six-way valve, a water trap communicated with the first six-way valve, a ten-way valve, a water sample collecting pipe communicated with the ten-way valve, a carbon dioxide trap, a high-temperature reaction pipe, a water trap, a second six-way valve, a quartz pipe communicated with the second six-way valve and a stable isotope mass spectrometer, wherein the ten-way valve is respectively communicated with the first six-way valve and the second six-way valve; the method comprises the following steps: loading mineral inclusion, heating to degas, oxidizing gaseous hydrocarbon in mineral inclusion, collecting gas, and H2O-vapourization sample introduction and isotope test, CO2Is sublimated intoSample and isotope test, standard isotope test, gaseous hydrocarbon oxidation in gas and gas collection test. The invention solves the technical problem that the content of the gaseous hydrocarbon can be tested from several ppm to 100 percent simultaneously, and the composition of carbon and hydrogen isotopes and the enrichment test of gas and mineral inclusion bodies on a set of device are realized.
Description
Technical Field
The invention belongs to the technical field of determination of isotope composition of gas and mineral inclusion, and particularly relates to an on-line continuous flow analysis and extraction device and method for composition of gaseous hydrocarbon carbon and hydrogen isotopes in the gas and mineral inclusion.
Background
The coal bed gas, the oil gas reservoir, the hot spring gas, the soil, the air and the fluid inclusion can contain single or mixed gaseous hydrocarbon, the carbon and hydrogen isotope composition of the gaseous hydrocarbon is tested, the nature and the thermal maturity of the hydrocarbon source rock formed by the coal bed gas can be discussed, the natural gas cause and the reservoir forming mode can be researched, the gas source and the characteristic and the greenhouse effect can be judged, and the properties of the mineral fluid, the fluid source and the oil gas transportation/accumulation space-time characteristic can be discussed.
The existing testing method for the composition of the gaseous hydrocarbon carbon and hydrogen isotopes comprises a vacuum ball milling method, a crushing method, a traditional bursting method, an improved sealing quartz tube bursting method and a gas chromatography-mass spectrometry combined method, because the content of the gaseous hydrocarbon in a gas or fluid inclusion is from a few ppm to nearly 100%, the testing method can only test the composition of the gaseous hydrocarbon carbon or hydrogen isotopes independently or only test the gaseous hydrocarbon with low concentration or high concentration, in addition, the standards of the gaseous hydrocarbon are few and are not easy to store, and the standard sample injection problem is not well solved, so that the testing of the composition of the gaseous hydrocarbon carbon and hydrogen isotopes has the defects of high sample preparation cost, low efficiency, difficult value setting and the like, and no certain experimental technology can be simultaneously used for testing and analyzing the composition of the gaseous hydrocarbon carbon and hydrogen isotopes in the gas and mineral inclusion at present time.
Disclosure of Invention
The invention aims to provide an on-line extraction device and method for gaseous hydrocarbon isotope composition in a gas and mineral inclusion, which solve the technical problem that the content of gaseous hydrocarbon can be tested from several ppm to 100 percent simultaneously, and the composition of carbon and hydrogen isotopes and the enrichment test of the gas and mineral inclusion on a set of device, and improve the analysis test precision and the analysis test efficiency.
The technical scheme for realizing the purpose of the invention is as follows: an on-line extraction device for gaseous hydrocarbon isotopes in gas and mineral inclusions comprises a first six-way valve, a multi-path water trap communicated with the first six-way valve, a ten-way valve, a water sample collecting pipe communicated with the ten-way valve, a carbon dioxide trap communicated with the ten-way valve, a high-temperature reaction pipe communicated with the ten-way valve, a multi-path water trap communicated with the ten-way valve, a second six-way valve, a quartz pipe communicated with the second six-way valve, and a stable isotope mass spectrometer communicated with the second six-way valve, wherein the ten-way valve is respectively communicated with the first six-way valve and the second six-way valve.
And the sixth port T of the first six-way valve is sequentially communicated with the quartz reaction tube, the first water trap and the first helium gas inlet.
And the first port O and the fourth port R of the first six-way valve are sequentially communicated with the three-way joint, the fourth water trap and the third helium gas inlet.
And the second port P of the first six-way valve is communicated with the gas collecting pipe, the fifth water trap and the fourth helium gas inlet in sequence.
And a first valve are respectively arranged at two ends of the gas collecting pipe, the first valve is positioned between the gas collecting pipe and the fifth water trap, and the first valve is positioned between the gas collecting pipe and the second port P.
And a first metal valve is arranged between the first valve and the fifth water trap, and a second metal valve is arranged between the first valve and the second port P.
And a second water trap, a carbon dioxide trap, a sample introduction column head and a copper oxide reaction tube are sequentially arranged between the first port O of the first six-way valve and the first port A of the ten-way valve.
The quartz reaction tube is arranged in the first temperature control heating furnace, and the copper oxide reaction tube is arranged in the second temperature control heating furnace.
And the ninth port I of the ten-way valve is communicated with the third water trap and the second helium gas inlet in sequence.
And a fifth port E of the ten-way valve is communicated with the sixth water trap and a fifth helium gas inlet in sequence.
And the eighth port H and the sixth port Z of the ten-way valve are respectively communicated with two ends of the high-temperature reaction tube.
And the seventh port G and the tenth port J of the ten-way valve are respectively communicated with two ends of the water sample collecting pipe.
And a third port C and a sixth port F of the ten-way valve are respectively communicated with two ends of the carbon dioxide collecting pipe.
And the second port B of the ten-way valve is communicated with the fourth port X of the second six-way valve.
And the first port U of the second six-way valve is communicated with the gas conversion interface and the stable isotope mass spectrometer in sequence.
And a pipeline of a fifth port Y of the second six-way valve is arranged in the first single-opening quartz tube, and a pipeline of a third port W of the second six-way valve is arranged in the second single-opening quartz tube.
The ten-way valve is arranged in the first temperature control heating box, and the second six-way valve is arranged in the second temperature control heating box.
The on-line extraction method of the gaseous hydrocarbon isotope in the gas and mineral inclusion by adopting the on-line extraction device of the gaseous hydrocarbon isotope in the gas and mineral inclusion specifically comprises the following steps:
step 4, H2O vaporization sample introduction and hydrogen isotope test;
and 7, oxidizing the gaseous hydrocarbon in the gas, collecting the gas and testing.
The specific steps of the step 1 are as follows:
step 1.1, introducing high-purity helium gas into a helium gas inlet, and adjusting a first six-way valve to be in a mineral inclusion sample purging mode
In the mineral inclusion sample purging mode in step 1.1, the helium flow direction of each port of the first six-way valve is as follows: the second port P is used for discharging air from the first port O after air is discharged; the third port Q and the fourth port R are the same in gas to form a closed loop; the sixth port T is used for discharging air from the fifth port S after air is discharged;
step 1.2, putting the mineral inclusion into a quartz reaction tube, and putting the quartz reaction tube into a first temperature control heating furnace
And (3) closing the first metal valve and the second metal valve in the step (1.2), opening the first valves of the gas collecting pipes and the first valves of the gas collecting pipes of the two valves of the gas collecting pipe, taking a fourth helium gas inlet as a carrier gas of the copper oxide reaction pipe, filling the mineral inclusion into the quartz reaction pipe, and putting the quartz reaction pipe into the first temperature control heating furnace.
The specific steps of the step 2 are as follows: setting a first temperature control heating furnace to a certain temperature, and drying helium in a first helium inlet 1 through a first water trap and then entering a quartz reaction tube; the water adsorbed on the surface of the mineral sample and the low-temperature secondary inclusion are brought out by helium and discharged into air through the first six-way valve.
The specific steps of the step 3 are as follows:
step 3.1, adjusting the first six-way valve, the ten-way valve and the second six-way valve to be in a mineral inclusion sample gaseous hydrocarbon oxidation and gas collection mode;
and 3.2, placing the water sample collecting pipe in the first cold trap, sleeving the carbon dioxide collecting pipe in the second cold trap 28, and collecting the gaseous hydrocarbon isotope in the mineral inclusion.
And 3.2, discharging gas after the gas-liquid inclusion enters the first six-way valve, and discharging gas H2O is removed by a second water trap, CO2Is absorbed by a carbon dioxide trap; other gases are introducedThe sample column head enters the copper oxide reaction tube to be oxidized into CO2And H2O back into the water sample collection tube, H2Freezing and collecting O and CO by alcohol dry ice in the first cold trap2And other gases are collected by freezing into the carbon dioxide collection tube.
The specific steps of the step 4 are as follows:
step 4.1, adjusting the ten-way valve and the second six-way valve to be H2O, a vaporization sample introduction mode;
and 4.2, heating a water sample collecting pipe, introducing the vaporized solid water into a high-temperature reaction pipe by helium, and introducing the gas generated by the reaction into a stable isotope mass spectrometer for testing the composition of hydrogen isotopes.
In the step 4.2, the first cold trap is removed, the electric heating device is switched on, solid water in the water sample collecting pipe is quickly vaporized and is brought into the high-temperature reaction pipe by helium gas to react with glassy carbon to generate H2And CO, H2And the CO enters the second six-way valve, the gas conversion interface device enters the stable isotope mass spectrometer to test the hydrogen isotope.
The specific steps of the step 5 are as follows:
step 5.1, adjusting the ten-way valve and the second six-way valve to be CO2A sublimation sample introduction mode;
step 5.2, enabling helium to pass through a sixth water trap, a carbon dioxide trap and CO in the carbon dioxide trap2The carbon isotope composition is quickly released to enter a stable isotope mass spectrometer for testing through the second six-way valve and the gas conversion interface device.
And 6, respectively injecting a water sample, methane and carbon dioxide into the sample injection column head by using a sample injection needle, and then respectively carrying out a standard water sample hydrogen isotope test, a standard methane hydrogen carbon isotope test and a standard carbon dioxide isotope test.
After the standard water sample water in the step 6 is vaporized, the water is frozen and collected by a water sample collecting pipe through a copper oxide reaction pipe and a ten-way valve, and hydrogen isotope test is carried out; standard methane enters a copper oxide reaction tube under the drive of helium to be oxidized by copper oxide to generate CO2And H2O, CO after heating2And H2O passes through the ten-way valve in a gaseous state and is cooled by waterAnd (5) freezing and collecting the sample collection tube, and testing the composition of hydrogen isotopes and carbon isotopes.
The standard CO in step 62After passing through the sample introduction column head, the copper oxide reaction tube and the water sample collecting tube, the gas is frozen and enriched by the carbon dioxide trap, and the carbon isotope composition test is carried out.
The specific steps of the step 7 are as follows:
step 7.1, adjusting the first six-way valve to be a purging mode of the gas collecting pipe;
step 7.2, adjusting the first six-way valve to be a sample introduction mode of the gas collection pipe;
and 7.3, carrying out gas collection and isotope test.
The invention has the beneficial technical effects that:
(1) the invention adopts high-purity helium as carrier gas, and connects a gas collecting pipe, a mineral inclusion bursting device, a standard sample injection column head, a gaseous hydrocarbon oxidation collecting and sample injection device and a stable isotope mass spectrometer to form a set of on-line continuous flow system, thereby realizing the simultaneous test of carbon and hydrogen isotope compositions in gaseous hydrocarbons with different contents.
(2) The gas collecting pipe of the invention has two valves at two ends respectively, can be vacuumized before loading a sample, can be conveniently sampled by opening one valve after reaching a sampling point, and is mainly used for collecting gas analysis of low-content gaseous hydrocarbon, including air samples, soil gas, geothermal gas and the like.
(3) The mineral inclusion bursting device is used for extracting fluid inclusions of various mineral samples, the temperature control heating furnace can control the temperature, different bursting temperatures can be selected and set according to research needs, one sample can also be used for extracting fluid inclusions of different mining periods, the fluid inclusions are instantly carried away from a high-temperature area by airflow under the protection of high-purity helium gas, and therefore the occurrence of isotope exchange between released gases is reduced.
(4) The standard sample injection column head can be injected with liquid water for standard CO isotope analysis2The gas is used for the standard of carbon isotope analysis, the methane gas is used for the standard of carbon and hydrogen isotope analysis,and a gas sample with higher content of gaseous hydrocarbon can be injected, a plurality of standard sample injection tests are adopted, a multi-standard calibration curve can be established, and the problem of difficult isotope accurate value determination caused by less gaseous hydrocarbon standards is solved.
(5) The invention adopts the combined technology of the ten-way valve and the six-way valve, can realize the conversion of the sampling mode of the gas collecting pipe and the mineral inclusion bursting, and generates H after the oxidation reaction of the gaseous hydrocarbon purified by the carbon dioxide trap and the water trap and the copper oxide2O、CO2Heating the pipeline to over 150 deg.C, H2O keeps the gas state to enter a water sample collecting pipe at minus 80 ℃ to be captured, and CO2The gas is collected by a carbon dioxide collecting pipe at the temperature of 196 ℃ below zero, and H can be tested firstly through the switching function of the ten-way valve and the six-way valve2O，H2O enters a high-temperature furnace to react with glassy carbon to generate H2And CO, consisting of the hydrogen isotope after chromatographic column separation, CO2Bypassing the high temperature furnace and directly injecting sample to test the carbon isotope composition.
(6) The invention adopts the connection of the detachable quick joint, which is convenient for the installation and the disassembly of the quartz reaction tube in the gas collecting tube and the fluid inclusion device, the joints of the ten-way valve and the six-way valve and the 1/16inch stainless steel pipeline are sealed by polytetrafluoroethylene gaskets, and the rest pipelines are sealed by metal gaskets, so that the whole online continuous flow system has better sealing and is not influenced by air.
Drawings
FIG. 1 is a schematic diagram of a gaseous hydrocarbon extraction apparatus for gas and mineral inclusions according to the present invention.
In the figure:
1 is a first helium gas inlet, 2 is a first water trap, 3 is a quartz reaction tube, and 4 is a first temperature control heating furnace;
5 is a first six-way valve, O is a first port of the first six-way valve, P is a second port of the first six-way valve, Q is a third port of the first six-way valve, R is a fourth port of the first six-way valve, S is a fifth port of the first six-way valve, and T is a sixth port of the first six-way valve;
6 is a second water trap, 7 is a carbon dioxide trap, 8 is a sample column head, 9 is a copper oxide reaction tube, 10 is a second temperature control heating furnace, 11 is a second helium gas inlet, 12 is a third water trap, 13 is a third helium gas inlet, 14 is a fourth water trap, 15 is a three-way joint, 16 is a fourth helium gas inlet, 17 is a fifth water trap, and 18 is a first metal valve;
19 is a gas collecting pipe, 19-1 is a first valve of the gas collecting pipe, and 19-2 is a second valve of the gas collecting pipe;
20 is a second metal valve, 21 is a high-temperature reaction tube, 22 is an electric heating device, 23 is a water sample collecting tube, 24 is a first cold trap, and 25 is a first temperature control heating box;
26 is a ten-way valve, a is a first port of the ten-way valve, B is a second port of the ten-way valve, C is a third port of the ten-way valve, D is a fourth port of the ten-way valve, E is a fifth port of the ten-way valve, F is a sixth port of the ten-way valve, G is a seventh port of the ten-way valve, H is an eighth port of the ten-way valve, I is a ninth port of the ten-way valve, and J is a tenth port of the ten-way valve;
27 is a carbon dioxide trap, 28 is a second cold trap, 29 is a sixth water trap, 30 is a fifth helium gas inlet, and 31 is a first single-opening quartz tube;
32 is a second six-way valve, U is a second six-way valve first port, V is a second six-way valve second port, W is a second six-way valve third port, X is a second six-way valve fourth port, Y is a second six-way valve fifth port, and Z is a second six-way valve sixth port;
33 is a second temperature control heating box, 34 is a gas conversion interface device, and 35 is a stable isotope mass spectrometer.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
As shown in fig. 1, the device for on-line extraction of gaseous hydrocarbon isotopes in a gas and mineral inclusion in this embodiment includes a first helium gas inlet 1, a second helium gas inlet 11, a third helium gas inlet 13, a fourth helium gas inlet 16, a fifth helium gas inlet 30, a first water trap 2, a second water trap 6, a third water trap 12, a fourth water trap 14, a fifth water trap 17, a sixth water trap 29, a quartz reaction tube 3, a first temperature-controlled heating furnace 4, a second temperature-controlled heating furnace 10, a first six-way valve 5, a second six-way valve 32, a carbon dioxide trap 7, a sample column head 8, a copper oxide reaction tube 9, a three-way joint 15, a first metal valve 18, a second metal valve 20, a gas collecting tube 19, a first gas collecting tube 19-1, a second gas collecting tube 19-2, a high-temperature reaction tube 21, an electric heating device 22, a water sample collecting tube 23, a high-temperature reaction tube 20, a gas collecting tube 21, a high-, The system comprises a first cold trap 24, a second cold trap 28, a first temperature-controlled heating box 25, a second temperature-controlled heating box 33, a ten-way valve 26, a carbon dioxide trap 27, a first single-opening quartz tube 31, a second single-opening quartz tube 36, a gas conversion interface 34 and a stable isotope mass spectrometer 35.
As shown in fig. 1, a first helium gas inlet 1 is connected with a sixth port T of a first six-way valve 5 through a first water trap 2 and a quartz reaction tube 3 in sequence; the first helium gas inlet 1 is communicated with an inlet of a first water trap 2 through a pipeline, an outlet of the first water trap 2 is communicated with an inlet of a quartz reaction tube 3 through a pipeline, and an outlet of the quartz reaction tube 3 is communicated with a sixth port T of a first six-way valve 5 through a pipeline.
Helium passes through a sixth port T of the first six-way valve 5, comes out of a first port O of the first six-way valve 5, then passes through a second water trap 6, a carbon dioxide trap 7, a sample introduction column head 8 and a copper oxide reaction tube 9, and reaches a first port A of a ten-way valve 26; the inlet of the second water trap 6 is communicated with the first port O of the first six-way valve 5 through a pipeline, the outlet of the second water trap 6 is communicated with the inlet of the carbon dioxide trap 7 through a pipeline, the outlet of the carbon dioxide trap 7 is communicated with the inlet of the sample injection column head 8 through a pipeline, the outlet of the sample injection column head 8 is communicated with the inlet of the copper oxide reaction tube 9 through a pipeline, and the outlet of the copper oxide reaction tube 9 is communicated with the first port A of the ten-way valve 26 through a pipeline.
The second helium gas inlet 11 is connected with the ninth port I of the ten-way valve 26 through the third water trap 12; the second helium gas inlet 11 is communicated with the inlet of the third water trap 12 through a pipeline, and the outlet of the third water trap 12 is communicated with the ninth port I of the ten-way valve through a pipeline.
A third helium gas inlet 13 is connected with a third port Q and a fourth port R of the first six-way valve 5 through a fourth water trap 14 and a three-way joint 15 in a shunting manner; the third helium gas inlet 13 is communicated with an inlet of a fourth water trap 14 through a pipeline, an outlet of the fourth water trap 14 is communicated with a first joint of a three-way joint 15 through a pipeline, and the other two joints of the three-way joint 15 are respectively communicated with a third port Q of the first six-way valve 5 and a fourth port R of the first six-way valve 5 through pipelines.
A fourth helium gas inlet 16 is connected with the second port P of the first six-way valve 5 through a fifth water trap 17 and a gas collecting pipe 19; the outlet of the fourth helium gas inlet 16 is in communication with the inlet of a fifth water trap 17 via a line; an outlet of the fifth water trap 17 is communicated with a first valve 19-1 of the gas collecting pipe 19 through a pipeline, and a first metal valve 18 is arranged on the pipeline between the fifth water trap 17 and the first valve 19-1 of the gas collecting pipe; the second valve 19-2 of the gas collecting pipe 19 is communicated with the second port P of the first six-way valve 5 through a pipeline, and a second metal valve 20 is arranged on the pipeline between the second valve 19-2 of the gas collecting pipe 1 and the second port P of the first six-way valve.
A fifth helium gas inlet 30 is connected to a fifth port E of the ten-way valve 26 via a sixth water trap 29; the fifth helium gas inlet 30 is in communication with the inlet of the sixth water trap 29 by a line and the outlet of the sixth water trap 29 is in communication with the fifth port E of the ten-way valve 26 by a line.
Two ends of the high-temperature reaction tube 21 are respectively communicated with the eighth port H of the ten-way valve 26 and the sixth port Z of the second six-way valve 32 through pipelines.
Two ends of the water sample collecting pipe 23 are respectively communicated with the seventh port G of the ten-way valve 26 and the tenth port J of the ten-way valve 26 through pipelines. Two ends of the water sample collecting pipe 23 are respectively communicated with two ends of the electric heating device 22 through cables.
Two ends of the carbon dioxide collecting pipe 27 are respectively communicated with the third port C of the ten-way valve 26 and the sixth port F of the ten-way valve 26 through pipelines.
The second port B of the ten-way valve 26 communicates through a line with the fourth port X of the second six-way valve 32. The stable isotope mass spectrometer 35 is connected to the first port U of the second six-way valve 32 via a gas switching port 34, and an outlet of the gas switching port 34 is communicated with the first port U of the second six-way valve 32 via a pipeline.
Wherein, the quartz reaction tube 3 is nested in the groove of the first temperature control heating furnace 4, the copper oxide reaction tube 9 is nested in the groove of the second temperature control heating furnace 10, the water sample collecting tube 23 is arranged in the first cold trap 24, and the carbon dioxide trap 27 is arranged in the second cold trap 28; the outlet pipeline is arranged at the bottom of the first single-opening quartz tube 31 and the second single-opening quartz tube 36, the pipeline communicated with the fifth port Y of the second six-way valve 32 is arranged in the first single-opening quartz tube 31, and the pipeline communicated with the third port W of the second six-way valve 32 is arranged in the second single-opening quartz tube 36. A ten-way valve 26 is placed in the first temperature-controlled heating tank 25 and a second six-way valve 32 is placed in the second temperature-controlled heating tank 33.
In this embodiment, the connecting lines between the components are made of stainless steel tubes with an outer diameter of 1/16 inch.
In this embodiment, the first metal valve 18 and the second metal valve 20 are made of stainless steel.
In this embodiment, the quartz reaction tube 3 is an 1/4inch quartz glass tube, and both ends are connected by a quick coupling, so as to facilitate disassembly and sample assembly.
In this embodiment, the first water trap 2, the third water trap 12, the fourth water trap 14, the fifth water trap 17 and the sixth water trap 29 can effectively adsorb moisture in helium, and the second water trap 6 and the carbon dioxide trap 7 are used for adsorbing a fluid inclusion and H in gas2O、CO2And purifying the gaseous hydrocarbon.
In this embodiment, the temperature of the first temperature control heating box 4 may be set to different temperatures according to different minerals, quartz may be set to 600 ℃, calcite may be set to 420 ℃, and fluid inclusions at different temperature stages may be extracted according to research needs, so as to achieve the purpose of stage heating.
In this embodiment, the second temperature-controlled heating box 10 is set at 800 ℃, heats the copper oxide in the copper oxide reaction tube 9, and provides an oxidant for the gaseous hydrocarbon to oxidize to generate CO2And H2And O, facilitating the enrichment of gas and the test of carbon and hydrogen isotope composition.
In this embodiment, when the first metal valve 18 and the second metal valve 20 are opened, and the first valve 19-1 of the two gas collecting pipes of the gas collecting pipe 19 and the second valve 19-2 of the gas collecting pipe are closed, the third helium gas inlet 13 and the fourth helium gas inlet 16 are mainly used for purging air at two ends of the gas collecting pipe 19, so as to reduce interference on gas in the gas collecting pipe.
In this embodiment, the sampling column head 8 is mainly used for sampling a water sample standard substance, the hydrogen isotope standard can be injected by sucking a 0.2 μ L water sample through a sealing pad of the sampling column head 8 by using a liquid sampling needle, the water is vaporized in a pipeline at 150 ℃ and is enriched by a water sample collecting pipe 23, the solid water in the water sample collecting pipe 23 is heated by an electric heating device 22 for about 5s from-80 ℃ to over 200 ℃, the vaporized water is brought into a 1380 ℃ high-temperature reaction pipe 21 by helium gas and reacts with glassy carbon to generate H2And CO, after being separated by the chromatographic column, sequentially enters a stable isotope mass spectrometer to test the hydrogen isotope composition, and tests the hydrogen isotope composition of different water sample standards, so that a multi-standard correction curve can be established for accurately determining the value of the gaseous hydrocarbon hydrogen isotope in the gas and mineral inclusion.
In this embodiment, the sample column head 8 can also be used for sampling gas standard methane or carbon dioxide, and the methane reacts with copper oxide in the copper oxide reaction furnace 9 at 800 ℃ to generate CO2And H2O, carbon dioxide passing through a copper oxide reaction furnace, CO2Collected by a carbon dioxide trap, CO2Sending the released carbon isotope into a stable isotope mass spectrometer for testing the carbon isotope composition and testing a plurality of gas standard CO2The carbon isotope composition can establish a carbon isotope multi-standard calibration curve for accurately determining the value of the gaseous hydrocarbon carbon isotope in the gas and mineral inclusion.
As shown in fig. 1, an on-line extraction method for gaseous hydrocarbon isotopes in gas and mineral inclusions specifically comprises the following steps:
Step 1.1, introducing high-purity helium gas into a helium gas inlet, and adjusting a first six-way valve 5 to be in a mineral inclusion sample purging mode
99.999 percent of high-purity helium is introduced into the first helium gas inlet 1, the second helium gas inlet 11, the third helium gas inlet 13, the fourth helium gas inlet 16 and the fifth helium gas inlet 30. And (3) adjusting the first six-way valve 5 to be in a mineral inclusion sample purging mode, wherein helium gas flow directions of all ports of the first six-way valve 5 in the mineral inclusion sample purging mode are as follows: the second port P is used for discharging air from the first port O after air is discharged; the third port Q and the fourth port R are the same in gas to form a closed loop; and the sixth port T is used for air inlet and then air outlet from the fifth port S.
Step 1.2, the mineral inclusion is put into a quartz reaction tube 3, and the quartz reaction tube 3 is put into a first temperature control heating furnace 4
The first metal valve 18 and the second metal valve 20 are closed, the first valves 19-1 and 19-2 of the two gas collecting pipes of the gas collecting pipe 19 are opened, and the fourth helium gas inlet 16 is used as carrier gas of the copper oxide reaction pipe 9; and (3) putting the mineral inclusion into the quartz reaction tube 3, opening the upper cover of the first temperature control heating furnace 4, and putting the quartz reaction tube 3 into the first temperature control heating furnace 4 through a quick connector.
Setting the temperature of a first temperature control heating furnace 4 to be 200 ℃, and drying helium in a first helium inlet 1 through a first water trap 2 and then entering a quartz reaction tube 3; gas adsorbed on the surface of the mineral sample, particularly water and low-temperature secondary inclusion are brought out by helium gas, enter the sixth port T of the first six-way valve 5, and are discharged into air from the fifth port S of the first six-way valve 5 for 10min, so that interference of other gases on primary gaseous hydrocarbon inclusion is reduced.
Step 3.1, adjusting the first six-way valve 5, the ten-way valve 26 and the second six-way valve 32 to be in a mode of oxidizing the gas-state hydrocarbon of the mineral inclusion sample and collecting the gas
After the degassing is completed, the first six-way valve 5 is adjusted to be in a mineral inclusion sample gaseous hydrocarbon oxidation and gas collection mode, and helium gas at each port of the first six-way valve 5 flows in the following mode: the second port P and the third port Q are in a communicated state; the fourth port R is used for discharging air from the fifth port S after air is discharged from the fourth port R; and the sixth port T is used for exhausting air from the first port O after air is input.
The ten-way valve 26 is adjusted to be in a mineral inclusion sample gaseous hydrocarbon oxidation and gas collection mode, and helium flows to all ports of the ten-way valve 26 in the mode are as follows: the first port A is used for discharging air from the tenth port J after air is fed, and the third port C is used for discharging air from the second port B after air is fed; the fifth port E is used for discharging air from the fourth port D after air is discharged from the fifth port E; the seventh port G is used for discharging air from the sixth port F after air is discharged; and the ninth port I is used for air inlet and then is used for air outlet from the eighth port H.
The second six-way valve 32 is adjusted to the mineral inclusion sample gaseous hydrocarbon oxidation and gas collection mode, in which helium gas flows to each port of the second six-way valve 32 as follows: the second port V is used for exhausting air from the third port W after air enters; the fourth port X is used for exhausting air from the fifth port Y after air is exhausted; and the sixth port Z is used for exhausting air from the first port U after air is exhausted.
3.2, placing the water sample collecting pipe 23 in the first cold trap 24, sleeving the carbon dioxide collecting pipe 27 in the second cold trap 28, and collecting the gaseous hydrocarbon isotope in the mineral inclusion
The water sample collecting pipe 23 is arranged in the first cold trap 24, and alcohol dry ice is added into the first cold trap 24; the carbon dioxide collecting pipe 27 is sleeved on the second cold trap 28, and liquid nitrogen is poured into the second cold trap 28; the carbon dioxide collecting pipe 27 is filled with nickel wires to prevent the generation of carbon dioxide crystal grains, which is beneficial to the complete collection and rapid release of carbon dioxide gas.
Because of the protection of the high-purity helium gas with the flow rate of 90mL/min, the mineral inclusion in the quartz reaction tube 3 bursts to release a gas-liquid inclusion and the gas-liquid inclusion is rapidly carried away from a high-temperature region by the helium gas, thereby reducing the occurrence of isotope exchange among the inclusion components. The gas-liquid inclusion enters the sixth port T of the first six-way valve 5, and is discharged from the first port O, H2O is removed by the second water trap 6, CO2Is adsorbed by the carbon dioxide trap 7. Other gases enter a copper oxide reaction tube 9 through a sample introduction column head 8 to be oxidized into CO2And H2And O, enters the first port A of the ten-way valve 26, is exhausted from the tenth port J and enters the water sample collecting pipe 23. H2The O is collected by freezing alcohol dry ice at-80 ℃ in the first cold trap 24, and CO2And other gases enter a seventh port G of the ten-way valve 26, the sixth port F enters a carbon dioxide collecting pipe 27 at the temperature of 196 ℃ below zero after exiting, the gases are collected by freezing, the other gases enter a third port C of the ten-way valve 26, exit from a second port B, enter a fourth port X of a second six-way valve 32, exit from a fifth port Y, enter a first open quartz pipe 31 and are discharged into air for 10 minutes.
Step 4, H2O-vapourization sample introduction and hydrogen isotope test
Step 4.1, adjust the ten-way valve 26 and the second six-way valve 32 to H2O vaporization sample introduction mode
Adjusting the ten-way valve 26 to H2O vaporization sample introduction mode, H2Helium flows to each port of the ten-way valve 26 in the O-vaporization sample injection mode are as follows: the first port A is used for discharging air from the second port B after air is fed, and the third port C is used for discharging air from the fourth port D after air is fed; the fifth port E is used for discharging air from the sixth port F after air is discharged from the fifth port E; the seventh port G is used for exhausting air from the eighth port H after air is exhausted; and the ninth port I is used for air inlet and then is used for air outlet from the tenth port J.
Adjusting the second six-way valve 32 to H2O vaporization sample introduction mode, H2The helium flow at each port of the second six-way valve 32 in the O-vaporization sample injection mode is as follows: the second port V is used for exhausting air from the third port W after air enters; the fourth port X is used for exhausting air from the fifth port Y after air is exhausted; and the sixth port Z is used for exhausting air from the first port U after air is exhausted.
And 4.2, heating a water sample collecting pipe 23, introducing the vaporized solid water into the high-temperature reaction pipe 21 by helium, and introducing the gas generated by the reaction into a stable isotope mass spectrometer 35 to test the composition of the hydrogen isotopes.
The first cold trap 24 is removed, the switch of the electric heating device 22 is switched on, the solid water in the water sample collecting pipe 23 is quickly vaporized and is brought into 1/16inch stainless steel pipeline with the temperature of 150 ℃ by helium, and the solid water enters the tenth valve 26, enters the 1380 ℃ high-temperature reaction pipe 21 after coming out from the eighth port H and reacts with glassy carbon in the reaction pipe to generate H2And CO, then H2And the CO enters a sixth port Z of the second six-way valve 32, and enters a stable isotope mass spectrometer 35 through a gas conversion interface device 34 after coming out of the first port U to test the hydrogen isotope composition.
Step 5.1, adjusting the ten-way valve 26 and the second six-way valve 32 to be CO2Sublimation sample introduction mode
Adjusting the ten-way valve 26 to CO2Sublimation sample introduction mode of CO2Helium flow to each port of the ten-way valve 26 in sublimation sample injection mode is as follows: the first port A is used for discharging air from the second port B after air is fed, and the third port C is used for discharging air from the fourth port D after air is fed(ii) a The fifth port E is used for discharging air from the sixth port F after air is discharged from the fifth port E; the seventh port G is used for exhausting air from the eighth port H after air is exhausted; and the ninth port I is used for air inlet and then is used for air outlet from the tenth port J.
Adjusting the second six-way valve 32 to CO2Sublimation sample introduction mode, CO2In the sublimation sample injection mode, the helium gas flows to the respective ports of the second six-way valve 32 as follows: the first port U is used for air inlet and then is used for air outlet from the second port V; the fourth port X is used for exhausting air from the third port W after air is exhausted; and the sixth port Z is used for exhausting air from the fifth port Y after air is exhausted.
Step 5.2, helium passes through a sixth water trap 29 and a carbon dioxide trap 27, and CO in the carbon dioxide trap 272Quickly released to enter a stable isotope mass spectrometer 35 for testing carbon isotope composition through a second six-way valve 32 and a gas conversion interface device 34
The helium gas from the fifth helium gas inlet 30 is dried by the sixth water trap 29, enters the fifth port E of the ten-way valve 26, exits from the sixth port F into the carbon dioxide trap 27, is removed from the second cold trap 28, and CO in the carbon dioxide trap 272The test gas is rapidly released and brought into the third port C of the ten-way valve 26, and then comes out of the fourth port D and enters the second port V of the second six-way valve 32, and then enters the stable isotope mass spectrometer 35 from the first port U through the gas conversion interface device 34 to test the carbon isotope composition.
Through the sealing gasket of the sampling column head 8, a liquid sampling needle can be used for injecting a water sample into the sampling column head 8, or a gas sampling needle can be used for injecting methane and carbon dioxide into the sampling column head 8.
Step 6.1, standard water sample hydrogen isotope test
Standard water samples: sucking 0.2 microliter of standard water sample by using a liquid sampling needle, injecting the standard water sample into the sampling column head 8, vaporizing the water in the sampling column head 8 when the temperature in the pipeline is more than 150 ℃, enabling the vaporized water to enter the first port A of the ten-way valve 26 through the copper oxide reaction tube 9, enabling the water to come out of the tenth port J of the ten-way valve 26 and then to be collected by the water sample collecting tube 23 in a freezing way, and carrying out hydrogen isotope test in the same step 4.
Step 6.2, standard methane hydrogen carbon isotope test
Standard methane: by using5mL of methane gas sucked by the gas sample injection needle is injected into the system through the sample injection column cap 8, enters the copper oxide reaction tube 9 under the drive of helium, and is oxidized by copper oxide to generate CO2And H2O, heating the pipeline to over 150 ℃ through a heating belt, and heating CO2And H2O enters the first port A of the ten-way valve 26 in a gas state, is frozen and collected by the water sample collecting pipe 23 after coming out of the tenth port J, and CO2And the hydrogen isotope composition test is performed in the same step 4 as the hydrogen isotope composition test, and the carbon isotope composition test is performed in the same step 5 as the carbon isotope composition test.
Step 6.3, Standard carbon dioxide isotope test
Standard carbon dioxide: 5mL of standard CO is sucked in by adopting a gas sample injection needle2Gas is injected into the system through the sample introduction column cap 8, CO2Enters the first port A of the ten-way valve 26 through the copper oxide reaction tube 9, enters the seventh port G of the ten-way valve 26 again through the water sample collecting tube 23 after exiting from the tenth port J, is frozen and enriched by the carbon dioxide trap 27 after exiting from the sixth port F, and CO is obtained2The sublimation sample introduction and the carbon isotope composition test are performed in the same step 5.
Step 7, oxidizing the gaseous hydrocarbon in the gas, collecting the gas and testing
Step 7.1, adjusting the first six-way valve 5 to be the purging mode of the gas collecting pipe 19
The gas containing gaseous hydrocarbon is generally stored in the gas collecting pipe 19 with two valves, and after the gas collecting pipe 19 is connected to the system, the first six-way valve 5 is adjusted to the purging mode of the gas collecting pipe 19, and the helium gas at each port of the first six-way valve 5 flows in the following direction when the gas collecting pipe 19 is in the purging mode: the third port Q is used for discharging air from the second port P after air enters; the fourth port R is used for discharging air from the fifth port S after air is discharged from the fourth port R; and the sixth port T is used for exhausting air from the first port O after air is input. Gas collecting pipe 19
The first valve 19-1 and the second valve 19-2 of the gas collecting pipe 19 are closed, the first metal valve 18 and the second metal valve 20 are opened, and the helium gas in the fourth helium gas inlet 16 is dried by the fifth water trap 17 and then is discharged into the air from the first metal valve 18 so as to purge the air at the first valve 19-1 of the gas collecting pipe 19. The helium gas in the third helium gas inlet 13 is absorbed by the fourth water trap 14, enters the third port Q of the first six-way valve 5 through the three-way joint 15, and exits from the second port P of the first six-way valve 5 to be discharged into the air from the second metal valve 20, so as to purge the air at the second valve 19-2 of the gas collecting pipe 19. The purge time lasted 10 min.
Step 7.2, adjusting the first six-way valve 5 to be the sample injection mode of the gas collection pipe 19
And adjusting the first six-way valve 5 to be in the sample injection mode of the gas collection pipe 19, wherein the helium gas flow direction of each port of the first six-way valve 5 in the sample injection mode of the gas collection pipe 19 is as follows: the second port P is used for discharging air from the first port O after air is discharged; the third port Q and the fourth port R are the same in gas to form a closed loop; and the sixth port T is used for air inlet and then air outlet from the fifth port S.
Step 7.3, gas collection and isotope testing
And (3) adjusting the first six-way valve 5 to be in a sample introduction mode of the gas collection pipe 19, opening a first valve 19-1 and a second valve 19-2 of the gas collection pipe 19, enabling gas in the gas collection pipe 19 to enter a second port P of the first six-way valve 5 under the driving of high-purity helium, and performing oxidation, gas collection and isotope test on the gas after the gas comes out from the first port O in the same steps as the steps 3, 4 and 5.
The present invention has been described in detail with reference to the drawings and examples, but the present invention is not limited to the examples, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. The prior art can be adopted in the content which is not described in detail in the invention.
Claims (29)
1. The utility model provides a gaseous hydrocarbon isotope on-line extraction element in gas and mineral inclusion which characterized in that: the device comprises a first six-way valve (5), a multi-path water trap communicated with the first six-way valve (5), a ten-way valve (26), a water sample collecting pipe (23) communicated with the ten-way valve (26), a carbon dioxide trap (27) communicated with the ten-way valve (26), a high-temperature reaction pipe (21) communicated with the ten-way valve (26), a multi-path water trap communicated with the ten-way valve (26), a second six-way valve (32), a quartz pipe communicated with the second six-way valve (32), and a stable isotope mass spectrometer (35) communicated with the second six-way valve (32), wherein the ten-way valve (26) is respectively communicated with the first six-way valve (5) and the second six-way valve (32).
2. The apparatus of claim 1, wherein the apparatus comprises: and a sixth port T of the first six-way valve (5) is sequentially communicated with the quartz reaction tube (3), the first water trap (2) and the first helium gas inlet (1).
3. The apparatus of claim 2, wherein the apparatus comprises: and the first port O and the fourth port R of the first six-way valve (5) are sequentially communicated with a three-way joint (15), a fourth water trap (14) and a third helium gas inlet (13).
4. The apparatus of claim 3, wherein the apparatus comprises: and a second port P of the first six-way valve (5) is sequentially communicated with a gas collecting pipe (19), a fifth water trap (17) and a fourth helium gas inlet (16).
5. The apparatus of claim 4, wherein the apparatus comprises: and a first valve (19-1) and a first valve (19-2) are respectively arranged at two ends of the gas collecting pipe (19), the first valve (19-1) is positioned between the gas collecting pipe (19) and the fifth water trap (17), and the first valve (19-2) is positioned between the gas collecting pipe (19) and the second port P.
6. The apparatus of claim 5, wherein the apparatus comprises: a first metal valve (18) is arranged between the first valve (19-1) and the fifth water trap (17), and a second metal valve (20) is arranged between the first valve (19-2) and the second port P.
7. The apparatus of claim 6, wherein the apparatus comprises: and a second water trap (6), a carbon dioxide trap (7), a sample introduction column head (8) and a copper oxide reaction tube (9) are sequentially arranged between the first port O of the first six-way valve (5) and the first port A of the ten-way valve (26).
8. The apparatus of claim 7, wherein the apparatus comprises: the quartz reaction tube (3) is arranged in the first temperature control heating furnace (4), and the copper oxide reaction tube (9) is arranged in the second temperature control heating furnace (10).
9. The apparatus of claim 8, wherein the apparatus comprises: and a ninth port I of the ten-way valve (26) is sequentially communicated with the third water trap (12) and the second helium gas inlet (11).
10. The apparatus of claim 9, wherein the apparatus comprises: and a fifth port E of the ten-way valve (26) is sequentially communicated with a sixth water trap (29) and a fifth helium gas inlet (30).
11. The apparatus of claim 10, wherein the apparatus comprises: and the eighth port H and the sixth port Z of the ten-way valve (26) are respectively communicated with two ends of the high-temperature reaction tube (21).
12. The apparatus of claim 11, wherein the apparatus comprises: and the seventh port G and the tenth port J of the ten-way valve (26) are respectively communicated with two ends of the water sample collecting pipe (23).
13. The apparatus of claim 12, wherein the apparatus comprises: and the third port C and the sixth port F of the ten-way valve (26) are respectively communicated with two ends of a carbon dioxide collecting pipe (27).
14. The apparatus of claim 13, wherein the apparatus comprises: and the second port B of the ten-way valve (26) is communicated with the fourth port X of the second six-way valve (32).
15. The apparatus of claim 14, wherein the apparatus comprises: and the first port U of the second six-way valve (32) is sequentially communicated with a gas conversion interface device (34) and a stable isotope mass spectrometer (35).
16. The apparatus of claim 15, wherein the apparatus comprises: and a pipeline of a fifth port Y of the second six-way valve (32) is placed in the first single-opening quartz tube (31), and a pipeline of a third port W of the second six-way valve (32) is placed in the second single-opening quartz tube (36).
17. The apparatus of claim 15, wherein the apparatus comprises: the ten-way valve (26) is arranged in the first temperature control heating box (25), and the second six-way valve (32) is arranged in the second temperature control heating box (33).
18. An on-line extraction method for gaseous hydrocarbon isotopes in gas and mineral inclusions, which comprises the steps of using the on-line extraction device for gaseous hydrocarbon isotopes in gas and mineral inclusions as claimed in any one of claims 1 to 17, and is characterized in that: the method specifically comprises the following steps:
step 1, loading a mineral inclusion;
step 2, heating the mineral inclusion to degas;
step 3, oxidizing the gaseous hydrocarbon in the mineral inclusion and collecting the gas;
step 4, H2O-vapourization sample injection and hydrogen isotopeTesting;
step 5, CO2Carrying out sublimation sample introduction and carbon isotope test;
step 6, testing a standard water sample, methane hydrogen carbon and carbon dioxide isotopes;
and 7, oxidizing the gaseous hydrocarbon in the gas, collecting the gas and testing.
19. The method of claim 18, wherein the gaseous hydrocarbon isotope is extracted from the gas and mineral inclusion on-line, and the method comprises: the specific steps of the step 1 are as follows:
step 1.1, introducing high-purity helium gas into a helium gas inlet, and adjusting a first six-way valve (5) to be in a mineral inclusion sample purging mode
In the mineral inclusion sample purging mode in the step 1.1, helium flows to each port of the first six-way valve (5) are as follows: the second port P is used for discharging air from the first port O after air is discharged; the third port Q and the fourth port R are the same in gas to form a closed loop; the sixth port T is used for discharging air from the fifth port S after air is discharged;
step 1.2, the mineral inclusion is put into a quartz reaction tube (3), and the quartz reaction tube (3) is put into a first temperature control heating furnace (4)
In the step 1.2, a first metal valve (18) and a second metal valve (20) are closed, a first valve (19-1) of a gas collecting pipe of two valves of a gas collecting pipe (19) and a second valve (19-2) of the gas collecting pipe are opened, at the moment, a fourth helium gas inlet (16) is used as a carrier gas of a copper oxide reaction pipe (9), a mineral inclusion is filled into a quartz reaction pipe (3), and the quartz reaction pipe (3) is placed into a first temperature control heating furnace (4).
20. The method of claim 19, wherein the gaseous hydrocarbon isotope is extracted from the gas and mineral inclusion on-line by: the specific steps of the step 2 are as follows: setting a first temperature control heating furnace (4) to a certain temperature, and drying helium in a first helium inlet (1) through a first water trap (2) and then entering a quartz reaction tube (3); the water adsorbed on the surface of the mineral sample and the low-temperature secondary inclusion are brought out by helium and discharged into the air through a first six-way valve (5).
21. The method of claim 20, wherein the gaseous hydrocarbon isotope is extracted from the gas and mineral inclusion on-line by: the specific steps of the step 3 are as follows:
step 3.1, adjusting the first six-way valve (5), the ten-way valve (26) and the second six-way valve (32) to be in a mode of oxidizing the mineral inclusion sample gas hydrocarbon and collecting the gas;
and 3.2, placing a water sample collecting pipe (23) in the first cold trap (24), sleeving a carbon dioxide collecting pipe (27) in the second cold trap (28), and collecting the gaseous hydrocarbon isotope in the mineral inclusion.
22. The method of claim 21, wherein the gaseous hydrocarbon isotope is extracted from the gas and mineral inclusion on-line by: 3.2, the gas-liquid inclusion enters a first six-way valve (5) and then is discharged, H2O is removed by a second water trap (6), CO2Is absorbed by a carbon dioxide trap (7); other gases enter the copper oxide reaction tube (9) through the sample introduction column cap (8) to be oxidized into CO2And H2O after the sample enters a water sample collecting pipe (23), H2The O is collected by freezing alcohol in the first cold trap (24) with dry ice, and the CO is collected2And other gases are collected by freezing in a carbon dioxide collecting pipe (27).
23. The method of claim 22, wherein the gaseous hydrocarbon isotope is extracted from the gas and mineral inclusion on-line by: the specific steps of the step 4 are as follows:
step 4.1, adjusting the ten-way valve (26) and the second six-way valve (32) to be H2O, a vaporization sample introduction mode;
and 4.2, heating a water sample collecting pipe (23), introducing the vaporized solid water into a high-temperature reaction pipe (21) by helium, and introducing the gas generated by the reaction into a stable isotope mass spectrometer (35) to test the composition of the hydrogen isotope.
24. The method of claim 23, wherein the gaseous hydrocarbon isotope is extracted from the gas and mineral inclusion on-line, and the method comprises: in the step 4.2, the catalyst is removedThe first cold trap (24) is switched on and switched on by the electric heating device (22), solid water in the water sample collecting pipe (23) is quickly vaporized and taken into the high-temperature reaction pipe (21) by helium gas to react with glassy carbon to generate H2And CO, H2And CO enters a second six-way valve (32), a gas conversion interface device (34) enters a stable isotope mass spectrometer (35) to test the hydrogen isotope composition.
25. The method of claim 24 for on-line extraction of gaseous hydrocarbon isotopes from gas and mineral inclusions, wherein the method comprises: the specific steps of the step 5 are as follows:
step 5.1, adjusting the ten-way valve (26) and the second six-way valve (32) to be CO2A sublimation sample introduction mode;
step 5.2, helium passes through a sixth water trap (29) and a carbon dioxide trap (27), and CO in the carbon dioxide trap (27)2The carbon isotope composition is rapidly released to enter a stable isotope mass spectrometer (35) for testing through a second six-way valve (32) and a gas conversion interface device (34).
26. The method of claim 25, wherein the gaseous hydrocarbon isotope is extracted from the gas and mineral inclusion on-line by: and step 6, respectively injecting a water sample, methane and carbon dioxide into the sample injection column head (8) by using a sample injection needle, and then respectively carrying out a standard water sample hydrogen isotope test, a standard methane hydrogen carbon isotope test and a standard carbon dioxide isotope test.
27. The method of claim 26, wherein the gaseous hydrocarbon isotope is extracted from the gas and mineral inclusion on-line by: after the standard water sample water in the step 6 is vaporized, the water is frozen and collected by a water sample collecting pipe (23) through a copper oxide reaction pipe (9) and a ten-way valve (26) for hydrogen isotope test; standard methane enters a copper oxide reaction tube (9) under the drive of helium to be oxidized by copper oxide to generate CO2And H2O, CO after heating2And H2And the O passes through the ten-way valve (26) in a gas state, is frozen and collected by the water sample collecting pipe (23), and is subjected to hydrogen isotope and carbon isotope composition test.
28. The method of claim 27, wherein the gaseous hydrocarbon isotope is extracted from the gas and mineral inclusion on-line by: the standard CO in step 62The gas passes through a sample injection column head (8), a copper oxide reaction tube (9) and a water sample collecting tube (23), and is frozen and enriched by a carbon dioxide trap (27) to carry out carbon isotope composition test.
29. The method of claim 2827, wherein the gaseous hydrocarbon isotope is extracted from the gas and mineral inclusion on-line by: the specific steps of the step 7 are as follows:
7.1, adjusting the first six-way valve (5) to be a purging mode of the gas collecting pipe (19);
7.2, adjusting the first six-way valve (5) to be in a sample introduction mode of the gas collection pipe (19);
and 7.3, carrying out gas collection and isotope test.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113514315A (en) * | 2021-07-09 | 2021-10-19 | 广东海洋大学 | Device and method for removing water during enrichment determination of nitrous oxide stable isotope |
| CN115112793A (en) * | 2022-06-20 | 2022-09-27 | 核工业北京地质研究院 | Device and method for online determination of carbon dioxide carbon isotope in inclusion by crushing method |
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2020
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113514315A (en) * | 2021-07-09 | 2021-10-19 | 广东海洋大学 | Device and method for removing water during enrichment determination of nitrous oxide stable isotope |
| CN113514315B (en) * | 2021-07-09 | 2024-01-05 | 广东海洋大学 | Device and method for removing water during enrichment determination of nitrous oxide stable isotope |
| CN115112793A (en) * | 2022-06-20 | 2022-09-27 | 核工业北京地质研究院 | Device and method for online determination of carbon dioxide carbon isotope in inclusion by crushing method |
| CN115112793B (en) * | 2022-06-20 | 2023-10-20 | 核工业北京地质研究院 | Device and method for online determination of carbon dioxide and carbon isotopes in inclusion by crushing method |
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