Device and method for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions

Abstract

The present invention belongs to the technical field of determination of gaseous hydrocarbon hydrogen isotope composition in mineral inclusions, and specifically discloses a device and method for extracting gaseous hydrocarbon hydrogen isotope composition in mineral inclusions. The present invention adopts helium as the protective carrier gas of the online continuous flow system, and each helium uses a water trap filled with magnesium perchlorate to absorb and dry the trace water that may exist in the helium, so as to avoid the influence of the trace water in the carrier gas on the test results of the gaseous hydrocarbon hydrogen isotope composition. The present invention adopts an online continuous flow method to connect the mineral inclusion explosion device, methane oxidation, and product water collection device with a stable isotope mass spectrometer, so as to realize the online heating explosion of the mineral in the helium flow environment, the online oxidation of methane, the online collection of the oxidation product water, and the electric heating and release of water into the stable isotope mass spectrometer for testing. Compared with the traditional offline method, the sample amount is greatly reduced, thereby effectively reducing the workload of mineral processing and the scientific research cost, and improving the scientific research efficiency.

Description

Technical Field

[0001] The invention belongs to the technical field of determination of hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions, and particularly relates to an online continuous flow explosion extraction device for gaseous hydrocarbons in mineral inclusions and a hydrogen isotope composition analysis method. Background Art

[0002] The liquid and gas components in mineral inclusions are the media that are captured and participate in the mineralization process. The study of the hydrogen isotope composition of gaseous hydrocarbons in the inclusions can be widely used in the genesis of natural gas reservoirs, oil and gas source tracing, sedimentary environment, reservoir evolution and the formation stage of oil and gas. In the existing technology, all hydrogen-containing substances in mineral inclusions are generally directly converted into water, which then reacts with metals to generate hydrogen, and finally the hydrogen isotope composition is tested using a double-channel mass spectrometer. Since hydrogen-containing substances can be H2O and gaseous hydrocarbons CH4, C2H6, etc., the hydrogen isotope composition of gaseous hydrocarbons is generally much more negative than that of H2O. For fluid inclusions with H2O content far greater than that of gaseous hydrocarbons, the hydrogen isotope composition is close to that of H2O, which cannot be used as an indicator of oil and gas. Although H2O and gaseous hydrocarbons have undergone isotope exchange, testing the hydrogen isotope composition of gaseous hydrocarbons alone is of great significance for the study of oil and gas reservoirs.

[0003] At present, the hydrogen isotope analysis of mineral inclusions generally uses offline mechanical crushing, grinding, thermal explosion and other methods to extract the inclusion components, and then uses the dual-path test of the isotope mass spectrometer to test the isotope ratio, or uses the online high-temperature cracking method to test. In the process of crushing the sample by the mechanical crushing method, some minerals will not be crushed, and even the crushed minerals still contain a large number of small inclusions, which requires a large amount of sample and is inefficient. The grinding method requires a special ball mill and needs to be connected to a vacuum device. The device is expensive and it is time-consuming and laborious to grind the sample. The traditional vacuum explosion method has a high temperature, and the isotope fractionation may occur between the various components of the inclusions released by the explosion under a vacuum state and between the inclusion components and the main ore. The online high-temperature cracking method directly tests the hydrogen isotope composition of all hydrogen-containing substances. When the hydrogen-containing substance is too little, the mass spectrum peak will be too low to detect its hydrogen isotope composition, and the hydrogen isotope composition of the gaseous hydrocarbons in the inclusions cannot be tested separately, which has little significance for indicating information such as the source of the gaseous hydrocarbons. Summary of the invention

[0004] The purpose of the present invention is to provide a device for the explosion extraction and conversion of gaseous hydrocarbons in mineral inclusions under an online continuous flow state and a method for analyzing the hydrogen isotope composition thereof, so as to solve the problems of low efficiency of offline pre-treatment sample preparation and isotope fractionation, and to improve the accuracy of isotope data and the testing efficiency.

[0005] The technical solution for realizing the purpose of the present invention is as follows: a device for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions, the device comprising a first temperature-controlled heating box, a second temperature-controlled heating box, a first six-way valve installed in the first temperature-controlled heating box, and a second six-way valve installed in the second temperature-controlled heating box; a first helium gas inlet is connected to the first six-way valve via a first water trap and a sampling column head in sequence; a second helium gas inlet is connected to the first six-way valve via a second water trap; a third helium gas inlet is connected to the first six-way valve via a quartz reaction tube and a third water trap in sequence; two ends of the copper oxide reaction tube are respectively connected to the first six-way valve and the second helium gas inlet is connected to the first six-way valve; It is connected to the first six-way valve and the second six-way valve; both ends of the water sample collection tube are connected to the second six-way valve, the water sample collection tube is placed in the freezing cup, and the electric heating device is connected to the water sample collection tube; the fourth helium gas inlet is connected to the second six-way valve via the fourth water trap; the opening of the single-opening quartz tube is connected to the second six-way valve; one end of the high-temperature cracking furnace is connected to the second six-way valve, and the other end of the high-temperature cracking furnace is connected to the gas chromatography column, the gas conversion interface device Conflo, and the stable isotope mass spectrometer in sequence, and the gas conversion interface device Conflo is also connected to the reference gas hydrogen.

[0006] The first helium gas inlet is connected to the second port of the first six-way valve via the first water trap and the injection column head in sequence.

[0007] The second helium gas inlet is communicated with the sixth port of the first six-way valve via the second water trap.

[0008] The third helium gas inlet is connected to the fourth port of the first six-way valve via the quartz reaction tube and the third water trap in sequence.

[0009] The two ends of the copper oxide reaction tube are respectively connected to the third port of the first six-way valve and the sixth port of the second six-way valve.

[0010] The two ends of the water sample collection tube are respectively connected to the second port and the fifth port of the second six-way valve.

[0011] The high temperature cracking furnace is connected to the fourth port of the second six-way valve.

[0012] The opening of the single-opening quartz tube is communicated with the first port of the second six-way valve.

[0013] A first quick connector is provided between the third helium gas inlet and the quartz reaction tube, and a second quick connector is provided between the quartz reaction tube and the third water trap.

[0014] The quartz reaction tube is nested in the first temperature-controlled heating furnace.

[0015] The copper oxide reaction tube is placed in a second temperature-controlled heating furnace.

[0016] A method for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions, the method specifically comprising the following steps:

[0017] Step 1: Load the mineral sample, heat it, introduce helium, purge it, and then exhaust it into the air;

[0018] Step 2, heating the mineral sample in the above step 1 to remove secondary inclusions and surface adsorbed gases;

[0019] Step 3: Explosion of mineral sample inclusions and oxidation and collection of gaseous hydrocarbons;

[0020] Step 4, water sample injection and hydrogen isotope composition test;

[0021] Step 5: Testing of hydrogen isotope composition of gaseous hydrocarbons.

[0022] The specific steps of step 1 are as follows:

[0023] Step 1.1, placing the mineral sample into a quartz reaction tube, and placing the quartz reaction tube into a first temperature-controlled heating furnace for heating;

[0024] Step 1.2, introducing helium into all helium inlets;

[0025] Step 1.3, adjusting the first six-way valve to the purge mode of the mineral sample;

[0026] Step 1.4, the helium from the third helium inlet passes through the quartz reaction tube, takes out the air therein, enters the fourth port of the first six-way valve, and is discharged into the air from the fifth port of the first six-way valve.

[0027] The specific steps of step 1.1 are as follows: after the quartz mineral sample or other mineral sample is loaded into the quartz reaction tube, the first quick connector and the second quick connector are connected to the quartz reaction tube, and the quartz reaction tube is placed in the groove of the first temperature-controlled heating furnace and ensures that the sample section is in the middle.

[0028] In the step 1.2, helium is introduced into the first helium inlet, the second helium inlet, the third helium inlet and the fourth helium inlet.

[0029] In the step 1.3, the helium flow of each port of the first six-way valve in the purge mode is as follows: the second port of the first six-way valve takes in air and then out of the third port, the fourth port takes in air and then out of the fifth port, and the sixth port takes in air and then out of the first port.

[0030] The specific steps of step 2 are as follows:

[0031] Step 2.1, heating the mineral sample, and releasing the low-temperature secondary inclusions of the mineral sample and the gas adsorbed on the surface after heating, and then being carried out by the helium gas to the third water trap;

[0032] Step 2.2: After the low-temperature secondary inclusions and the water adsorbed on the surface of the mineral sample in the above step 2.2 are absorbed, other gases enter the first six-way valve and are discharged into the air.

[0033] The specific steps of step 3 are as follows:

[0034] Step 3.1, place the water sample collection tube into a freezing cup, set the first temperature-controlled heating furnace to 11 and the second temperature-controlled heating furnace to the same temperature;

[0035] Step 3.2, adjusting the first six-way valve to the burst collection mode of mineral samples and the second six-way valve to the water sample collection mode;

[0036] Step 3.3, the mineral sample in the quartz reaction tube is heated and exploded, and the released gaseous hydrocarbons react chemically with copper oxide at high temperature to generate a mixed gas, and the mixed gas is heated to ensure that H2O is always in a gaseous state;

[0037] Step 3.4: The mixed gas enters the water sample collection tube through the second six-way valve, H2O is frozen and collected, and other gases are discharged into the air.

[0038] In the burst collection mode in step 3.2, the helium flow directions of each port of the first six-way valve are as follows: the second port takes in air and then exits from the first port; the fourth port takes in air and then exits from the third port; the sixth port takes in air and then exits from the fifth port.

[0039] In the water sample collection mode in step 3.2, the helium flow directions of the ports of the second six-way valve are as follows: the second port takes in air and then out of the first port; the third port takes in air and then out of the fourth port; the sixth port takes in air and then out of the fifth port.

[0040] A method for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions, characterized in that the specific steps of step 4 are as follows:

[0041] Step 4.1, adjust the second six-way valve to the water sample injection mode;

[0042] Step 4.2, the helium from the fourth helium inlet is dried by the fourth water trap and then enters the second six-way valve and the water sample collection tube in sequence;

[0043] Step 4.3, while removing the freezing cup, the water sample collection tube is heated and the solid water is vaporized and enters the second six-way valve and the high-temperature cracking furnace in sequence;

[0044] Step 4.4, H2O reacts to generate H2 and CO, which enter the gas chromatography column, the gas conversion interface device Conflo, and the stable isotope mass spectrometer in sequence.

[0045] The specific steps of step 5 are as follows:

[0046] Step 5.1, select water or methane gas as the standard substance, and adjust the first six-way valve to the standard collection mode;

[0047] Step 5.2, the standard water sample is heated and vaporized and enters the first six-way valve, and the vaporized water is collected and the gaseous hydrocarbon hydrogen isotope test is performed according to the above steps 3 to 5;

[0048] Step 5.3: The standard methane gas enters the first six-way valve, and after oxidation reaction with the copper oxide reaction tube, is collected and sampled for testing and the above steps 3 to 5 are performed.

[0049] In the standard collection mode in step 5.1, the helium flow directions of the ports of the first six-way valve are as follows: the second port takes in air and the third port takes out air; the fourth port takes in air and the fifth port takes out air; the sixth port takes in air and the first port takes out air.

[0050] The beneficial technical effects of the present invention are:

[0051] (1) The present invention uses helium as the protective carrier gas of the online continuous flow system. Each helium gas channel uses a water trap filled with magnesium perchlorate to absorb and dry the trace water that may exist in the helium gas, thereby avoiding the influence of the trace water in the carrier gas on the test results of the hydrogen isotope composition of gaseous hydrocarbons.

[0052] (2) The present invention adopts an online continuous flow method to connect the mineral inclusion explosion device, methane oxidation, and product water collection device with the stable isotope mass spectrometer, so as to realize the online heating explosion of the mineral in a helium flow environment, the online oxidation of methane, the online collection of the oxidation product water, and the electric heating and release of water into the stable isotope mass spectrometer for testing. Compared with the traditional offline method, the sample amount is reduced from 10-20g to 1-2g of the system, and the sample amount is greatly reduced, thereby effectively reducing the workload of mineral processing and the scientific research cost, and improving the scientific research efficiency.

[0053] (3) The present invention adopts a straight-through quartz tube as a reaction tube for mineral explosion. Both ends of the quartz tube are connected to the online system using quick connectors, which is convenient for disassembly, rapid sample loading and sample replacement. Through the design of a six-way valve, the air in the reaction tube can be purged with high-purity helium for 10 minutes, and then the sample is exploded at 200°C for 10 minutes to remove the gas, moisture and low-temperature secondary inclusions adsorbed on the surface of the sample. Different explosion temperatures are set for different minerals and different research needs. The exploded water and gas are quickly taken away from the high-temperature zone by the helium. After the inclusions are released, they can be quickly transferred away under the protection of the helium, thereby reducing the occurrence of isotope exchange. The water trap filled with magnesium perchlorate absorbs water.

[0054] (4) The present invention uses gaseous hydrocarbons and other gases to pass through a reactor filled with copper oxide. The gaseous hydrocarbons react with copper oxide at 800°C to generate CO2 and H2O. The H2O is frozen and collected by alcohol dry ice at -80°C for hydrogen isotope composition analysis. The CO2 and other gases are discharged into the air. This method can meet the hydrogen isotope analysis of gaseous hydrocarbons only, which is conducive to obtaining more effective scientific research data.

[0055] (5) The present invention adopts a method of instantaneously connecting the current to quickly heat the water sample collection tube, thereby achieving the instantaneous vaporization requirement of solid water. Driven by helium, the water vapor enters a high-temperature cracking furnace at 1380°C and reacts with glassy carbon to generate H2 and CO, which are separated by a chromatographic column and then enter a mass spectrometer to test the hydrogen isotope composition.

[0056] (6) The present invention uses a temperature-controlled heating box to heat the six-way valve, heating belt and related pipelines to above 150° C., ensuring that the pipelines through which H2O passes are in a gas state, thereby preventing the pipeline from adsorbing H2O and causing isotope fractionation.

[0057] (7) The present invention adopts a double six-way valve design, which facilitates the switching between the oxidation enrichment of gaseous hydrocarbons in mineral inclusions and the standard injection enrichment. The collection, vaporization, high-temperature decomposition reaction, and chromatographic separation injection paths of samples and standards are consistent, solving the problem of online accurate determination of hydrogen isotopes in gaseous hydrocarbons. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] Figure 1 This is a schematic structural diagram of a device for extracting gaseous hydrocarbons from mineral inclusions provided by the present invention.

[0059] In the figure: 1 is the first helium inlet, 2 is the first water trap, 3 is the injection column head, and 4 is the first temperature-controlled heating box;

[0060] 5 is a first six-way valve, wherein 5-1 is a first port of the first six-way valve, 5-2 is a second port of the first six-way valve, 5-3 is a third port of the first six-way valve, 5-4 is a fourth port of the first six-way valve, 5-5 is a fifth port of the first six-way valve, and 5-6 is a sixth port of the first six-way valve;

[0061] 6 is a second helium inlet, 7 is a second water trap, 8 is a third helium inlet, 9 is a first quick connector, 10 is a quartz reaction tube, 11 is a first temperature-controlled heating furnace, 12 is a second quick connector, 13 is a third water trap, 14 is a copper oxide reaction tube, and 15 is a second temperature-controlled heating furnace;

[0062] 16 is a second six-way valve, wherein 16-1 is a first port of the six-way valve, 16-2 is a second port of the six-way valve, 16-3 is a third port of the six-way valve, 16-4 is a fourth port of the six-way valve, 16-5 is a fifth port of the six-way valve, and 16-6 is a sixth port of the six-way valve;

[0063] 17 is a second temperature-controlled heating box, 18 is a single-opening quartz tube, 19 is a fourth water trap, 20 is a fourth helium inlet, 21 is a water sample collection tube, 22 is a freezing cup, 23 is an electric heating device, 24 is a high-temperature cracking furnace, 25 is a gas chromatography column, 26 is a reference gas hydrogen, 27 is a gas conversion interface device Conflo, and 28 is a stable isotope mass spectrometer. DETAILED DESCRIPTION

[0064] The present invention is further described in detail below with reference to the accompanying drawings and embodiments.

[0065] like Figure 1 As shown, an online continuous flow analysis and extraction device for gaseous hydrocarbon hydrogen isotope composition in mineral inclusions of this embodiment comprises a first helium inlet 1, a second helium inlet 6, a third helium inlet 8, a fourth helium inlet 20, a first water trap 2, a second water trap 7, a third water trap 13, a fourth water trap 19, a sampling column head 3, a first temperature-controlled heating box 4, a second temperature-controlled heating box 17, a first six-way valve 5, a second six-way valve 16, a first quick connector 9, a second quick connector 12, a quartz reaction tube 10, a first temperature-controlled heating furnace 11, a second temperature-controlled heating furnace 15, a copper oxide reaction tube 14, a single-opening quartz tube 18, a water sample collection tube 21, a freezing cup 22, an electric heating device 23, a high-temperature cracking furnace 24, a gas chromatography column 25, a reference gas hydrogen 26, a gas conversion interface device Conflo 27 and a stable isotope mass spectrometer 28. Figure 1 As shown, the first helium gas inlet 1 is connected to the second port 5-2 of the first six-way valve 5 through the first water trap 2 and the injection column head 3 in sequence; the first helium gas inlet 1 is connected to the inlet of the first water trap 2 through a pipeline, the outlet of the first water trap 2 is connected to the inlet of the injection column head 3 through a pipeline, and the outlet of the injection column head 3 is connected to the second port 5-2 of the first six-way valve 5 through a pipeline.

[0066] The second helium inlet 6 is connected to the sixth port 5-6 of the first six-way valve 5 through the second water trap 7; the second helium inlet 6 is connected to the inlet of the second water trap 7 through a pipeline, and the outlet of the second water trap 7 is connected to the sixth port 5-6 of the first six-way valve through a pipeline.

[0067] The third helium gas inlet 8 is connected to the fourth port 5-4 of the first six-way valve 5 via the first quick connector 9, the quartz reaction tube 10, the second quick connector 12 and the third water trap 13 in sequence; the third helium gas inlet 8 is connected to one end of the first quick connector 9 through a pipeline, the other end of the first quick connector 9 is connected to the inlet of the quartz reaction tube 10 through a pipeline, the outlet of the quartz reaction tube 10 is connected to one end of the second quick connector 12 through a pipeline, the other end of the second quick connector 12 is connected to the inlet of the third water trap 13 through a pipeline, and the outlet of the third water trap 13 is connected to the fourth port 5-4 of the first six-way valve 5 through a pipeline.

[0068] The two ends of the copper oxide reaction tube 14 are respectively connected to the third port 5-3 of the first six-way valve 5 and the sixth port 16-6 of the second six-way valve 16; one end of the copper oxide reaction tube 14 is connected to the third port 5-3 of the first six-way valve 5 through a pipeline, and the other end of the copper oxide reaction tube 14 is connected to the sixth port 16-6 of the second six-way valve through a pipeline.

[0069] The two ends of the water sample collection tube 21 are respectively connected to the second port 16-2 and the fifth port 16-5 of the second six-way valve 16; one end of the water sample collection tube 21 is connected to the second port 16-2 of the second six-way valve 16 through a pipeline, and the other end of the water sample collection tube 21 is connected to the fifth port 16-5 of the second six-way valve 16 through a pipeline.

[0070] The fourth helium gas inlet 20 is connected to the third port 16-3 of the second six-way valve 16 via the fourth water well 19; the fourth helium gas inlet 20 is connected to the inlet of the fourth water well 19 through a pipeline, and the outlet of the fourth water well 19 is connected to the third port 16-3 of the second six-way valve 16 through a pipeline.

[0071] The fourth port 16-4 of the second six-way valve 16 is connected to the inlet of the high-temperature cracking furnace 24 through a pipeline, the outlet of the high-temperature cracking furnace 24 is connected to the inlet of the gas chromatographic column 25 through a pipeline, the outlet of the gas chromatographic column 25 and the outlet of the reference gas hydrogen 26 are respectively connected to the inlet of the gas conversion interface device Conflo 27 through pipelines, and the outlet of the gas conversion interface device Conflo 27 is connected to the inlet of the stable isotope mass spectrometer 28 through a pipeline. Helium comes out of the fourth port 16-4 of the second six-way valve 16 and passes through the high-temperature cracking furnace 24, the gas chromatographic column 25, and the gas conversion interface device Conflo 27 to reach the stable isotope mass spectrometer 28.

[0072] The quartz reaction tube 10 is nested in the groove of the first temperature-controlled heating furnace 11; the copper oxide reaction tube 14 is placed in the groove of the second temperature-controlled heating furnace 15. The opening of the single-opening quartz tube 18 is downward and the pipeline is placed at its bottom. The opening of the single-opening quartz tube 18 is connected to the first port 16-1 of the second six-way valve 16 through the pipeline. The water sample collection tube 21 is placed in the freezing cup 22; the two ends of the electric heating device 23 are connected to the two ends of the water sample collection tube 21 respectively.

[0073] In this embodiment, the connecting pipelines between the components are stainless steel pipes with an outer diameter of 1 / 16 inch.

[0074] In this embodiment, the purity of helium in the first helium inlet 1, the second helium inlet 6, the third helium inlet 8 and the fourth helium inlet 20 is 99.999%.

[0075] In this embodiment, the desiccant used in the first water trap 2, the second water trap 7, the third water trap 13 and the fourth water trap 19 is magnesium perchlorate.

[0076] In this embodiment, the injection column head 3 is provided with a polytetrafluoroethylene sealing gasket, and can be used for online injection of liquid water and gaseous methane.

[0077] In this embodiment, the first six-way valve 5 is placed in the first temperature-controlled heating box 4, and the second six-way valve 16 is placed in the second temperature-controlled heating box 17. The first six-way valve 5 and the second six-way valve 16 are heated to above 150°C by the first temperature-controlled heating box 4 and the second temperature-controlled heating box 17 respectively. The pipes through which standard water and water generated by oxidation of gaseous hydrocarbons pass are wrapped with heating belts and heated to above 150°C to ensure that water passes in a gaseous state to avoid water adsorption and isotope fractionation.

[0078] In this embodiment, the first quick connector 9 and the second quick connector 12 facilitate the loading and unloading of the quartz reaction tube 10 and the loading of samples.

[0079] In this embodiment, the maximum temperature of the first temperature-controlled heating furnace 11 and the second temperature-controlled heating furnace 15 can both reach 1100°C.

[0080] In this embodiment, the copper oxide reaction tube 14 is used to oxidize gaseous hydrocarbons to generate CO2 and H2O.

[0081] In this embodiment, the electric heating device 23 can heat the water sample collection tube from -80°C to above 200°C in about 5 seconds.

[0082] In this embodiment, the reaction tube of the high temperature cracking furnace 24 is filled with glassy carbon particles, which can decompose and reduce H2O into H2 and CO at 1380°C.

[0083] like Figure 1As shown, a method for online continuous flow explosion extraction and hydrogen isotope composition analysis of gaseous hydrocarbons in mineral inclusions, the method specifically comprises the following steps:

[0084] Step 1: Load the mineral sample, heat it, introduce helium, purge it, and then exhaust it into the air

[0085] Step 1.1: Place the mineral sample into the quartz reaction tube 10, and place the quartz reaction tube 10 into the first temperature-controlled heating furnace 11 for heating.

[0086] After 1-2g of 40-60 mesh quartz mineral sample or other mineral sample is loaded into the quartz reaction tube 10, the first quick connector 9 and the second quick connector 12 are connected to the quartz reaction tube 10, the upper cover of the first temperature-controlled heating furnace 11 is opened, and the quartz reaction tube 10 is placed in the groove of the first temperature-controlled heating furnace 11 and ensure that the sample section is in the middle, so that the heat can be evenly applied and the sample is heated in the high temperature area.

[0087] Step 1.2: Introduce helium into all helium inlets

[0088] Helium is introduced into the first helium inlet 1 , the second helium inlet 6 , the third helium inlet 8 and the fourth helium inlet 20 .

[0089] Step 1.3: Adjust the first six-way valve 5 to the purge mode for the mineral sample

[0090] The first six-way valve 5 is adjusted to the purging mode for mineral samples. In the purging mode, the helium flow directions of the ports of the first six-way valve 5 are as follows: the second port 5-2 of the first six-way valve 5 takes in air and then discharges air from the third port 5-3, the fourth port 5-4 takes in air and then discharges air from the fifth port 5-5, and the sixth port 5-6 takes in air and then discharges air from the first port 5-1.

[0091] Step 1.4, the helium from the third helium inlet 8 passes through the quartz reaction tube 10 and takes out the air therein, enters the fourth port 5-4 of the first six-way valve 5, and is discharged into the air from the fifth port 5-5 of the first six-way valve 5.

[0092] The helium from the third helium inlet 8 enters the quartz reaction tube 10 through the first quick connector 9 to take out the air therein, passes through the second quick connector 12 and the third water trap 13, enters the fourth port 5-4 of the first six-way valve 5, and is discharged into the air from the fifth port 5-5 of the first six-way valve 5. The exhaust time is 10 minutes.

[0093] Step 2: Heat the mineral sample in step 1 to remove secondary inclusions and surface adsorbed gases.

[0094] Step 2.1, heating the mineral sample, and releasing the low-temperature secondary inclusions of the mineral sample and the gas adsorbed on the surface after heating, and then being carried out by the helium gas to reach the third water trap 13.

[0095] The temperature of the first temperature-controlled heating furnace 11 is set to 200° C. After the low-temperature secondary inclusions of the mineral sample and the gases adsorbed on the surface, especially water, are released by heating, they are carried out of the quartz reaction tube 10 by helium and reach the third water trap 13 through the second quick connector 12 .

[0096] Step 2.2: After the low-temperature secondary inclusions of the mineral sample and the water adsorbed on the surface in the above step 2.2 are absorbed, the other gases enter the first six-way valve 5 and are discharged into the air.

[0097] After the water is absorbed, other gases enter the fourth port 5-4 of the first six-way valve 5 and are discharged into the air from the fifth port 5-5 of the first six-way valve 5. The exhaust lasts for 10 minutes.

[0098] Step 3: Mineral sample inclusion explosion and gaseous hydrocarbon oxidation collection

[0099] Step 3.1: Place the water sample collection tube 21 into the freezing cup 22, and set the first temperature-controlled heating furnace 11 and the second temperature-controlled heating furnace 15 to the same temperature.

[0100] Place the water sample collection tube 21 into the freezing cup 22 and add alcohol dry ice, set the temperature of the first temperature-controlled heating furnace 11 to 550°C and the temperature of the second temperature-controlled heating furnace 15 to 800°C,

[0101] Step 3.2: Adjust the first six-way valve 5 to the burst collection mode for mineral samples and the second six-way valve 16 to the water sample collection mode.

[0102] The first six-way valve 5 is adjusted to the burst collection mode of the mineral sample. In the burst collection mode, the helium flow directions of the ports of the first six-way valve 5 are as follows: the second port 5-2 takes in air and then outgases from the first port 5-1; the fourth port 5-4 takes in air and then outgases from the third port 5-3; the sixth port 5-6 takes in air and then outgases from the fifth port 5-5.

[0103] The second six-way valve 16 is adjusted to the water sample collection mode. In the water sample collection mode, the helium flow directions of the ports of the second six-way valve 16 are as follows: the second port 16-2 takes in air and then outgases from the first port 16-1; the third port 16-3 takes in air and then outgases from the fourth port 16-4; the sixth port 16-6 takes in air and then outgases from the fifth port 16-5.

[0104] Step 3.3: The mineral sample in the quartz reaction tube 10 is heated and exploded, and the released gaseous hydrocarbons react with copper oxide at high temperature to generate a mixed gas, and the mixed gas is heated to ensure that the H2O is always in a gaseous state.

[0105] The mineral sample in the quartz reaction tube 10 is heated and exploded, and water, gaseous hydrocarbons and other gases are released and quickly taken away from the high temperature zone by high-purity helium. After entering the third water trap 13, the water is removed, and the gaseous hydrocarbons and other gases enter the fourth port 5-4 of the first six-way valve 5, and enter the copper oxide reaction tube 14 after coming out from the third port 5-3 of the first six-way valve 5. The gaseous hydrocarbons and copper oxide react chemically at a high temperature of 800°C to generate a mixed gas of CO2 and H2O. The pipe through which the mixed gas of CO2 and H2O passes is heated to above 150°C to ensure that H2O is always in a gaseous state to avoid fractionation.

[0106] Step 3.4: The mixed gas enters the water sample collection tube through the second six-way valve 16, the H2O is frozen and collected, and the other gases are discharged into the air.

[0107] The mixed gas of CO2 and H2O enters the sixth port 16-6 of the second six-way valve 16, and comes out from the fifth port 16-5 of the second six-way valve 16 and enters the -80°C water sample collection tube 21, where the H2O is frozen and collected, and other gases enter the second port 16-2 of the second six-way valve 16 and are discharged into the air from the first port 16-1 of the second six-way valve 16. This collection process takes 10 minutes.

[0108] Step 4: Water sample injection and hydrogen isotope composition test

[0109] Step 4.1: Adjust the second six-way valve 16 to the water sample injection mode

[0110] The second six-way valve 16 is adjusted to the water sample injection mode. In the water sample injection mode, the helium flow of the second six-way valve 16 is as follows: the third port 16-3 takes in air and then exhausts it from the second port 16-2; the fifth port 16-5 takes in air and then exhausts it from the fourth port 16-4; the sixth port 16-6 takes in air and then exhausts it from the first port 16-1.

[0111] Step 4.2: After the helium from the fourth helium inlet 20 is dried by the fourth water trap 19, it enters the second six-way valve 16 and the water sample collection tube 21 in sequence.

[0112] The helium from the fourth helium inlet 20 is dried by the fourth water trap 19 , enters the third port 16 - 3 of the second six-way valve 16 through a 1 / 16-inch stainless steel pipe, comes out from the fourth port 16 - 4 of the second six-way valve 16 , and enters the water sample collection tube 21 .

[0113] Step 4.3: While removing the freezing cup 22, heat the water sample collection tube 21, and the solid water vaporizes and enters the second six-way valve 16 and the high-temperature cracking furnace 24 in sequence.

[0114] When the freezing cup 22 outside the water sample collection tube 21 is removed, the electric heating device 23 is turned on. The temperature of the water sample collection tube 21 rises from -80°C to about 200°C in about 5 seconds. After the solid water is vaporized, it enters the fifth port 16-5 of the second six-way valve 16 driven by helium, and then comes out from the fourth port 16-4 of the second six-way valve 16 and enters the high-temperature cracking furnace 24 at 1380°C.

[0115] Step 4.4, H2O reacts to generate H2 and CO, which enter the gas chromatography column 25, the gas conversion interface device Conflo 27, and the stable isotope mass spectrometer 28 in sequence.

[0116] H2O reacts with glassy carbon to generate H2 and CO, which enter the gas chromatography column 25 for separation and then enter the gas conversion interface device Conflo 27, and then enter the stable isotope mass spectrometer 28 through the quartz capillary. The reference gas H2 enters the stable isotope mass spectrometer 28 from the quartz capillary through the gas conversion interface device Conflo 27 to compare and test the hydrogen isotope composition.

[0117] Step 5: Gaseous hydrocarbon hydrogen isotope composition test

[0118] Step 5.1: Select water or methane gas as the standard substance and adjust the first six-way valve 5 to the standard collection mode.

[0119] The main function of the present invention is to test the hydrogen isotope composition of gaseous hydrocarbons. The standard material can use water or pure methane gas. The injection column head 3 can meet the injection of water or methane. The first six-way valve is adjusted to the standard collection mode. In the standard collection mode, the helium flow directions of each port of the first six-way valve 5 are as follows: the second port 5-2 takes in air and then exhausts from the third port 5-3; the fourth port 5-4 takes in air and then exhausts from the fifth port 5-5; the sixth port 5-6 takes in air and then exhausts from the first port 5-1.

[0120] Step 5.2: After the standard water sample is heated and vaporized, it enters the first six-way valve 5, and the vaporized water is collected and the gaseous hydrocarbon hydrogen isotope test is performed according to the above steps 3 to 5.1.

[0121] 0.2 μL of standard water sample is injected through a micro-syringe, the temperature in the pipeline is above 150°C, the water vaporizes and enters the second port 5-2 of the first six-way valve 5, and after coming out of the third port 5-3 of the first six-way valve 5, the vaporized water is collected and the gaseous hydrocarbon hydrogen isotope test is performed according to the above steps 3 to 5.

[0122] Step 5.3: The standard methane gas enters the first six-way valve 5, and after oxidation reaction with the copper oxide reaction tube 14, is collected and sampled for testing to perform the above steps 3 to 5.1.

[0123] 5 mL of standard methane gas is injected through the gas injection needle and enters the second port 5-2 of the first six-way valve 5. After coming out from the third port 5-3 of the first six-way valve 5 and undergoing oxidation reaction in the copper oxide reaction tube 14, the methane gas of the oxidation reaction is collected and the gaseous hydrocarbon hydrogen isotope test is performed according to the above steps 3 to 5.

[0124] The present invention is described in detail above with reference to the accompanying drawings and embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of ordinary technicians in the field without departing from the purpose of the present invention. The contents not described in detail in the present invention can adopt the existing technology.

Claims

1. A device for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions, characterized in that: The device comprises a first temperature-controlled heating box (4), a second temperature-controlled heating box (17), a first six-way valve (5) installed in the first temperature-controlled heating box (4), and a second six-way valve (16) installed in the second temperature-controlled heating box (17); a first helium gas inlet (1) is connected to the first six-way valve (5) via a first water trap (2) and an injection column head (3) in sequence; the first helium gas inlet (1) is connected to the second port (5-2) of the first six-way valve (5) via the first water trap (2) and the injection column head (3); the second helium gas inlet (6) is connected to the first six-way valve (5) via the second water trap (7); the third helium gas inlet (8) is connected to the first six-way valve (5) via a quartz reaction tube (10) and a third water trap (13) in sequence; the second helium gas inlet (6) is connected to the sixth port (5-6) of the first six-way valve (5) via the second water trap (7); The third helium gas inlet (8) is connected to the fourth port (5-4) of the first six-way valve (5) via the quartz reaction tube (10) and the third water trap (13) in sequence; the two ends of the copper oxide reaction tube (14) are connected to the first six-way valve (5) and the second six-way valve (16) respectively; the two ends of the water sample collection tube (21) are connected to the second six-way valve (16), the water sample collection tube (21) is placed in the freezing cup (22), and the electric heating device (23) is connected to the water sample collection tube (21); the fourth helium gas inlet (20) is connected to the second six-way valve (16) via the fourth water trap (19); the opening of the single-opening quartz tube (18) is connected to the second six-way valve (16); one end of the high-temperature cracking furnace (24) is connected to the second six-way valve (16), and the other end of the high-temperature cracking furnace (24) is connected to the gas chromatography column (25), the gas conversion interface device Conglomerate (26) in sequence. (27) and a stable isotope mass spectrometer (28), and the gas conversion interface device Conflo (27) is also connected to the reference gas hydrogen (26); the desiccant used in the first water trap (2), the second water trap (7), the third water trap (13) and the fourth water trap (19) is magnesium perchlorate.

2. The device for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 1, characterized in that: The two ends of the copper oxide reaction tube (14) are respectively connected to the third port (5-3) of the first six-way valve (5) and the sixth port (16-6) of the second six-way valve (16).

3. The device for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 2, characterized in that: The two ends of the water sample collection tube (21) are respectively connected to the second port (16-2) and the fifth port (16-5) of the second six-way valve (16).

4. The device for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 3, characterized in that: The high-temperature cracking furnace (24) is in communication with the fourth port (16-4) of the second six-way valve (16).

5. The device for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 4, characterized in that: The opening of the single-opening quartz tube (18) is in communication with the first port (16-1) of the second six-way valve (16).

6. The device for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 5, characterized in that: A first quick connector (9) is provided between the third helium gas inlet (8) and the quartz reaction tube (10), and a second quick connector (12) is provided between the quartz reaction tube (10) and the third water trap (13).

7. The device for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 6, characterized in that: The quartz reaction tube (10) is nested in the first temperature-controlled heating furnace (11).

8. The device for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 7, characterized in that: The copper oxide reaction tube (14) is placed in a second temperature-controlled heating furnace (15).

9. A method for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions using the device for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to any one of claims 1 to 8, characterized in that: The method specifically comprises the following steps: Step 1: Load the mineral sample, heat it, introduce helium, purge it, and then discharge it into the air; the specific steps of step 1 are as follows: Step 1.1, placing a mineral sample into a quartz reaction tube (10), and placing the quartz reaction tube (10) into a first temperature-controlled heating furnace (11) for heating; Step 1.2, introducing helium into all helium inlets; Step 1.3, adjusting the first six-way valve (5) to a purge mode for the mineral sample; Step 1.4, the helium gas from the third helium gas inlet (8) passes through the quartz reaction tube (10), takes out the air therein, enters the fourth port (5-4) of the first six-way valve (5), and is discharged into the air from the fifth port (5-5) of the first six-way valve (5); Step 2: heating the mineral sample in step 1 to remove secondary inclusions and surface adsorbed gases; the specific steps of step 2 are as follows: Step 2.1, heating the mineral sample, and releasing the low-temperature secondary inclusions of the mineral sample and the gas adsorbed on the surface after heating, and then being carried out by the helium gas to the third water trap (13); Step 2.2: After the low-temperature secondary inclusions and the water adsorbed on the surface of the mineral sample in the above step 2.2 are absorbed, other gases enter the first six-way valve (5) and are discharged into the air; Step 3, mineral sample inclusion explosion and gaseous hydrocarbon oxidation collection; the specific steps of step 3 are as follows: Step 3.1, placing the water sample collection tube (21) into the freezing cup (22), and setting the temperature of the first temperature-controlled heating furnace 11 and the second temperature-controlled heating furnace (15) to the same temperature; Step 3.2, adjusting the first six-way valve (5) to the burst collection mode for mineral samples and the second six-way valve (16) to the water sample collection mode; Step 3.3, the mineral sample in the quartz reaction tube (10) is heated and exploded, and the released gaseous hydrocarbons react chemically with copper oxide at high temperature to generate a mixed gas, and the mixed gas is heated to ensure that the H2O is always in a gaseous state; Step 3.4, the mixed gas enters the water sample collection tube through the second six-way valve (16), the H2O is frozen and collected, and the other gases are discharged into the air; Step 4: water sample injection and hydrogen isotope composition test; the specific steps of step 4 are as follows: Step 4.1, adjusting the second six-way valve (16) to the water sample injection mode; Step 4.2, the helium gas from the fourth helium gas inlet (20) is dried by the fourth water trap (19) and then enters the second six-way valve (16) and the water sample collection tube (21) in sequence; Step 4.3, while removing the freezing cup (22), the water sample collection tube (21) is heated and the solid water is vaporized and enters the second six-way valve (16) and the high-temperature cracking furnace (24) in sequence; Step 4.4, H2O reacts to generate H2 and CO, which enter the gas chromatography column (25), the gas conversion interface device Conflo (27), and the stable isotope mass spectrometer (28) in sequence; Step 5, gaseous hydrocarbon hydrogen isotope composition test; the specific steps of step 5 are as follows: Step 5.1, select water or methane gas as the standard substance, and adjust the first six-way valve (5) to the standard collection mode; Step 5.2, the standard water sample is heated and vaporized and then enters the first six-way valve (5), and the vaporized water is collected and the gaseous hydrocarbon hydrogen isotope test is performed according to the above steps 3 to 5; Step 5.3: The standard methane gas enters the first six-way valve (5), undergoes oxidation reaction with the copper oxide reaction tube (14), and is then collected and sampled for testing to perform the above steps 3 to 5.

10. The method for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 9, characterized in that: The specific steps of step 1.1 are as follows: after the quartz mineral sample or other mineral sample is loaded into the quartz reaction tube (10), the first quick connector (9) and the second quick connector (12) are connected to the quartz reaction tube (10), and the quartz reaction tube (10) is placed in the groove of the first temperature-controlled heating furnace (11) and ensures that the sample section is in the middle.

11. The method for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 10, characterized in that: In the step 1.2, helium is introduced into the first helium inlet (1), the second helium inlet (6), the third helium inlet (8) and the fourth helium inlet (20).

12. The method for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 11, characterized in that: In the step 1.3, the helium flow directions of the ports of the first six-way valve (5) in the purge mode are as follows: the second port (5-2) of the first six-way valve (5) takes in air and then outtakes air from the third port (5-3), the fourth port (5-4) takes in air and then outtakes air from the fifth port (5-5), and the sixth port (5-6) takes in air and then outtakes air from the first port (5-1).

13. The method for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 12, characterized in that: In the burst collection mode in step 3.2, the helium flow directions of the various ports of the first six-way valve (5) are as follows: the second port (5-2) takes in air and then exits from the first port (5-1); the fourth port (5-4) takes in air and then exits from the third port (5-3); the sixth port (5-6) takes in air and then exits from the fifth port (5-5).

14. The method for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 13, characterized in that: In the water sample collection mode in step 3.2, the helium flow directions of the various ports of the second six-way valve (16) are as follows: the second port (16-2) takes in air and then exits the first port (16-1); the third port (16-3) takes in air and then exits the fourth port (16-4); the sixth port (16-6) takes in air and then exits the fifth port (16-5).

15. The method for extracting hydrogen isotope composition of gaseous hydrocarbons in mineral inclusions according to claim 14, characterized in that: In the standard collection mode in step 5.1, the helium flow directions of the ports of the first six-way valve (5) are as follows: the second port (5-2) takes in air and then exits the third port (5-3); the fourth port (5-4) takes in air and then exits the fifth port (5-5); the sixth port (5-6) takes in air and then exits the first port (5-1).

Images