Purifying and enriching device, measuring device, gas collecting method and gas measuring method

Abstract

The invention relates to a purification and enrichment device, a measurement device, a gas collection method and a measurement method, and belongs to the technical field of carbonate rock analysis. The purification and enrichment device comprises a reaction container used for containing a carbonate sample to be detected, reaction acid liquor is contained in the reaction container, the separation system comprises a first pipe column and a refrigerating instrument, the first pipe column comprises at least four separation pipe sections connected end to end, a vacuum valve is arranged between any two adjacent separation pipe sections, and the refrigerating instrument is connected with the first pipe column. Each separation pipe section is also connected with a heating temperature control device; one end of the first tubular column is communicated with the reaction container, the other end of the first tubular column is communicated with a collecting container, and the first tubular column is further communicated with vacuumizing equipment. Air in the device can be exhausted before gas production, the temperature of the separation pipe section can be flexibly controlled, impurities in carbon dioxide gas can be conveniently separated, the temperature difference of front heat and rear cold can be conveniently formed, the gas is enriched on the rear side of the pipeline, and purification and enrichment of carbon dioxide are achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of carbonate rock analysis, and in particular to a purification and enrichment device, a measuring device, a gas collection method and a measuring method. Background Art

[0002] Mass spectrometry analysis of carbon, oxygen isotopes, and their cluster isotopes using carbonate rocks can reflect important parameters such as the evolution of the carbon cycle, paleotemperature, the metabolic processes of marine organisms, and the rock-forming and mineralization processes during geological history. It is one of the hot subjects in the field of geochemistry. At the same time, in the field of petroleum geology, these isotope characteristics are closely related to reservoir formation and fluid properties.

[0003] Currently, carbon and oxygen isotope mass spectrometry analysis of hydrochloric acid rocks relies on online phosphoric acidization, carbon dioxide gas preparation, and a capillary inlet system. Specifically, during the pretreatment phase, helium is used as a purge gas to remove contaminants from the system. Then, carbon dioxide gas is prepared through online phosphoric acidization and, using helium as the carrier gas, introduced through a capillary inlet system into an isotope mass spectrometer for isotope measurement.

[0004] However, current pretreatment technologies often direct the gas produced by carbonate acidification into a mass spectrometer. However, the acidification process inevitably contaminates the gas with water, air, and other pollutants. These pollutants interfere with the accuracy of mass spectrometry analysis, making existing pretreatment methods inadequate for carbonate cluster isotope analysis. Summary of the Invention

[0005] The present invention provides a purification and enrichment device, a measuring device, a gas collection method and a measuring method, which are used to reduce the interference of pollutants on mass spectrometry analysis and improve the accuracy of carbonate rock cluster isotope testing and analysis.

[0006] In a first aspect, the present invention provides a purification and enrichment device for reacting a carbonate sample to be tested to generate gas, and purifying and enriching carbon dioxide in the generated gas, comprising:

[0007] A gas production system comprising a reaction container for accommodating a carbonate sample to be tested, wherein the reaction container further contains a reaction acid liquid, wherein the reaction acid liquid is used to react with the carbonate sample to be tested to generate a mixed gas containing carbon dioxide;

[0008] A separation system comprising a first tubular column and a refrigerator, wherein the first tubular column comprises at least four separation tubular segments connected end to end, at least a portion of each separation tubular segment extending into the refrigerator to form a cold sink, a vacuum valve being provided between any two adjacent separation tubular segments, and each separation tubular segment being further connected to a heating and temperature control device;

[0009] One end of the first tube column is connected to the reaction container, the other end of the first tube column is connected to a collection container, and the first tube column is also connected to a vacuum pumping device.

[0010] In one embodiment, the separation tube section includes a U-shaped tube body and a straight tube body connected to both ends of the U-shaped tube body, the U-shaped tube body extends into the refrigerator to form the cold depression, and the straight tube body is located outside the refrigerator and is used to connect with adjacent straight tube bodies.

[0011] In one embodiment, at least a portion of the U-shaped tube of the separation tube segment is filled with silver wire and / or Porapak Q filler.

[0012] In one embodiment, the vacuum pumping device includes a mechanical pump and a molecular pump, and both the mechanical pump and the molecular pump are connected to the first column.

[0013] In one embodiment, the collecting container at least partially extends into the processing apparatus.

[0014] In one embodiment, the gas production system further includes an electromagnetic heating stirrer, and the reaction container is disposed in a heating functional area of ​​the electromagnetic heating stirrer.

[0015] In a second aspect, the present invention further provides a measuring device for measuring the carbon and oxygen stable isotope ratio in a silicate sample to be measured, comprising:

[0016] The purification and enrichment device described above; and

[0017] Mass spectrometer.

[0018] In a third aspect, the present invention further provides a gas collection method for reacting a carbonate sample to be tested to generate gas, and purifying and enriching carbon dioxide in the generated gas, wherein the purification and enrichment device comprises the following steps:

[0019] Placing a carbonate sample to be tested in a reaction container, and separating the carbonate sample to be tested from the reaction acid solution in the reaction container;

[0020] Using a vacuum pump connected to the first tubing column to evacuate the first tubing column, the reaction container, and the collection container;

[0021] Close each vacuum valve to prevent the separation pipe sections of the first pipe string from being connected to each other;

[0022] Immersing the carbonate sample to be tested in the reaction container into the reaction acid solution to generate a mixed gas including carbon dioxide;

[0023] heating the first separation pipe segment to a first temperature using a heating and temperature control device, wherein the first temperature is lower than the melting point of water and higher than the temperature of the second separation pipe segment, wherein the first separation pipe segment is the separation pipe segment closest to the reaction vessel, and the second separation pipe segment is the separation pipe segment second closest to the reaction vessel;

[0024] Controlling the opening state of each vacuum valve so that the first separation pipe section and the second separation pipe section are connected to the reaction container, while the remaining separation pipe sections are not connected to the reaction container;

[0025] After a first period of time, the vacuum valve disposed between the first separation pipe section and the second separation pipe section is closed;

[0026] heating the second separation pipe segment to room temperature, the third separation pipe segment to a second temperature, and the fourth separation pipe segment to a third temperature, wherein the second temperature is lower than room temperature and higher than the third temperature, the third separation pipe segment refers to the separation pipe segment third closest to the reaction vessel, and the fourth separation pipe segment refers to the separation pipe segment fourth closest to the reaction vessel;

[0027] Opening the vacuum valve between the second separation pipe section and the third separation pipe section, opening the vacuum valve between the third separation pipe section and the fourth separation pipe section, and closing the vacuum valve between the fourth separation pipe section and the collection container;

[0028] After the second period of time, the temperature of the fourth separation pipe section is raised to room temperature, and then the vacuum valve disposed between the fourth separation pipe section and the collection container is opened.

[0029] In a fourth aspect, the present invention further provides a measurement method for measuring the carbon-oxygen stable isotope ratio of a carbonate sample to be measured, wherein the purified and enriched carbon dioxide gas is prepared using the above-mentioned gas extraction method; after the vacuum valve provided between the fourth separation section and the collection container is opened, the measurement method further comprises the following steps:

[0030] After the third period of time, the collection container is sealed and connected to the mass spectrometer.

[0031] In one embodiment, the measuring method further comprises the following steps:

[0032] Open all vacuum valves and connect the first tubing string to the outside world;

[0033] The refrigerator is turned off, and each separation pipe segment is heated to a fourth temperature and maintained for a third time period using a heating temperature control device, wherein the fourth temperature is not lower than the evaporation temperature of water.

[0034] Compared with the existing technology, the advantage of the present invention is that the air in the device can be discharged before gas production through vacuum equipment, thereby reducing the contamination of air to carbon dioxide. When the produced gas passes through the first pipe column, the water vapor contained in it will be liquefied under the action of cold collapse, reducing the contamination of water vapor to carbon dioxide and improving the purity of the produced carbon dioxide.

[0035] Furthermore, a vacuum valve is installed between adjacent separation pipe sections, ensuring that the pressure in the rear section of the first pipe string remains at a vacuum after evacuation, while the pressure in the front section remains above the vacuum pressure after acidification and gas production. This pressure differential allows the produced gas to flow smoothly to the collection container, shortening experimental time.

[0036] In addition, the temperature of the separation pipe section can be adjusted using a heating temperature control device, which can flexibly adjust the temperature of each separation pipe section and conveniently form a temperature difference between hot front and cold back, so that the gas is enriched at the rear side of the pipeline, thereby increasing the total amount of carbon dioxide collected by the collection container at the rear side of the device.

[0037] In summary, the present application provides a purification and enrichment device, a measuring device, a gas collection method and a measurement method with high purity, high enrichment and short experimental time. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Hereinafter, the present invention will be described in more detail based on embodiments with reference to the accompanying drawings.

[0039] Figure 1 Schematic diagram of the structure of the purification and enrichment device in an embodiment of the present invention;

[0040] Figure 2 is a flow chart of a gas collection method provided by an embodiment of the present invention;

[0041] Figure 3 This is a flow chart of a measurement method provided by an embodiment of the present invention.

[0042] Reference numerals:

[0043] 1. Reaction vessel;

[0044] 2. First pipe column; 21. Air inlet pipe section; 22. First separation pipe section; 23. Second separation pipe section; 24. Third separation pipe section; 25. Fourth separation pipe section; 26. Air outlet pipe section; 27. Vacuum valve;

[0045] 3. Mechanical pump; 4. Molecular pump;

[0046] 5. Collection container;

[0047] 6. Refrigeration device; 61. Refrigeration container;

[0048] 7. Electromagnetic heating mixer;

[0049] 8. First container. DETAILED DESCRIPTION

[0050] The present invention will be further described below with reference to the accompanying drawings.

[0051] Example 1

[0052] like Figure 1 As shown, the present application provides a measuring device for reacting a carbonate sample to be measured to generate gas, and purifying and enriching carbon dioxide in the generated gas, which includes: a gas production system, a separation system, a collection container and a vacuum pumping device.

[0053] The gas production system includes a reaction container 1, which is used to accommodate the carbonate sample to be tested. The reaction container 1 also contains a reaction acid liquid, which is used to react with the carbonate sample to be tested to generate a mixed gas containing carbon dioxide.

[0054] Preferably, the reaction acid solution is a phosphoric acid solution.

[0055] During use, carbonate can be decomposed into carbon dioxide through the gas production system. Since the first pipe column 2 of the separation system is connected to the reaction vessel 1, after a mixed gas containing carbon dioxide is generated in the reaction vessel 1, the mixed gas can be introduced into the first pipe column 2, and the mixed gas can be separated by using multiple separation pipe sections.

[0056] Among them, since at least part of the separation pipe section extends into the refrigerator to form a cold sink, the temperature of the mixed gas in the separation pipe section can be reduced, thereby liquefying the water molecules in the mixed gas to form water droplets, thereby achieving separation of water vapor in the mixed gas.

[0057] A vacuum valve 27 is provided between adjacent separation pipe sections, and the mixed gas can be intercepted in one or several separation pipe sections by opening the vacuum valve 27, so that the water vapor in the mixed gas can be fully cooled.

[0058] In the present application, the first pipe column 2 includes four separation pipe sections, namely, a first separation pipe section 22, a second separation pipe section 23, a third separation pipe section 24, and a fourth separation pipe section 25, which are sequentially connected. The first separation pipe section 22, the second separation pipe section 23, the third separation pipe section 24, and the fourth separation pipe section 25 are sequentially separated from the reaction vessel 1.

[0059] In other implementations, more separation pipe sections may be further connected at the rear side of the fourth separation pipe section 25 .

[0060] like Figure 1As shown, the first pipe column 2 also includes an air inlet pipe section 21 arranged at one end of the first separation pipe section 22 close to the reaction vessel 1. The air inlet pipe section 21 is used to connect the first separation pipe section 22 and the reaction vessel 1, and a vacuum valve 27 is provided between the air inlet pipe and the first separation pipe section 22.

[0061] The first pipe column 2 also includes an air outlet pipe section 26, which is located between the fourth separation pipe section 25 and the collection container. The air outlet pipe section 26 is used to connect the fourth separation pipe section 25 and the collection container, and a vacuum valve 27 is provided between the air outlet pipe section 26 and the fourth separation pipe section 25.

[0062] Since the first tubing column 2 is also connected to a vacuum pumping device, the vacuum pumping device can be used to evacuate the first tubing column 2 and the collection container and reaction container 1 connected to the first tubing column 2 before the carbonate sample to be tested reacts.

[0063] Prevents residual air in the purification and enrichment device from contaminating the gases produced by the reaction. It can also reduce the error in oxygen element measurement results caused by gases such as oxygen and carbon dioxide in the air during mass spectrometry analysis.

[0064] Moreover, since the vacuum valve 27 is provided between adjacent separation pipe sections, the vacuum valve 27 in the closed state has a better sealing effect than a conventional valve body.

[0065] After evacuation, the vacuum valve 27 can be closed to maintain the internal cavity of each separation pipe section in a vacuum environment. Subsequently, the vacuum valve 27 can be opened to connect the separation pipe section in a vacuum environment with the previous pipe section. Under the action of the air pressure difference, the gaseous components can be driven to flow smoothly into the newly connected separation pipe section. This improves the speed of gas circulation and shortens the time for gas purification.

[0066] In addition, a heating temperature control device is provided at the separation pipe section, which can flexibly adjust the temperature of the separation pipe section. Compared with maintaining each separation pipe section near the refrigeration temperature of the refrigerator, the temperature of the separation pipe section can be adjusted in a larger range, so that a larger temperature difference is formed between the two adjacent separation pipe sections.

[0067] Due to gas diffusion, at the same pressure, the gas in the high-temperature area will be relatively rarefied, while the gas in the low-temperature area will be relatively enriched. Because the temperature difference between the hot front and the cold back can be easily created, more gas will be retained in the lower temperature rear area without changing the equipment volume, achieving gas enrichment.

[0068] Furthermore, since the present invention utilizes a heating temperature control device to achieve temperature increase, temperature adjustment is simpler than directly changing the refrigeration temperature of the refrigerator, and there is no need to replace the refrigerant inside the refrigerator.

[0069] The refrigerant in the refrigerator is preferably liquid nitrogen, which has a lower refrigeration temperature and can achieve a more rapid water vapor separation effect. Preferably, the refrigeration temperature of the refrigerator is -196°C. The separation pipe section extending into the refrigerator can be cooled to -196°C.

[0070] The refrigerator may be connected to a refrigeration cylinder for accommodating a low-temperature refrigeration medium, and the refrigeration of the separated pipe sections is achieved by extending the separated pipe sections into the same refrigeration cylinder.

[0071] You can also Figure 1 As shown, the refrigerator is connected to multiple refrigeration cylinders, each of which contains a low-temperature refrigeration medium. When in use, the separate pipe sections are refrigerated by extending each separate pipe section into a different refrigeration cylinder.

[0072] By connecting each separation pipe section to a heating and temperature control device, the separation pipe section can be heated to increase the temperature of the separation pipe section, so that each separation pipe section has a different temperature, thereby realizing different separation processes.

[0073] The heating and temperature control device is preferably an electric heating device. Compared to fuel heating devices, this device avoids the generation of open flames during the heating process, making it safer to use the heating and temperature control device to regulate the temperature of the first tubular column 2. Furthermore, the electric heating device can flexibly control the heating power by controlling the current and voltage, making temperature control more convenient.

[0074] In this application, each separation segment can be inserted into the same refrigerator, and the temperature of each segment can be adjusted by heating the heating and temperature control device connected to each separation segment. Compared to directly using multiple refrigerators to directly control the temperature of each separation segment, the number of refrigerators is reduced, thereby reducing the cost of the purification and enrichment device.

[0075] Moreover, by cooperating with the heating temperature control device and the refrigerator, the temperature of the preceding separation pipe section can be made higher than that of the following separation pipe section, thereby utilizing the gas diffusion effect to enrich the gas in the following separation pipe section and improve the gas enrichment degree.

[0076] In particular, an electric heating wire wrapped around the first pipe column 2 can be used as a heating element of the heating and temperature control device. The heating and temperature control device is directly in contact with the first pipe column 2, which can improve the heating efficiency of the heating and temperature control device.

[0077] The heating temperature control device also includes a proportional integral derivative controller and a solid-state relay. The proportional integral derivative controller can realize proportional integral derivative control (PID control) of the heating temperature of the electric heating wire.

[0078] By setting a proportional-integral-differential controller, precise control of the heating temperature can be achieved, so that the separation pipe section is stabilized at the set temperature.

[0079] In some implementations, the separation tube segment includes a U-shaped tube body and a straight tube body connected to both ends of the U-shaped tube body. The U-shaped tube body extends into the refrigerator to form a cold depression. The straight tube body is located outside the refrigerator and is used to connect to adjacent straight tube bodies.

[0080] That is, the straight tube bodies at both ends of the separation tube section are used to connect the separation tube section with the adjacent tube section, and the U-shaped tube body is used as a cold sink to cool the gas flowing through the separation tube body.

[0081] The cold sink temperature can liquefy the water molecules in the mixed gas into liquid water or solidify into ice crystals. The U-shaped structure of the U-shaped tube body can prevent the liquefied water or solidified ice crystals from escaping the separation section, preventing the separated water molecules from flowing into the collection container.

[0082] In some implementations, at least some of the U-shaped tubes of the separation tube segments are filled with silver wire and / or PorapakQ filler. That is, the U-shaped tubes of all separation tube segments may be filled with the filler, or the U-shaped tubes of one or more separation tube segments may be filled with the filler.

[0083] The U-shaped tube body can be filled with either silver wire or Porapak Q filler, or can be filled with both silver wire and Porapak Q fillers at the same time.

[0084] Porapak Q is a porous polymer composed of ethylvinylbenzene and divinylbenzene, primarily used to separate hydrocarbons, organic analytes, and nitrogen oxides from water. Organic matter is produced during carbonate acidification, and Porapak Q can be used within a U-shaped tube to separate the organic matter from the gas.

[0085] Since relevant fillers are arranged inside the U-shaped tube body, organic matter and sulfide impurities in the mixed gas can be separated in the U-shaped tube body.

[0086] Furthermore, placing the filler inside the U-shaped tube and cooling the mixed gas to assist the filler can more thoroughly remove organic impurities from the mixed gas than simply cooling the mixed gas to separate impurities or simply using the filler to adsorb impurities. This results in higher impurity separation efficiency.

[0087] In some implementations, the vacuum pumping device includes a mechanical pump 3 and a molecular pump 4 , and both the mechanical pump 3 and the molecular pump 4 are connected to the first tubing column 2 .

[0088] When the first tubular column 2 is evacuated by the vacuum equipment, the first tubular column 2 may be evacuated to 10 by the mechanical pump 3. -2 ~10 -3 bar, and then start the molecular pump 4 to further evacuate the first column 2, so that the vacuum degree of the first column 2 is 10 -6 ~10 -7 Compared with single-step vacuuming, the residual gas inside the first column 2 can be more fully removed, reducing the pollution of the residual gas to carbon dioxide.

[0089] like Figure 1 As shown, the first tubing column 2 is provided with three first connection interfaces connected to the molecular pump 4, wherein one first connection interface is provided between the first separation tube segment 22 and the second separation tube segment 23, one first connection interface is provided between the second separation tube segment 23 and the third separation tube segment 24, and another first connection interface is provided between the third separation tube segment 24 and the fourth separation tube segment 25.

[0090] By arranging the first connection interfaces connected to the molecular pump 4 at intervals, the gas remaining in the first column 2 can be completely evacuated.

[0091] like Figure 1 As shown, the first pipe string 2 is provided with a second connection interface communicating with the mechanical pump 3 .

[0092] In some implementations, the collection container is at least partially extended into the refrigerator 6. This allows the collection container 5 to be cooled, so that the collected carbon dioxide is liquid and more carbon dioxide molecules can be collected.

[0093] like Figure 1 As shown, the refrigerator 6 includes multiple refrigeration containers 61, which are filled with liquid nitrogen or other refrigerants to cool the separation pipe section or the collection container 5. In other implementations, multiple refrigerators 6 can be matched, with each separation pipe section corresponding to a refrigerator 6.

[0094] Compared with each separation pipe section corresponding to a refrigerator 6, multiple separation pipe sections are cooled by the same refrigerator 6, which reduces the cost of the purification and enrichment device.

[0095] In some implementations, the gas production system further includes an electromagnetic heating stirrer 7 , and the reaction vessel 1 is disposed in a heating functional area of ​​the electromagnetic heating stirrer 7 .

[0096] The electromagnetic heating stirrer 7 is used to heat the reaction vessel 1, so that the carbonate sample to be tested is at an appropriate reaction temperature, thereby improving the reaction efficiency. The heating temperature of the electromagnetic heating stirrer in this embodiment is 90° C., and the stirring speed is 400 r / min.

[0097] At the same time, the stirring function of the electromagnetic heating stirrer 7 can be used to stir the reaction acid during the reaction process, so that the reaction acid and the carbonate sample to be tested can react more fully.

[0098] The gas production system further includes a first container 8 and a regulating device, wherein the first container 8 is connected to the regulating device. The first container 8 is used to contain the carbonate sample to be tested, and the regulating device is used to adjust the position and tilt angle of the first container 8.

[0099] The regulating device can keep the first container 8 in the first position, so that the first container 8 is separated from the reaction acid in the reaction container 1, thereby preventing the carbonate sample to be tested in the first container 8 from contacting the reaction acid to react and generate gas.

[0100] The adjusting device can also adjust the first container 8 from the first position to the second position, so that the first container 8 moves downward or rotates tiltedly, thereby allowing the carbonate sample to be tested in the first container 8 to contact the reaction acid solution to generate gas.

[0101] like Figure 1 The first container 8 can be a glass, wherein the glass can be selected with a capacity of 0.027 ml.

[0102] Before the reaction begins, the first container 8 is placed inside the reaction vessel 1 and connected to the regulating device. The reaction vessel 1 is then connected to the first tubing string 2, and the interface is sealed so that the reaction vessel 1, the first tubing string 2, and the collection container form a sealed cavity. The first tubing string 2 is then evacuated using a vacuum pump connected to the first tubing string 2 to remove any residual gas from the first tubing string 2, the reaction vessel 1, and the collection container.

[0103] Then, the first container 8 is adjusted to the second position by the adjusting device, so that the carbonate sample to be tested in the first container 8 contacts the reaction acid solution and starts to react to generate a mixed gas.

[0104] The provision of a regulating device avoids the need to open the reaction vessel 1 and adjust the carbonate sample after evacuating the reaction vessel 1. This not only allows the reaction to start after evacuation, but also prevents the introduction of air into the reaction vessel 1 after evacuation. This better ensures the purity of the collected gas.

[0105] like Figure 1 As shown, in some implementations, the reaction container 1 is a conical flask, and the first column 2 is a metal tube. The inner diameter of the first column 2 is preferably 3 mm.

[0106] The purification and enrichment device provided in this embodiment utilizes a vacuum pump to completely remove any remaining air from the first column 2, thereby improving the purity of the carbon dioxide within the collection container. Furthermore, the cold trap formed by the separation section of the first column 2 removes moisture and organic impurities from the produced gas, reducing interference from these impurities on isotope measurements.

[0107] Furthermore, since vacuum valves 27 are provided between adjacent separation pipe sections, the movement space of the prepared gas can be flexibly controlled, and a pressure difference can be formed between the pipe sections before and after the vacuum valves 27 are opened. This pressure difference can improve the gas circulation efficiency and shorten the measurement time.

[0108] Furthermore, the separation pipe section can be heated by a heating and temperature control device connected to the separation pipe section to adjust its temperature. Compared to setting up multiple refrigerators with different cooling temperatures, setting up a heating and temperature control device can reduce the number of refrigerators, making the measurement device more cost-effective.

[0109] Example 2

[0110] This embodiment provides a purification and enrichment device, which is generally similar to the purification and enrichment device provided in Example 1, except that it also includes a timing device and a controller, which are connected to the controller. Furthermore, the gas production system, vacuum equipment, vacuum valve 27, heating control device, and refrigerator are all connected to the controller. The controller can control the activation of the vacuum equipment, vacuum valve 27, heating control device, and refrigerator based on time, thereby automating the gas extraction process.

[0111] Specifically, before starting the gas production system, the controller first opens the vacuum valves 27 and then uses the vacuum equipment to evacuate the first column 2, the reaction container 1 and the collection container;

[0112] After the vacuuming is completed, the controller sends a control instruction to each vacuum valve 27 to control each vacuum valve 27 to close and enable the gas making system to start gas making work;

[0113] After the gas production system produces gas, the controller controls the refrigerator to cool the separation pipe section so that the separation pipe section forms a cold sag, and then controls the heating control device to heat the first separation pipe section 22 so that the temperature of the first separation pipe section 22 reaches the first temperature (preferably -90°C to -60°C), while the temperature of the second separation pipe section 23 is -196°C;

[0114] The controller opens the vacuum valve 27 before the third separation pipe section 24, so that the mixed gas generated by the gas production system flows between the first separation pipe section 22 and the second separation pipe section 23, so that the water is liquefied and separated in the first pipe section.

[0115] After a 15-minute timer, the first separation section 22 is returned to room temperature, the second separation section 23 is heated to a second temperature (preferably -20°C to -15°C), and the temperature of the third separation section 24 is controlled at -196°C. A controller opens the vacuum valve 27 between the third and second separation sections 24, allowing the mixed gas to flow into the third separation section 24. Further purification is then performed, wherein organic impurities can be separated by a U-shaped tube filled with adsorbent filler (silver wire and / or PorapakQ filler).

[0116] After the timing device counts down to 15 minutes, the controller opens the vacuum valve 27 between the fourth separation pipe section 25 and the collection container, allowing the purified carbon dioxide gas to flow into the collection container, completing the purification and enrichment of carbon dioxide.

[0117] By using the measurement method provided in this embodiment, the mixed gas can be purified and enriched through the multiple separation sections of the first column 2 to collect pure carbon dioxide gas.

[0118] The vacuum pump and vacuum valve 27 work together to maintain each separation pipe section in a vacuum state before the reaction. This not only prevents residual air inside the pipe from contaminating the produced carbon dioxide, but also creates a pressure difference between the separation pipe section connected to the reaction vessel 1 and the separation pipe section not connected to the reaction vessel 1 after gas production in the reaction vessel 1. This pressure difference drives the gas to flow smoothly within the first column 2 to the collection container.

[0119] The separation work can also be completed by forming a cold depression under the action of a refrigerator, and the temperature of each separation pipe section can be adjusted by a heating temperature control device, so that there is a temperature difference between the front and rear separation pipe sections, so that the gas is enriched in the separation pipe section on the rear side, thereby improving the enrichment degree of the gas.

[0120] Example 3

[0121] The present invention also provides a measuring device for measuring the carbon and oxygen isotope ratio in a carbonate sample to be measured, which includes the purification and enrichment device in the above embodiment and also includes a mass spectrometer.

[0122] The generated carbon dioxide gas is purified and enriched by a purification and enrichment device and collected in a collection container. The collection container is then connected to a mass spectrometer, which analyzes the carbon and oxygen isotope ratios in the gas collected by the collection container to obtain the carbon and oxygen isotope ratios in the carbonate sample to be tested.

[0123] In some implementations, the measuring device further includes a dual-path sampling system, which connects the collection container and the mass spectrometer.

[0124] Dual injection technology is the ultimate solution for pure gas isotope analysis applications seeking the highest possible precision and sensitivity. This is due to a unique ultra-low volume changeover valve that performs multiple comparisons between sample and reference gases to enhance analytical precision.

[0125] Especially when analyzing carbonate and water samples in paleoclimate studies, the highest precision in stable isotope analysis is achieved through precise and sensitive dual-path sampling technology.

[0126] Because the measurement device includes the purification and enrichment device described in the above embodiment, the remaining air in the first tubing column 2 can be completely evacuated using a vacuum device, thereby improving the purity of the carbon dioxide in the collection container. Furthermore, the cold trap formed by the separation section of the first tubing column 2 can remove water vapor and organic impurities from the produced gas, reducing interference from these impurities on isotope measurement.

[0127] Furthermore, since vacuum valves 27 are provided between adjacent separation pipe sections, the movement space of the prepared gas can be flexibly controlled, and a pressure difference can be formed between the pipe sections before and after the vacuum valves 27 are opened. This pressure difference can improve the gas circulation efficiency and shorten the measurement time.

[0128] Furthermore, the separation pipe section can be heated by a heating and temperature control device connected to the separation pipe section to adjust its temperature. Compared to setting up multiple refrigerators with different cooling temperatures, setting up a heating and temperature control device can reduce the number of refrigerators, making the measurement device more cost-effective.

[0129] Example 4

[0130] See also Figure 1 as well as Figure 2 As shown, the present invention also provides a gas collection method for reacting a carbonate sample to be tested to generate gas and purifying and enriching carbon dioxide in the generated gas, which uses the purification and enrichment device as described in Example 1 or Example 2, and includes the following steps:

[0131] Step S1: placing a carbonate sample to be tested in a reaction container 1, and separating the carbonate sample to be tested from the reaction acid solution in the reaction container 1;

[0132] Step S2: using a vacuum pump connected to the first tubing column 2 to evacuate the first tubing column 2, the reaction container 1, and the collection container;

[0133] Step S3: closing each vacuum valve 27 so that each separation pipe section of the first pipe string 2 is not connected to each other;

[0134] Step S4: immersing the carbonate sample to be tested in the reaction container 1 into the reaction acid solution to generate a mixed gas including carbon dioxide;

[0135] Step S5: using a heating and temperature control device to heat the first separation pipe section 22 to a first temperature, wherein the first temperature is lower than the melting point of water and higher than the temperature of the second separation pipe section 23;

[0136] The first separation pipe section 22 refers to the separation pipe section closest to the reaction vessel 1, and the second separation pipe section 23 refers to the separation pipe section second closest to the reaction vessel 1;

[0137] Step S6: Controlling the opening state of each vacuum valve 27 so that the first separation pipe section 22 and the second separation pipe section 23 are connected to the reaction container 1, while the remaining separation pipe sections are not connected to the reaction container 1;

[0138] Step S7: After a first period of time, the vacuum valve 27 disposed between the first separation pipe section 22 and the second separation pipe section 23 is closed;

[0139] Step S8: heating the second separation pipe segment 23 to room temperature, and heating the third separation pipe segment 24 to a second temperature, wherein the second temperature is lower than room temperature and higher than the temperature of the fourth separation pipe segment 25, the third separation pipe segment 24 is the third separation pipe segment closest to the reaction vessel 1, and the fourth separation pipe segment 25 is the fourth separation pipe segment closest to the reaction vessel 1;

[0140] Step S9: Opening the vacuum valve 27 disposed between the second separation pipe section 23 and the third separation pipe section 24, opening the vacuum valve 27 disposed between the third separation pipe section 24 and the fourth separation pipe section 25, and closing the vacuum valve 27 disposed between the fourth separation pipe section 25 and the collection container;

[0141] Step S10: After the second period of time, close the vacuum valve 27 between the fourth separation pipe segment 25 and the third separation pipe segment 24, increase the temperature of the fourth separation pipe segment 25 to room temperature, extend the collection container into the refrigerator, and then open the vacuum valve 27 between the fourth separation pipe segment 25 and the collection container.

[0142] Through the above steps, the carbonate sample to be tested can be reacted with the gas production system to obtain a mixed gas containing carbon dioxide. The mixed gas is then purified and enriched through the multiple separation sections of the first column 2 to collect pure carbon dioxide gas.

[0143] Here, before step S4: immersing the carbonate sample to be tested in the reaction acid solution, step S2: vacuuming by using a vacuuming device and step S3: closing each vacuum valve 27 are first performed.

[0144] By keeping each separation pipe section in a vacuum state before the reaction, it not only avoids the residual air inside the pipeline from contaminating the prepared carbon dioxide, but also enables the separation pipe section connected to the reaction vessel 1 to have a pressure difference with the separation pipe section not connected to the reaction vessel 1 after the reaction vessel 1 produces gas.

[0145] In step S6 , when the first separation pipe section 22 and the second separation pipe section 23 are connected to the reaction container 1 , the mixed gas in the reaction container 1 can be smoothly passed into the first separation pipe section 22 and the second separation pipe section 23 by the pressure difference.

[0146] In step S5 , the first separation pipe section 22 is heated to a first temperature by the heating control device, so that the temperature of the first separation pipe section 22 is higher than the second separation pipe section 23 but lower than the melting point of water.

[0147] Among them, the first temperature refers to -90℃~-60℃, and at this time, the temperature of the second separation pipe section 23 is stabilized at -196℃, which is lower than the liquefaction temperature of carbon dioxide. When the mixed gas passes through the first separation pipe section 22, the water vapor in the mixed gas is liquefied or solidified, thereby separating the water vapor in the mixed gas. The carbon dioxide is liquefied in the second separation pipe section 23. In some embodiments, the second separation pipe section 23 can be set to other temperatures lower than the liquefaction temperature of carbon dioxide (the liquefaction temperature at standard atmospheric pressure is -78.5℃) in step S5. For example, the temperature of the second separation pipe section 23 is controlled at -160℃ or -150℃.

[0148] At the same time, since the temperature of the first separation pipe section 22 after being heated by the heating and temperature control device is higher than the temperature of the second separation pipe section 23, the gas density in the second separation pipe section 23 can be made higher than the gas density in the first separation pipe section 22, so that the carbon dioxide gas is enriched in the second separation pipe section 23 which is farther away from the reaction vessel 1.

[0149] like Figure 1 As shown, the separation section includes a U-shaped tube body and straight tube bodies arranged at both ends of the U-shaped tube body. The U-shaped tube body extends into the refrigerator to form a cold sag, so that the water vapor separated in the first separation section 22 is concentrated in the U-shaped tube body. The U-shaped structure of the U-shaped tube body prevents the concentrated liquid or solid water molecules from escaping the U-shaped tube body, further improving the separation effect of the first separation section 22.

[0150] After step S6, step S7 is executed: after the first period of time, the vacuum valve 27 arranged between the first separation pipe section 22 and the second separation pipe section 23 is closed, so that after the water vapor is separated in the first separation pipe section 22, the first separation pipe section 22 is disconnected from the subsequent separation pipe sections, thereby preventing the water vapor in the first separation pipe section 22 from entering the second separation pipe section 23 and contaminating the carbon dioxide.

[0151] The first time duration is preferably 15 minutes. In another implementation, the first time duration can be appropriately extended according to the weight of the carbonate sample to be tested, for example, the first time duration can be adjusted to 16 minutes or 17 minutes.

[0152] In step S8 , the second separation pipe section 23 is heated to room temperature, and the third separation pipe section 24 is heated to a second temperature, which is lower than room temperature and higher than the temperature of the fourth separation pipe section 25 .

[0153] The second temperature is preferably -20°C to -15°C. The temperature of the fourth separation pipe section 25 is -196°C.

[0154] The second separation tube section 23 can be separated from the refrigerator and heated by a heating and temperature control device connected to the second separation tube section 23 to reach room temperature. The third separation tube section 24 can be inserted into the refrigerator and heated by the heating and temperature control device to a temperature higher than the refrigerator's refrigeration temperature but lower than 0°C.

[0155] Since the second separation pipe section 23 is heated to a room temperature higher than the liquefaction temperature of carbon dioxide, the originally liquid carbon dioxide is converted into gaseous state.

[0156] After step S9, as the vacuum valve 27 is regulated, the second separation pipe section 23 and the fourth separation pipe section 25 are connected, and the gas is transferred from the second separation pipe section 23 to the third separation pipe section 24 and the fourth separation pipe section 25 under the action of the pressure difference.

[0157] As can be seen above, the fourth separation section 25 is the coldest of the three separation sections (the second separation section 23, the third separation section 24, and the fourth separation section 25). Due to the diffusion effect of the gas, the gas is concentrated in the fourth separation section 25. Since the temperature of the fourth separation section 25 is lower than the liquefaction temperature of carbon dioxide, the carbon dioxide accumulated in the fourth separation section 25 is liquefied into a liquid state.

[0158] like Figure 1 As shown, the third separation pipe section 24 is the third separation pipe section closest to the reaction vessel 1, and the fourth separation pipe section 25 is the fourth separation pipe section closest to the reaction vessel 1. By gradually increasing the temperature among the fourth separation pipe section 25, the third separation pipe section 24, and the second separation pipe section 23, the gas can be gradually enriched in the fourth pipe section with the lowest temperature due to the temperature difference.

[0159] In some implementations, the temperature of the fourth separation pipe section 25 is maintained at -196° C. in step S9. In other implementations, the fourth separation pipe section 25 may be set at a temperature lower than the liquefaction temperature of carbon dioxide (the liquefaction temperature at standard atmospheric pressure is -78.5° C.) in step S5, for example, the temperature of the fourth separation pipe section 25 may be controlled at -160° C. or -150° C.

[0160] As the gas is transferred from the second separation pipe section 23 to the fourth separation pipe section 25, impurities in the gas can be removed through multiple separation pipe sections. In particular, for the separation pipe section filled with silver wire and Porapak Q filler, organic impurities can also be adsorbed to prevent organic impurities from remaining in the carbon dioxide gas, making the carbon dioxide gas collected in the collection container purer.

[0161] After separation in multiple separation pipe sections, the purity of the carbon dioxide gas in the fourth separation pipe section 25 is significantly improved. The cold sink and the U-shaped pipe body cooperate to remove most of the water vapor, organic impurities and sulfide impurities.

[0162] Then, after step S10, the vacuum valve 27 between the fourth separation pipe segment 25 and the third separation pipe segment 24 is closed to prevent the carbon dioxide enriched in the fourth separation pipe segment 25 from flowing back into the third separation pipe segment 24, and then the temperature of the fourth separation pipe segment 25 is heated to room temperature, and then the vacuum valve 27 set between the fourth separation pipe segment 25 and the collection container is opened to achieve communication between the fourth separation pipe segment 25 and the collection container.

[0163] Since the vacuum valve 27 between the fourth separation pipe section 25 and the collection container is immediately closed after the vacuum is drawn in step S2 and is not opened in subsequent steps, the collection container is always in a vacuum environment. When the vacuum valve 27 is opened, the carbon dioxide in the fourth separation pipe section 25 can be smoothly passed into the mobile phone container due to the pressure difference.

[0164] Furthermore, since the fourth separation pipe section 25 is heated to room temperature and the collection container is placed in a refrigerator for cooling, the temperature of the collection container can be lower than that of the fourth separation pipe section 25. Consequently, after the fourth separation pipe section 25 and the collection container are connected, the concentration of carbon dioxide in the collection container is higher than that within the fourth separation pipe section 25, thereby enriching carbon dioxide in the collection container.

[0165] After the temperature of the collection container drops to -196°C, the vacuum valve 27 between the fourth separation pipe section 25 and the collection container can be opened to increase the temperature difference between the collection container and the fourth separation pipe section 25, thereby improving the enrichment degree of the collection container.

[0166] In order to facilitate understanding of the temperature settings at each stage in the above test steps and the opening degree of each vacuum valve 27, the following table is provided.

[0167] Phase 1 Phase II Phase 3 Stage 4 Stage 5 First vacuum valve Open closure Open closure First separation pipe section -90℃～-60℃ Second vacuum valve Open closure Open closure Second separation pipe section -196℃ Room temperature The third vacuum valve Open closure closure Open The third separation pipe section -20℃～-15℃ Fourth vacuum valve Open closure closure Open closure Fourth separation pipe section -196℃ Room temperature Fifth vacuum valve Open closure closure closure Open Collection container -196℃

[0168] The first vacuum valve in the above table refers to the vacuum valve 27 arranged between the first separation pipe section 22 and the reaction vessel 1, the second vacuum valve refers to the vacuum valve 27 arranged between the first separation pipe section 22 and the second separation pipe section 23, the third vacuum valve refers to the vacuum valve 27 arranged between the second separation pipe section 23 and the third separation pipe section 24, the fourth vacuum valve refers to the vacuum valve 27 arranged between the third separation pipe section 24 and the fourth separation pipe section 25, and the fifth vacuum valve refers to the vacuum valve 27 arranged between the fourth separation pipe section 25 and the collection container.

[0169] The first stage refers to the process before step S3, in which each vacuum valve 27 is opened to facilitate vacuuming. Then, in step S3, i.e., the second stage, the vacuuming process is completed and each vacuum valve 27 is closed to form an independent vacuum environment in each separated pipe section, with the help of the vacuum valve 27 having good sealing performance.

[0170] It should be noted that step S2: using a vacuum pump connected to the first tubing column 2 to vacuum the first tubing column 2, the reaction container 1 and the collection container includes:

[0171] The first column 2, the reaction vessel 1 and the collection vessel are evacuated to 10 -2 ~10 -3 bar;

[0172] Then, the molecular pump 4 is used to evacuate the first column 2, the reaction container 1 and the collection container to a vacuum of 10 -6 ~10 -7 bar.

[0173] After rough evacuation with mechanical pump 3, further evacuation is performed with molecular pump 4. Compared to evacuation with mechanical pump 3 alone, evacuation with molecular pump 4 produces a purer vacuum environment. Furthermore, by first performing a preliminary evacuation with mechanical pump 3 and then evacuating with molecular pump 4, direct evacuation with molecular pump 4 prevents damage to the molecular pump 4.

[0174] Steps S5 and S6 refer to the third stage of the aforementioned table. At this point, reaction vessel 1 is connected to the first two separation segments (first separation segment 22 and second separation segment 23), and the temperature of first separation segment 22 is maintained between -90°C and -60°C. This stage of the purification and enrichment apparatus must be maintained for at least 15 minutes to achieve separation of the mixed gas between first separation segment 22 and second separation segment 23.

[0175] The fourth stage, step S9, occurs when the second separation pipe section 23 is disconnected from the first separation pipe section 22 and connected to the third separation pipe section 24 and the fourth separation pipe section 25. The second, third, and fourth separation pipe sections 23, 24, and 25 are used to further separate the carbon dioxide gas. This improves the purity of the carbon dioxide. As the temperatures of the second, third, and fourth separation pipe sections 23, 24, and 25 decrease in sequence, the carbon dioxide is concentrated in the fourth pipe section.

[0176] Example 5

[0177] See also Figure 1 as well as Figure 3 As shown, the present invention also provides a measurement method for measuring the carbon and oxygen stable isotope ratio of a carbonate sample to be measured, which comprises the following steps:

[0178] Step S1: placing a carbonate sample to be tested in a reaction container 1, and separating the carbonate sample to be tested from the reaction acid solution in the reaction container 1;

[0179] Step S2: using a vacuum pump connected to the first tubing column 2 to evacuate the first tubing column 2, the reaction container 1, and the collection container;

[0180] Step S3: closing each vacuum valve 27 so that each separation pipe section of the first pipe string 2 is not connected to each other;

[0181] Step S4: immersing the carbonate sample to be tested in the reaction container 1 into the reaction acid solution to generate a mixed gas including carbon dioxide;

[0182] Step S5: using a heating and temperature control device to heat the first separation pipe section 22 to a first temperature, wherein the first temperature is lower than the melting point of water and higher than the temperature of the second separation pipe section 23;

[0183] The first separation pipe section 22 refers to the separation pipe section closest to the reaction vessel 1, and the second separation pipe section 23 refers to the separation pipe section second closest to the reaction vessel 1;

[0184] Step S6: Controlling the opening state of each vacuum valve 27 so that the first separation pipe section 22 and the second separation pipe section 23 are connected to the reaction container 1, while the remaining separation pipe sections are not connected to the reaction container 1;

[0185] Step S7: After a first period of time, the vacuum valve 27 disposed between the first separation pipe section 22 and the second separation pipe section 23 is closed;

[0186] Step S8: heating the second separation pipe segment 23 to room temperature, and heating the third separation pipe segment 24 to a second temperature, wherein the second temperature is lower than room temperature and higher than the temperature of the fourth separation pipe segment 25, the third separation pipe segment 24 is the third separation pipe segment closest to the reaction vessel 1, and the fourth separation pipe segment 25 is the fourth separation pipe segment closest to the reaction vessel 1;

[0187] Step S9: Opening the vacuum valve 27 disposed between the second separation pipe section 23 and the third separation pipe section 24, opening the vacuum valve 27 disposed between the third separation pipe section 24 and the fourth separation pipe section 25, and closing the vacuum valve 27 disposed between the fourth separation pipe section 25 and the collection container;

[0188] Step S10: After the second period of time, close the vacuum valve 27 between the fourth separation pipe segment 25 and the third separation pipe segment 24, increase the temperature of the fourth separation pipe segment 25 to room temperature, extend the collection container into the refrigerator, and then open the vacuum valve 27 between the fourth separation pipe segment 25 and the collection container.

[0189] Step S11: After the third period of time, the collection container is sealed and connected to the mass spectrometer.

[0190] That is, the purified carbon dioxide gas is first enriched in a collection container using the gas extraction method provided in Example 4, and then the collection container is connected to a mass spectrometer to measure the carbon and oxygen isotope content in the carbon dioxide using the mass spectrometer.

[0191] Specifically, the mass spectrometer was used to measure 13 C. 12 C. 18 O. 16 O, R47, R46 and R45 content,

[0192] in, 13 C represents the measured abundance of carbon 13, 12 C represents the measured abundance of carbon 12, 18 O represents the measured abundance of oxygen-18, 16 O represents the measured abundance of oxygen-16, R47 represents the abundance of the isotopologue with a mass number of 47, R46 represents the abundance of the isotopologue with a mass number of 46, and R45 represents the abundance of the isotopologue with a mass number of 45.

[0193] According to the above parameters measured by mass spectrometer, the carbon isotope ratio δ can be calculated based on the following formula: 13 C. Oxygen isotope ratio δ 18 O and carbon dioxide cluster isotope values ​​Δ 47

[0194] δ 13 C=[(13 C / 12 C) / ( 13 C 标准 / 12 C 标准 )-1]×1000‰

[0195] δ 18 O=[( 18 O / 16 O) / ( 18 O 标准 / 16 O 标准 )-1]×1000‰

[0196] Δ 47 =[(R47 / R47 理论 -1)-(R46 / R46 理论 -1)-(R45 / R45 理论 -1)]×1000‰

[0197] Among them, multiple carbon isotope ratios, oxygen isotope ratios, and carbon dioxide isotope values ​​can be calculated by multiple measurements to obtain the carbon isotope ratio δ 13 Mean and standard deviation of C; oxygen isotope ratio δ 18 The mean and standard deviation of O; and the carbon dioxide cluster isotope value Δ 47 The mean and standard deviation of .

[0198] In one measurement, the sample was tested 8 times, where δ 13 The mean value of C is -5.1‰, and the standard deviation is 0.011‰;

[0199] δ 18 The mean value of O is -2.1‰, with a standard deviation of 0.034‰;

[0200] Δ 47 The mean is 0.52‰, the standard deviation is 0.049‰, and the standard error is 0.019‰.

[0201] By using the measurement method provided in this embodiment, the mixed gas can be purified and enriched through the multiple separation sections of the first column 2 to collect pure carbon dioxide gas.

[0202] The vacuum pump and vacuum valve 27 work together to maintain each separation pipe section in a vacuum state before the reaction. This not only prevents residual air inside the pipe from contaminating the produced carbon dioxide, but also creates a pressure difference between the separation pipe section connected to the reaction vessel 1 and the separation pipe section not connected to the reaction vessel 1 after gas production in the reaction vessel 1. This pressure difference drives the gas to flow smoothly within the first column 2 to the collection container.

[0203] The separation work can also be completed by forming a cold depression under the action of a refrigerator, and the temperature of each separation pipe section can be adjusted by a heating temperature control device, so that there is a temperature difference between the front and rear separation pipe sections, so that the gas is enriched in the separation pipe section on the rear side, thereby improving the enrichment degree of the gas.

[0204] Example 6

[0205] like Figure 1 as well as Figure 3 As shown, this embodiment further provides a measurement method, which is based on the measurement method provided in the fifth embodiment, except that, after step S11, the measurement method further includes the following steps:

[0206] Step S12: Open all vacuum valves 27 and connect the first tubing string 2 to the outside world;

[0207] Step S13: Turn off the refrigerator, and use the heating temperature control device to heat each separation pipe segment to a fourth temperature and maintain it for a third time period, wherein the fourth temperature is not lower than the evaporation temperature of water.

[0208] Through step S13, the water vapor remaining in the separation pipe section after the separation process can be evaporated, and the gaseous water molecules will gradually float out of the first pipe column 2, thereby removing the impurity water in the first pipe column 2 and preventing the residual impurities from affecting subsequent measurements.

[0209] Moreover, organic impurities attached to the liquid water will be removed simultaneously with the removal of the impure water.

[0210] In some embodiments, the fourth temperature is 100° C., and the third time period is 10 minutes. In other implementations, the removal effect can be improved by increasing the heating temperature of each separation pipe segment.

[0211] Furthermore, after step S13, the first column 2, the reaction container 1 and the collection container may be evacuated by using a vacuum device so that the vacuum degree of the first column 2, the reaction container 1 and the collection container is maintained at 10 -6 ~10 - 7 bar, effectively removing residual impure water, organic matter, and sulfide in the device. The vaporized impure water, organic matter, and sulfide are drawn out of the first column 2, reaction vessel 1, and collection vessel, reducing contamination of the purification and enrichment device.

[0212] By using the measurement method provided in this embodiment, the mixed gas can be purified and enriched through the multiple separation sections of the first column 2 to collect pure carbon dioxide gas.

[0213] The vacuum pump and vacuum valve 27 work together to maintain each separation pipe section in a vacuum state before the reaction. This not only prevents residual air inside the pipe from contaminating the produced carbon dioxide, but also creates a pressure difference between the separation pipe section connected to the reaction vessel 1 and the separation pipe section not connected to the reaction vessel 1 after gas production in the reaction vessel 1. This pressure difference drives the gas to flow smoothly within the first column 2 to the collection container.

[0214] The separation work can also be completed by forming a cold depression under the action of a refrigerator, and the temperature of each separation pipe section can be adjusted by a heating temperature control device, so that there is a temperature difference between the front and rear separation pipe sections, so that the gas is enriched in the separation pipe section on the rear side, thereby improving the enrichment degree of the gas.

[0215] While the present invention has been described with reference to preferred embodiments, various modifications may be made and equivalent components may be substituted without departing from the scope of the present invention. In particular, the various technical features described in the various embodiments may be combined in any manner, provided no structural conflicts exist. The present invention is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions within the scope of the claims.

Claims

1. A purification and enrichment device for reacting a carbonate sample to be tested to generate gas, and purifying and enriching carbon dioxide in the generated gas, characterized in that: It includes: A gas production system comprising a reaction container for accommodating a carbonate sample to be tested, wherein the reaction container further contains a reaction acid liquid, wherein the reaction acid liquid is used to react with the carbonate sample to be tested to generate a mixed gas containing carbon dioxide; A separation system comprising a first tubular column and a refrigerator, wherein the first tubular column comprises at least four separation tubular segments connected end to end, at least a portion of each separation tubular segment extending into the refrigerator to form a cold sink, a vacuum valve being provided between any two adjacent separation tubular segments, and each separation tubular segment being further connected to a heating and temperature control device; One end of the first tube column is connected to the reaction container, the other end of the first tube column is connected to a collection container, and the first tube column is also connected to a vacuum pumping device.

2. The purification and enrichment device according to claim 1, characterized in that The separation tube section includes a U-shaped tube body and a straight tube body connected to both ends of the U-shaped tube body. The U-shaped tube body extends into the refrigerator to form the cold sink. The straight tube body is located outside the refrigerator and is used to connect with adjacent straight tube bodies.

3. The purification and enrichment device according to claim 2, characterized in that: The interior of the U-shaped tube of at least a portion of the separation tube section is filled with silver wire and / or Porapak Q filler.

4. The purification and enrichment device according to claim 1 or 2, characterized in that: The vacuum pumping equipment includes a mechanical pump and a molecular pump, and both the mechanical pump and the molecular pump are connected to the first column.

5. The purification and enrichment device according to claim 1 or 2, characterized in that: The collecting container at least partially extends into the processing apparatus.

6. The purification and enrichment device according to claim 1 or 2, characterized in that: The gas production system further includes an electromagnetic heating stirrer, and the reaction container is arranged in a heating function area of ​​the electromagnetic heating stirrer.

7. A measuring device for measuring the carbon and oxygen stable isotope ratios in a silicate sample to be measured, characterized in that: It includes: The purification and enrichment device according to any one of claims 1 to 6; as well as Mass spectrometer.

8. A gas collection method for reacting a carbonate sample to be tested to generate gas, and purifying and enriching carbon dioxide in the generated gas, characterized in that: The purification and enrichment device according to any one of claims 1 to 6 is used, which comprises the following steps: Placing a carbonate sample to be tested in a reaction container, and separating the carbonate sample to be tested from the reaction acid solution in the reaction container; Using a vacuum pump connected to the first tubing column to evacuate the first tubing column, the reaction container, and the collection container; Close each vacuum valve to prevent the separation pipe sections of the first pipe string from being connected to each other; Immersing the carbonate sample to be tested in the reaction container into the reaction acid solution to generate a mixed gas including carbon dioxide; heating the first separation pipe segment to a first temperature using a heating and temperature control device, wherein the first temperature is lower than the melting point of water and higher than the temperature of the second separation pipe segment, wherein the first separation pipe segment is the separation pipe segment closest to the reaction vessel, and the second separation pipe segment is the separation pipe segment second closest to the reaction vessel; Controlling the opening state of each vacuum valve so that the first separation pipe section and the second separation pipe section are connected to the reaction container, while the remaining separation pipe sections are not connected to the reaction container; After a first period of time, the vacuum valve disposed between the first separation pipe section and the second separation pipe section is closed; heating the second separation pipe segment to room temperature, the third separation pipe segment to a second temperature, and the fourth separation pipe segment to a third temperature, wherein the second temperature is lower than room temperature and higher than the third temperature, the third separation pipe segment refers to the separation pipe segment third closest to the reaction vessel, and the fourth separation pipe segment refers to the separation pipe segment fourth closest to the reaction vessel; Opening the vacuum valve between the second separation pipe section and the third separation pipe section, opening the vacuum valve between the third separation pipe section and the fourth separation pipe section, and closing the vacuum valve between the fourth separation pipe section and the collection container; After the second period of time, close the vacuum valve between the fourth separation pipe segment and the third separation pipe segment, raise the temperature of the fourth separation pipe segment to room temperature, extend the collection container into the refrigerator, and then open the vacuum valve between the fourth separation pipe segment and the collection container.

9. A method for measuring the carbon and oxygen stable isotope ratio of a carbonate sample to be measured, characterized in that: Purified and enriched carbon dioxide gas is prepared using the gas extraction method according to claim 8; after the vacuum valve provided between the fourth separation section and the collection container is opened, the measurement method further comprises the following steps: After the third period of time, the collection container is sealed and connected to the mass spectrometer.

10. The measuring method according to claim 9, characterized in that After the collection container is connected to the mass spectrometer, the measurement method further comprises the following steps: Open all vacuum valves and connect the first tubing string to the outside world; The refrigerator is turned off, and each separation pipe segment is heated to a fourth temperature and maintained for a third time period using a heating temperature control device, wherein the fourth temperature is not lower than the evaporation temperature of water.

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