A type of 14 Automated CO2 enrichment device and method for atmospheric samples measured by C

Abstract

This invention discloses a method for 14 An automated CO2 enrichment device and method for atmospheric samples, involving atmospheric chemistry and isotope geochemistry, integrates an atmospheric sample supply unit, an enrichment and purification unit, a quantitative unit, a collection unit, a vacuum control unit, and a control and monitoring system. It automates the processes of ground system pumping, sample loading, enrichment and purification, carbon content determination, CO2 collection, and system purification and vacuum status verification, achieving efficient separation and enrichment of CO2 from atmospheric samples. Based on the different sublimation points of different gaseous substances in the atmosphere, this invention selectively captures CO2 from atmospheric samples through multi-stage cryogenic cooling, and further employs cryogenic collection technology to achieve quantitative collection of high-purity CO2 gas. The entire process is automated, significantly improving the efficiency and accuracy of the enrichment process. 14 High-precision CO2 measurement provides a reliable pretreatment solution.

Description

Technical Field

[0001] This invention relates to the fields of atmospheric chemistry and isotope geochemistry, and particularly to a method for... 14 An automated CO2 enrichment device and method for atmospheric samples measured by C. Background Technology

[0002] CO2 emissions from the combustion of fossil fuels account for more than 70% of global anthropogenic greenhouse gas emissions (IPCC, 2021). Radiocarbon isotopes ( 14 C) Because it has decayed and been depleted in fossil fuels, it has become the most accurate and effective means of quantitatively tracing atmospheric fossil source CO2. Currently, the atmosphere... 14 CO2 monitoring has become a key component in tracing greenhouse gas sources and reducing emissions.

[0003] because 14 The extremely low natural abundance of C (1.2 × 10⁻⁶) -12 %), atmospheric samples are being processed 14 CO2 requires rigorous enrichment and purification before measurement to effectively remove interfering gases (such as nitrogen, oxygen, and water vapor) and obtain a high-purity CO2 sample. During the enrichment and purification process, the recovery rate and purity of CO2 directly affect the accuracy and reliability of the final measurement results. Currently, although various techniques exist for enriching and purifying CO2 from mixed gas sources, existing methods still have certain limitations and cannot fully meet the requirements of atmospheric... 14 High precision is required for CO2 measurement.

[0004] I. Chemical Absorption Method: This method selectively absorbs CO2 using an alkaline solution (such as amine solution), then regenerates the absorbent by heating to desorb and release high-purity CO2. This is one of the most widely used methods in industry, especially in carbon capture in large power plants and chemical plants. However, this method suffers from problems such as high energy consumption (mainly due to desorption heat), easy degradation of the absorbent, generation of corrosive substances, large equipment size, complex operation, and risks of solvent loss and environmental pollution.

[0005] II. Physical Adsorption Method: This method utilizes the selective adsorption capacity of solid adsorbents (such as zeolite molecular sieves, activated carbon, and metal-organic framework materials) for CO2, achieving CO2 enrichment and desorption through pressure swing adsorption (PSA) or temperature swing adsorption (TSA) cycles. PSA / TSA technology offers advantages such as relatively low energy consumption, simple operation, and high automation. However, its main challenges are: ① Adsorption capacity and selectivity need further improvement to achieve higher product purity and recovery rates; ② Adsorbents may become poisoned or experience performance degradation due to impurities (such as water vapor and sulfides) during long-term operation; ③ Adsorbent regeneration (purging or heating) still consumes energy; ④ When treating gas sources containing high concentrations of inert gases (such as nitrogen) or multiple competing adsorbents, purification efficiency may decrease, requiring multi-stage complex processes, increasing equipment cost and operational difficulty.

[0006] III. Membrane Separation: This method utilizes the difference in permeation rates of different gas components within a membrane material to achieve separation. It offers significant advantages such as compact equipment, simple operation, low energy consumption, ease of modular scaling up or down, and no secondary pollution. However, traditional polymer membranes often face a trade-off between selectivity and permeability in CO2 / nitrogen or CO2 / methane separation, making it difficult to simultaneously meet the requirements of high purity (>99%) and high recovery rate. Furthermore, membrane materials are highly sensitive to impurities (such as oil mist, water vapor, and hydrogen sulfide), which can easily lead to performance degradation, typically requiring complex and sophisticated pretreatment systems. When treating high-flow-rate or high-concentration impurity gases, membrane methods offer limited improvement in product gas purity and often need to be coupled with other technologies (such as PSA). Summary of the Invention

[0007] The purpose of this invention is to provide a method for 14 An automated CO2 enrichment device and method for atmospheric samples measured by C is proposed to solve the problems existing in the prior art. Based on the characteristic that different gaseous substances in the atmosphere have different sublimation points, the device achieves selective separation and efficient enrichment of CO2 in the atmospheric samples by performing multi-stage low-temperature cooling, and further obtains pure CO2 gas by low-temperature collection.

[0008] To achieve the above objectives, the present invention provides the following solution:

[0009] This invention provides a method for 14 An automated CO2 enrichment device for atmospheric samples measured by C includes:

[0010] An atmospheric sample supply unit includes at least one sample bottle, at least one gas delivery pipe, and at least one gas delivery valve. The sample bottle, gas delivery pipe, and gas delivery valve are arranged in a group. The outlet of the sample bottle is connected to the inlet of the gas delivery pipe, the outlet of the gas delivery pipe is connected to the inlet of the gas delivery valve, and the outlet of the gas delivery valve serves as the outlet of the atmospheric sample supply unit.

[0011] An enrichment and purification unit includes at least two collectors connected in series. The inlet end of the first collector connected in series serves as the inlet end of the enrichment and purification unit, and the outlet end of the last collector connected in series serves as the outlet end of the enrichment and purification unit. A flow meter is installed at the inlet end of the enrichment and purification unit. When there are two collectors, the cooling device for the first collector connected in series is an ethanol-liquid nitrogen cold trap cup, and the cooling device for the second collector connected in series is a liquid nitrogen cold trap cup. When there are more than two collectors, the cooling devices for the first and last collectors connected in series are ethanol-liquid nitrogen cold trap cups, and the cooling devices for the other collectors connected in series are liquid nitrogen cold trap cups.

[0012] The metering unit includes a main pipe, the air inlet of the main pipe is the air inlet of the metering unit, the air outlet of the main pipe is the air outlet of the metering unit, the air inlet of the pressure gauge is connected to the main pipe, the air inlet of the metering tube is connected to the main pipe, and also includes a metering unit cold trap cup for holding the metering tube.

[0013] The collection unit includes a collection pipe, at least one test sample collection tube, at least one backup sample collection tube, and a cold trap cup for holding the test sample collection tube and the backup sample collection tube. The inlet end of the collection pipe is the inlet end of the collection unit, and the outlet end of the collection pipe is the outlet end of the collection unit. The number of test sample collection tubes and backup sample collection tubes is the same. The inlet end of the test sample collection tube is connected to the collection pipe. A test sample collection valve is provided between the test sample collection tube and the collection pipe. The inlet end of the backup sample collection tube is connected to the collection pipe. A backup sample collection valve is provided between the backup sample collection tube and the collection pipe.

[0014] The vacuum control unit includes a first vacuum gauge, a second vacuum gauge, a molecular pump, and a first-stage pump. The outlet of the collection unit is connected to the inlet of the fifth valve and the inlet of the seventh valve, respectively. The outlet of the fifth valve is connected to the inlet of the first vacuum gauge. The outlet of the first vacuum gauge is connected to the inlet of the ninth valve. The outlet of the second vacuum gauge is connected to the inlet of the first-stage pump. The outlet of the first-stage pump is connected to the inlet of the eighth valve. The outlet of the eighth valve is connected to the inlet of the molecular pump.

[0015] The outlet of the atmospheric sample supply unit is connected to the inlet of the first valve, the outlet of the first valve is connected to the inlet of the second valve, the outlet of the second valve is connected to the inlet of the enrichment and purification unit, the outlet of the enrichment and purification unit is connected to the inlet of the third valve, the outlet of the third valve is connected to the inlet of the quantitative unit, the outlet of the quantitative unit is connected to the inlet of the fourth valve, the outlet of the fourth valve is connected to the inlet of the collection unit, the outlet of the collection unit is connected to the inlet of the vacuum control unit with independent airflow control function, the outlet of the first valve is also connected to the inlet of the sixth valve, and the outlet of the sixth valve is connected to the inlet of the vacuum control unit.

[0016] The control and monitoring system includes a computer and a control box. The computer receives data from the enrichment and purification unit, the quantification unit, the collection unit, and the vacuum control unit in real time, and sends working step instructions to the control box. The control box then converts the instructions into action instructions to regulate the enrichment and purification unit, the quantification unit, the collection unit, and the vacuum control unit. The control box also regulates the opening and closing status of the first valve, the second valve, the third valve, the fourth valve, the fifth valve, the sixth valve, the seventh valve, the eighth valve, the ninth valve, the gas supply valve, the collection valve, the test sample collection valve, and the backup sample collection valve. The control and monitoring system also includes an automatic lifting unit for the cold trap cup that is directly controlled by the control box.

[0017] In one embodiment, the first valve, second valve, third valve, fourth valve, fifth valve, sixth valve, seventh valve, eighth valve, ninth valve, gas supply valve, test sample collection valve, and backup sample collection valve are solenoid valves.

[0018] In one embodiment, the automatic lifting unit for the cold trap cup includes an automatic lifting platform for the cold trap cup, which is configured to support the ethanol-liquid nitrogen cold trap cup, the liquid nitrogen cold trap cup, the metering unit cold trap cup, and the collection unit cold trap cup. The automatic lifting platform for the cold trap cup includes a support plate that supports the ethanol-liquid nitrogen cold trap cup, the liquid nitrogen cold trap cup, the metering unit cold trap cup, or the collection unit cold trap cup, and a cylinder that drives the support plate to rise and fall.

[0019] In one embodiment, the atmospheric sample supply unit includes 1 to 12 sample bottles, 1 to 12 gas delivery pipes, and 1 to 12 gas delivery valves. Each group includes one sample bottle, one gas delivery pipe, and one gas delivery valve. The gas outlet of the gas delivery valve is connected to the same gas outlet pipe, and the gas outlet of the gas outlet pipe serves as the gas outlet of the atmospheric sample supply unit.

[0020] In one embodiment, there are four collectors, including a primary collector, a secondary collector, a tertiary collector, and a quaternary collector, which are connected in series. The collection valves are controlled by a control box and are solenoid valves. There are four cold trap cups, including a primary ethanol-liquid nitrogen cold trap cup for holding the primary collector, a primary liquid nitrogen cold trap cup for holding the secondary collector, a secondary liquid nitrogen cold trap cup for holding the tertiary collector, and a secondary ethanol-liquid nitrogen cold trap cup for holding the quaternary collector.

[0021] In one embodiment, the number of test sample collection tubes is 1 to 12, and the number of backup sample collection tubes is 1 to 12.

[0022] In one embodiment, the outlet of the collection unit, the inlet of the fifth valve, and the inlet of the seventh valve are connected by a three-way pipe; the outlet of the seventh valve, the inlet of the second vacuum gauge, and the outlet of the sixth valve are connected by a three-way pipe; the outlet of the eighth valve, the outlet of the ninth valve, and the inlet of the molecular pump are connected by a three-way pipe; and the outlet of the first valve, the inlet of the second valve, and the inlet of the sixth valve are connected by a three-way pipe.

[0023] The present invention also provides a method for 14 An automated CO2 enrichment method for atmospheric samples measured by C, based on the above-mentioned method for... 14 An automated CO2 enrichment device for atmospheric samples measured by C includes the following steps:

[0024] S1. The system is evacuated. The gas inlet of the gas supply pipe is sealed. The control box issues an action command to open the first valve, second valve, third valve, fourth valve, fifth valve, sixth valve, seventh valve, eighth valve, ninth valve, gas supply valve, collection valve, test sample collection valve, and backup sample collection valve. The molecular pump and primary pump are started to evacuate the gas inside the system. The vacuum measurement values ​​of the first vacuum gauge and the second vacuum gauge are fed back to the computer. The vacuum measurement values ​​are kept below the standard preset value until the vacuum measurement values ​​drop to below the standard preset value. The computer then issues an instruction to the control box to execute the next step.

[0025] S2. Sample loading: Based on step S1, the control box issues an action command to first close the first valve, the second valve, and the gas supply valve. Then, the sample bottle is loaded, ensuring that its mouth is tightly closed. Next, the connection between the vacuum control unit and the collection unit is disconnected to avoid gas backflow. After the above steps are completed, the first valve and the gas supply valve are slowly opened. At this time, the vacuum control unit begins to perform a evacuation operation on the atmospheric sample supply unit, so that the air that enters the atmospheric sample supply unit during the sample bottle loading process passes through the sixth valve and is extracted from the system by the vacuum control unit until the vacuum degree measurement value of the vacuum control unit drops below the standard preset value.

[0026] S3. Enrichment and Purification: Based on step S2, the control box issues an action command to open the second valve, activating the automatic lifting unit of the cold trap cup. The ethanol-liquid nitrogen cold trap cup and the liquid nitrogen cold trap cup slowly rise until the corresponding collector is completely immersed in the ethanol-liquid nitrogen cold trap cup or the liquid nitrogen cold trap cup. After closing the sixth valve, the vacuum control unit is connected to the collection unit, and the molecular pump and the first-stage pump continue to pump air. Then, the port of the sample bottle is unsealed. The collector cooled by the ethanol-liquid nitrogen cold trap cup captures water vapor in the atmospheric sample and condenses it into ice. The collector cooled by the liquid nitrogen cold trap cup captures CO2 in the atmospheric sample and condenses it into dry ice. Other gas components that cannot be condensed into solids are extracted from the system through the vacuum control unit. During this period, the gas flow rate delivered from the atmospheric sample supply unit to the enrichment and purification unit is observed through the flow meter. The gas delivery valve is controlled to keep the gas flow rate at approximately 200 mL / min until the flow meter reading becomes 0 mL / min. The atmospheric sample CO2 in the sample bottle is enriched and purified. The computer issues a command to the control box to execute the next step.

[0027] S4. Carbon content determination: Based on step S3, the control box issues an action command to close the collection valve and the third valve. The liquid nitrogen cold trap cup slowly descends, separating it from the collection tube containing dry ice. The collection tube is then placed at room temperature, allowing the dry ice to naturally sublimate into CO2 gas. The quantitative unit cold trap cup is then raised until the quantitative tube is completely immersed in the quantitative unit cold trap cup. The fourth valve is closed, and the third valve is opened. The low-temperature quantitative tube converts CO2 gas into dry ice. After all the dry ice in the collection tube has been transferred to the quantitative tube, the third valve is closed again, and the quantitative unit cold trap cup descends, placing the quantitative tube at room temperature. The dry ice in the quantitative tube sublimates into CO2 gas. After the dry ice has completely sublimated, the pressure of the CO2 gas in the quantitative tube is measured. The carbon content of the enriched CO2 sample is calculated based on the pre-calibrated PM working curve of CO2 pressure versus mass.

[0028] S5. CO2 Collection: Based on step S4, the control box issues an action command to open the fifth valve until the vacuum measurement value of the first vacuum gauge drops below the standard preset value. Then, the fifth and seventh valves are closed. Next, a cold trap cup of the collection unit is raised until the corresponding test sample collection tube is completely immersed in the cold trap cup. Then, the fourth valve and the corresponding test sample collection valve are opened, allowing the CO2 gas in the metering tube to enter the low-temperature test sample collection tube. The collection continues until the carbon content of the CO2 in the test sample collection tube reaches 1... After mg, close the fourth valve and the corresponding test sample collection valve, and raise the cold trap cup of another collection unit until the corresponding backup sample collection tube is completely immersed in the cold trap cup of the collection unit. Then open the fourth valve and the corresponding backup sample collection valve to allow the remaining CO2 gas in the quantitative tube to enter the low-temperature backup sample collection tube until the backup sample collection tube collects the same amount of CO2 gas as the test sample collection tube. Then close the fourth valve and the corresponding backup sample collection valve. If the quantitative tube can no longer provide a sufficient amount of CO2 gas after the test sample collection tube has collected the CO2 gas, then the corresponding backup sample collection tube will collect all the collectable CO2 gas.

[0029] S6. System purification and vacuum status confirmation: Based on step S4 and while performing step S5, the control box issues an action command to close the first valve, then lower the ethanol liquid nitrogen cold trap cup to place the first-stage collector and the fourth-stage collector at room temperature, open the collection valve, and keep the inlet of the enrichment and purification unit connected to the second vacuum gauge until the vacuum level of the second vacuum gauge drops below the standard preset value.

[0030] In one embodiment, in steps S1, S2, and S5, the preset value of the vacuum level standard of the first vacuum gauge is... millibar, the preset value of the vacuum level standard for the second vacuum gauge is [value missing]. millibar; in step S6, the preset value of the vacuum level standard of the second vacuum gauge is... millibar.

[0031] In one embodiment, in step S1, when the number of available gas delivery tubes exceeds one, all gas delivery tubes are evacuated; in step S2, when the number of available sample bottles exceeds one, only one sample bottle is used at a time.

[0032] The present invention achieves the following technical effects compared to the prior art:

[0033] This invention provides a method for 14An automated CO2 enrichment device and method for atmospheric samples is described. This method utilizes the differences in the sublimation points of different gaseous substances in the atmosphere, employing multi-stage cryogenic cooling technology to achieve selective separation and efficient enrichment of CO2 in atmospheric samples. Furthermore, cryogenic collection technology is used to obtain purified CO2 gas, thus providing a basis for accurately measuring CO2 in the atmosphere. 14 The CO2 content provides support. In this invention, atmospheric sample vials are used to hold atmospheric samples collected from different areas. The vacuum control unit is responsible for extracting gas from the system to create a near-vacuum environment, thereby ensuring smooth flow of atmospheric samples and expelling water vapor and other non-CO2 gases separated from the atmospheric samples. The enrichment and purification unit uses temperature zone control to separate the dry ice formed by CO2 vaporization and sublimation from the ice crystals formed by water vapor sublimation. Subsequently, the dry ice is reduced back to CO2 gas, achieving CO2 enrichment and purification. During the process, gaseous substances that are not liquefied or sublimated are extracted and separated by the system. The quantification unit first uses low temperature to convert CO2 gas into dry ice while maintaining a low internal pressure to ensure that CO2 gas can continuously enter the quantification tube. After collection is complete, the inlet and outlet of the quantification unit are sealed, and the quantification unit is allowed to return to room temperature, allowing all the dry ice to sublimate into CO2 gas. The collected CO2 carbon content is calculated by measuring the gas pressure. The metering unit and the collection unit are then connected. The collection unit is kept at a low temperature. CO2 gas entering the collection unit is captured and converted into dry ice. The pressure inside the collection unit is always lower than the pressure inside the metering unit, allowing the CO2 gas to diffuse continuously. Quantitative collection of CO2 can be achieved based on changes in the pressure gauge reading. In this invention, direct action commands for all working units and valve states are issued by the control box. The computer can receive and analyze feedback signals from all working units, process them, and send commands to the control box for specific working units or valves based on the processing results. The entire process requires no manual operation, achieving full automation. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0035] Figure 1 This is a schematic diagram of a system structure without a cold trap cup, a metering unit cold trap cup, and a collection unit cold trap cup in an embodiment of the present invention;

[0036] Figure 2 This is a schematic diagram showing the positional relationship between the primary ethanol liquid nitrogen cold trap cup and the automatic lifting platform of the cold trap cup in an embodiment of the present invention;

[0037] Figure 3 This is a schematic diagram showing the positional relationship between the quantitative unit cold trap cup and the automatic lifting platform of the cold trap cup in an embodiment of the present invention.

[0038] Figure 4 This is a schematic diagram showing the positional relationship between the test sample collection tube / backup sample collection tube and the automatic lifting platform of the cold trap cup in an embodiment of the present invention.

[0039] Among them, 1. Atmospheric sample supply unit; 101. Sample bottle; 102. Gas delivery pipe; 103. Gas delivery valve;

[0040] 2. First valve;

[0041] 3. Second valve;

[0042] 4. Enrichment and purification unit; 401. Flow meter; 402. Primary collector; 403. Secondary collector; 404. Tertiary collector; 405. Quaternary collector; 406. Primary ethanol liquid nitrogen cold trap cup; 407. Primary liquid nitrogen cold trap cup; 408. Secondary liquid nitrogen cold trap cup; 409. Secondary ethanol liquid nitrogen cold trap cup; 410. Collection valve;

[0043] 5. Third valve;

[0044] 6. Metering unit; 601. Main pipe; 602. Pressure gauge; 603. Metering tube; 604. Metering unit cold trap cup;

[0045] 7. Fourth valve;

[0046] 8. Collection unit; 801. Test sample collection tube; 802. Backup sample collection tube; 803. Test sample collection valve; 804. Backup sample collection valve; 805. Collection unit cold trap cup;

[0047] 9. Fifth valve;

[0048] 10. First vacuum gauge;

[0049] 11. Molecular pump;

[0050] 12. The sixth valve;

[0051] 13. Second vacuum gauge;

[0052] 14. Primary pump;

[0053] 15. Seventh valve;

[0054] 16. Eighth valve;

[0055] 19. Ninth valve;

[0056] 20. Vacuum control unit;

[0057] 21. Control and monitoring system;

[0058] 22. Computer;

[0059] 23. Control box;

[0060] 24. Automatic lifting platform for cold trap cups. Detailed Implementation

[0061] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0062] It should be understood that the structures, proportions, sizes, etc., depicted in the accompanying drawings of this specification are merely for illustrative purposes to aid those skilled in the art and are not intended to limit the implementation conditions of the invention. Therefore, they have no substantial technical significance. Any modifications to the structure, changes in proportions, or adjustments to size, without affecting the effectiveness and purpose of the invention, should still fall within the scope of the technical content disclosed in this invention. In the description of this invention, it should be understood that the terms "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings. They are merely for the convenience of describing the invention and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the invention. Furthermore, the terms "first," "second," and "third," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance. Thus, features defined with "first," "second," etc., may explicitly or implicitly include one or more of those features. In the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0063] It should also be noted that in the embodiments of this application, the same reference numerals are used to denote the same component or the same part.

[0064] The purpose of this invention is to provide a method for 14An automated CO2 enrichment device and method for atmospheric samples measured by C is proposed to solve the problems existing in the prior art. Based on the characteristic that different gaseous substances in the atmosphere have different sublimation points, the device achieves selective separation and efficient enrichment of CO2 in the atmospheric samples by performing multi-stage low-temperature cooling, and further obtains pure CO2 gas by low-temperature collection.

[0065] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0066] Example 1

[0067] like Figures 1-4 As shown, the present invention provides a method for 14 An automated CO2 enrichment device for atmospheric samples measured by C, characterized in that it comprises:

[0068] An atmospheric sample supply unit 1 includes at least one sample bottle 101, at least one gas supply pipe 102, and at least one gas supply valve 103. The sample bottle 101, gas supply pipe 102, and gas supply valve 103 are arranged in a group. The outlet of the sample bottle 101 is connected to the inlet of the gas supply pipe 102, and the outlet of the gas supply pipe 102 is connected to the inlet of the gas supply valve 103. The outlet of the gas supply valve 103 serves as the outlet of the atmospheric sample supply unit 1.

[0069] The enrichment and purification unit 4 includes at least two collectors connected in series. The inlet end of the first collector connected in series serves as the inlet end of the enrichment and purification unit 4, and the outlet end of the last collector connected in series serves as the outlet end of the enrichment and purification unit 4. A flow meter 401 is installed at the inlet end of the enrichment and purification unit 4. When there are two collectors, the cooling device for the first collector connected in series is an ethanol-liquid nitrogen cold trap cup, and the cooling device for the second collector connected in series is a liquid nitrogen cold trap cup. When there are more than two collectors, the cooling devices for the first and last collectors connected in series are ethanol-liquid nitrogen cold trap cups, and the cooling devices for the other collectors connected in series are liquid nitrogen cold trap cups.

[0070] The metering unit 6 includes a main pipe 601, the air inlet of the main pipe 601 is the air inlet of the metering unit 6, the air outlet of the main pipe 601 is the air outlet of the metering unit 6, the air inlet of the pressure gauge 602 is connected to the main pipe 601, the air inlet of the metering tube 603 is connected to the main pipe 601, and also includes a metering unit cold trap cup 604 for holding the metering tube 603.

[0071] The collection unit 8 includes a collection pipe, at least one test sample collection pipe 801, at least one backup sample collection pipe 802, and a collection unit cold trap cup 805 for holding the test sample collection pipe 801 and the backup sample collection pipe 802. The air inlet end of the collection pipe is the air inlet end of the collection unit 8, and the air outlet end of the collection pipe is the air outlet end of the collection unit 8. The number of test sample collection pipes 801 and backup sample collection pipes 802 is the same. The air inlet end of the test sample collection pipe 801 is connected to the collection pipe. A test sample collection valve 803 is provided between the test sample collection pipe 801 and the collection pipe. The air inlet end of the backup sample collection pipe 802 is connected to the collection pipe. A backup sample collection valve 804 is provided between the backup sample collection pipe 802 and the collection pipe.

[0072] The vacuum control unit 20 includes a first vacuum gauge 10, a second vacuum gauge 13, a molecular pump 11, and a primary pump 14. The outlet of the collection unit 8 is connected to the inlet of the fifth valve 9 and the inlet of the seventh valve 15, respectively. The outlet of the fifth valve 9 is connected to the inlet of the first vacuum gauge 10. The outlet of the first vacuum gauge 10 is connected to the inlet of the ninth valve 19. The outlet of the second vacuum gauge 13 is connected to the inlet of the primary pump 14. The outlet of the primary pump 14 is connected to the inlet of the eighth valve 16. The outlet of the eighth valve 16 is connected to the inlet of the molecular pump 11.

[0073] The outlet of the atmospheric sample supply unit 1 is connected to the inlet of the first valve 2. The outlet of the first valve 2 is connected to the inlet of the second valve 3. The outlet of the second valve 3 is connected to the inlet of the enrichment and purification unit 4. The outlet of the enrichment and purification unit 4 is connected to the inlet of the third valve 5. The outlet of the third valve 5 is connected to the inlet of the quantitative unit 6. The outlet of the quantitative unit 6 is connected to the inlet of the fourth valve 7. The outlet of the fourth valve 7 is connected to the inlet of the collection unit 8. The outlet of the collection unit 8 is connected to the inlet of the vacuum control unit 20, which has an independent airflow control function. The outlet of the first valve 2 is also connected to the inlet of the sixth valve 12. The outlet of the sixth valve 12 is connected to the inlet of the vacuum control unit 20.

[0074] The control and monitoring system 21 includes a computer 22 and a control box 23. The computer 22 is used to receive data information from the enrichment and purification unit 4, the quantitative unit 6, the collection unit 8 and the vacuum control unit 20 in real time, and send working step instructions to the control box 23. The control box 23 then converts the instructions into action instructions to regulate the enrichment and purification unit 4, the quantitative unit 6, the collection unit 8 and the vacuum control unit 20. The control box 23 also regulates the opening and closing status of the first valve 2, the second valve 3, the third valve 5, the fourth valve 7, the fifth valve 9, the sixth valve 12, the seventh valve 15, the eighth valve 16, the ninth valve 19, the gas supply valve 103, the collection valve 410, the test sample collection valve 803 and the backup sample collection valve 804. The control and monitoring system 21 also includes an automatic lifting unit for the cold trap cup that is directly controlled by the control box 23.

[0075] The computer 22 and control box 23, and the control box 23 and each working unit, can be connected by wired or wireless means. Wired connections offer strong anti-interference capabilities and stable signal transmission, ensuring reliable transmission of command signals. However, wired connections require cabling and have certain site requirements, while wireless connections have lower site requirements and allow for flexible arrangement of working units. The computer 22 uses LabVIEW language to program the control program. In one embodiment, the first valve 2, second valve 3, third valve 5, fourth valve 7, fifth valve 9, sixth valve 12, seventh valve 15, eighth valve 16, ninth valve 19, gas supply valve 103, test sample collection valve 803, and backup sample collection valve 804 are solenoid valves. The solenoid valves can be directly controlled by the control box 23 to perform actions, with rapid response and reliable opening and closing. It is understood that the valves in this application can also be other types of valves that can be directly controlled by the control box 23.

[0076] In one embodiment, the automatic lifting unit for the cold trap cup includes an automatic lifting platform 24, which is configured to support the ethanol-liquid nitrogen cold trap cup, the liquid nitrogen cold trap cup, the metering unit cold trap cup 604, and the collection unit cold trap cup 805. The automatic lifting platform 24 includes a support plate supporting the ethanol-liquid nitrogen cold trap cup, the liquid nitrogen cold trap cup, the metering unit cold trap cup 604, or the collection unit cold trap cup 805, and a cylinder for lifting the support plate. The cylinder-driven method provides smooth start-stop and rapid response. It is understood that other devices capable of automatically lifting the cold trap cup can also be used in this application. The arrangement of the liquid nitrogen cold trap cup is exactly the same as that of the ethanol-liquid nitrogen cold trap cup.

[0077] In one embodiment, the atmospheric sample supply unit 1 includes 1 to 12 sample bottles 101, 1 to 12 gas supply pipes 102, and 1 to 12 gas supply valves 103. Each group includes one sample bottle 101, one gas supply pipe 102, and one gas supply valve 103. The gas outlet of the gas supply valve 103 is connected to the same gas outlet pipe, and the gas outlet of the gas outlet pipe serves as the gas outlet of the atmospheric sample supply unit 1.

[0078] In one embodiment, there are four collectors, including a primary collector 402, a secondary collector 403, a tertiary collector 404, and a quaternary collector 405. The primary collector 402, the secondary collector 403, the tertiary collector 404, and the quaternary collector 405 are connected in series. The collection valve 410 is controlled by the control box 23 and is a solenoid valve.

[0079] There are four cold trap cups, including a primary ethanol-liquid nitrogen cold trap cup 406 for holding the primary collector 402, a primary liquid nitrogen cold trap cup 407 for holding the secondary collector 403, a secondary liquid nitrogen cold trap cup 408 for holding the tertiary collector 404, and a secondary ethanol-liquid nitrogen cold trap cup 409 for holding the quaternary collector 405.

[0080] In one embodiment, the number of test sample collection tubes 801 is 1 to 12, and the number of backup sample collection tubes 802 is 1 to 12.

[0081] In one embodiment, the outlet of the collection unit 8, the inlet of the fifth valve 9, and the inlet of the seventh valve 15 are connected by a three-way pipe. The outlet of the seventh valve 15, the inlet of the second vacuum gauge 13, and the outlet of the sixth valve 12 are connected by a three-way pipe. The outlet of the eighth valve 16, the outlet of the ninth valve 19, and the inlet of the molecular pump 11 are connected by a three-way pipe. The outlet of the first valve 2, the inlet of the second valve 3, and the inlet of the sixth valve 12 are connected by a three-way pipe.

[0082] Example 2

[0083] like Figures 1-4 As shown, the present invention also provides a method for... 14 An automated CO2 enrichment method for atmospheric samples measured by C, based on the above-mentioned method for... 14 An automated CO2 enrichment device for atmospheric samples measured by C includes the following steps:

[0084] S1. The system is evacuated, and the inlet end of the gas supply pipe 102 is sealed. The control box 23 issues an action command to open the first valve 2, the second valve 3, the third valve 5, the fourth valve 7, the fifth valve 9, the sixth valve 12, the seventh valve 15, the eighth valve 16, the ninth valve 19, the gas supply valve 103, the collection valve 410, the test sample collection valve 803, and the backup sample collection valve 804. The molecular pump 11 and the first-stage pump 14 are started to evacuate the gas inside the system. The vacuum degree measurement signals of the first vacuum gauge 10 and the second vacuum gauge 13 are fed back to the computer 22. The vacuum degree measurement value is maintained until it drops below the standard preset value. The computer 22 then issues an instruction to the control box 23 to execute the next step.

[0085] S2. Sample loading: Based on step S1, the control box 23 issues an action command to first close the first valve 2, the second valve 3, and the gas supply valve 103. Then, the sample bottle 101 is loaded, ensuring that its mouth is tightly closed. Next, the connection between the vacuum control unit 20 and the collection unit 8 is disconnected to avoid gas backflow. After the above steps are completed, the first valve 2 and the gas supply valve 103 are slowly opened. At this time, the vacuum control unit 20 begins to perform a evacuation operation on the atmospheric sample supply unit 1, so that the air that enters the atmospheric sample supply unit 1 during the loading of the sample bottle 101 passes through the sixth valve 12 and is extracted from the system by the vacuum control unit 20 until the vacuum degree measurement value of the vacuum control unit 20 drops below the standard preset value.

[0086] S3. Enrichment and Purification: Based on step S2, control box 23 issues an action command to open the second valve 3. The automatic lifting unit of the cold trap cup is activated, and the ethanol-liquid nitrogen cold trap cup and the liquid nitrogen cold trap cup slowly rise until the corresponding collector is completely immersed in the ethanol-liquid nitrogen cold trap cup or the liquid nitrogen cold trap cup. After closing the sixth valve 12, the vacuum control unit 20 is connected to the collection unit 8, and the molecular pump 11 and the first-stage pump 14 continue to pump air. Then, the port of sample bottle 101 is unsealed. The collector cooled by the ethanol-liquid nitrogen cold trap cup captures water vapor in the atmospheric sample and condenses it into ice. The collector cooled by the liquid nitrogen cold trap cup captures CO2 in the atmospheric sample and condenses it into dry ice. Other gas components that cannot be condensed into solids are extracted from the system through the vacuum control unit 20. During this period, the gas flow rate delivered from the atmospheric sample supply unit 1 to the enrichment and purification unit 4 is observed through the flow meter 401. The gas delivery valve 103 is controlled to keep the gas flow rate at approximately 200 mL / min until the flow meter 401 reading becomes 0. At a rate of mL / min, the atmospheric CO2 sample in sample vial 101 is enriched and purified, and computer 22 sends a command to control box 23 to execute the next step.

[0087] S4. Carbon content determination: Based on step S3, control box 23 issues an action command to close collection valve 410 and third valve 5. The liquid nitrogen cold trap cup slowly descends, separating it from the collection tube containing dry ice. The collection tube is then placed at room temperature, allowing the dry ice to naturally sublimate into CO2 gas. Then, the quantitative unit cold trap cup 604 is raised until the quantitative tube 603 is completely immersed in the quantitative unit cold trap cup 604. The fourth valve 7 is closed, and the third valve 5 is opened. The low-temperature quantitative tube 603 converts CO2 gas into dry ice. After all the dry ice in the collection tube has been transferred to the quantitative tube 603, the third valve 5 is closed again, and the quantitative unit cold trap cup 604 descends, placing the quantitative tube 603 at room temperature, allowing the dry ice in the quantitative tube 603 to sublimate into CO2 gas. After the dry ice has completely sublimated, the pressure of the CO2 gas in the quantitative tube 603 is measured. The carbon content of the enriched CO2 sample is calculated based on the pre-calibrated PM working curve of CO2 pressure versus mass.

[0088] S5. CO2 Collection: Based on step S4, control box 23 issues an action command to open the fifth valve 9 until the vacuum measurement value of the first vacuum gauge 10 drops below the standard preset value. Then, the fifth valve 9 and the seventh valve 15 are closed. Subsequently, a cold trap cup 805 of the collection unit is raised until the corresponding test sample collection tube 801 is completely immersed in the cold trap cup 805. Then, the fourth valve 7 and the corresponding test sample collection valve 803 are opened, allowing the CO2 gas in the metering tube 603 to enter the low-temperature test sample collection tube 801. The collection continues until the carbon content of the CO2 in the test sample collection tube 801 reaches 1... After mg, close the fourth valve 7 and the corresponding test sample collection valve 803, and raise the other collection unit cold trap cup 805 until the corresponding backup sample collection tube 802 is completely immersed in the collection unit cold trap cup 805. Then open the fourth valve 7 and the corresponding backup sample collection valve 804 to allow the remaining CO2 gas in the metering tube 603 to enter the low-temperature backup sample collection tube 802 until the backup sample collection tube 802 collects the same amount of CO2 gas as the test sample collection tube 801. Then close the fourth valve 7 and the corresponding backup sample collection valve 804. If the metering tube 603 can no longer provide a sufficient amount of CO2 gas after the test sample collection tube 801 has collected it, then the corresponding backup sample collection tube 802 will collect all the collectable CO2 gas.

[0089] S6. System purification and vacuum status confirmation: Based on step S4 and while performing step S5, the control box 23 issues an action command to close the first valve 2, and then lowers the ethanol liquid nitrogen cold trap cup to place the first-stage collector 402 and the fourth-stage collector 405 at room temperature. The collection valve 410 is opened to maintain the connection between the gas inlet of the enrichment and purification unit 4 and the second vacuum gauge 13 until the vacuum level detection value of the second vacuum gauge 13 drops below the standard preset value.

[0090] In one embodiment, in steps S1, S2, and S5, the preset value of the vacuum level of the first vacuum gauge 10 is... The preset value of the vacuum level of the second vacuum gauge 13 is millibar. millibars. In step S6, the preset value of the vacuum level of the second vacuum gauge 13 is [value missing]. millibar.

[0091] In one embodiment, during step S1, when the number of available gas delivery tubes 102 exceeds one, all gas delivery tubes 102 are evacuated. During step S2, when the number of available sample vials 101 exceeds one, only one sample vial 101 is used at a time.

[0092] In the description of this application, it should be noted that, unless otherwise expressly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to fixed connections, detachable connections, or integral connections; they can refer to mechanical connections or electrical connections; they can refer to direct connections or indirect connections through an intermediate medium; and they can refer to the internal communication between two components. Those skilled in the art can understand the specific meaning of the above terms in this application based on the specific circumstances.

[0093] If this invention discloses or relates to components or structural parts that are fixedly connected to each other, then, unless otherwise stated, a fixed connection can be understood as: a fixed connection that can be detached (e.g., using bolts or screws), or a fixed connection that cannot be detached (e.g., riveting, welding). Of course, a fixed connection can also be replaced by an integral structure (e.g., manufactured in one piece using a casting process) (except where it is obviously impossible to use an integral molding process).

[0094] In addition, unless otherwise stated, the terms used in any of the technical solutions disclosed in this invention to indicate positional relationships or shapes include states or shapes that are similar to, close to, or approximate with those states or shapes.

[0095] Any component provided by this invention can be assembled from multiple individual components or can be a single component manufactured by a one-piece molding process.

[0096] Any adaptive changes made according to actual needs are within the scope of protection of this invention.

[0097] It should be noted that, for those skilled in the art, it is obvious that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered illustrative and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0098] Specific examples have been used to illustrate the principles and implementation methods of this invention. The descriptions of the above embodiments are only for the purpose of helping to understand the method and core ideas of this invention. Furthermore, those skilled in the art will recognize that, based on the ideas of this invention, there will be changes in the specific implementation methods and application scope. Therefore, the content of this specification should not be construed as a limitation of this invention.

Claims

1. A device for 14 A device for automated enrichment of atmospheric samples for CO2 measurement, characterized by: The application relates to an atmospheric sample supply unit (1), an enrichment and purification unit (4), a quantitative unit (6) and a collection unit (8). The enrichment and purification unit (4) comprises at least two collectors connected in series, the gas inlet end of the first collector connected in series is the gas inlet end of the enrichment and purification unit (4), the gas outlet end of the last collector connected in series is the gas outlet end of the enrichment and purification unit (4), the gas inlet end of the enrichment and purification unit (4) is provided with a flow meter (401), when the number of collectors is two, the refrigerating device of the first collector connected in series is an ethanol liquid nitrogen cold trap cup, the cooling device of the second collector connected in series is a liquid nitrogen cold trap cup, when the number of collectors is more than two, the refrigerating device of the first collector and the last collector connected in series is an ethanol liquid nitrogen cold trap cup, and the cooling device of the other collectors connected in series is a liquid nitrogen cold trap cup. The quantitative unit (6) comprises a main pipe (601), the gas inlet end of the main pipe (601) is the gas inlet end of the quantitative unit (6), the gas outlet end of the main pipe (601) is the gas outlet end of the quantitative unit (6), the gas inlet end of a pressure gauge (602) is communicated with the main pipe (601), the gas inlet end of a quantitative pipe (603) is communicated with the main pipe (601), and the quantitative unit (6) further comprises a quantitative unit cold trap cup (604) for containing the quantitative pipe (603). The collection unit (8) comprises a collection pipeline, at least one test sample collection pipe (801), at least one backup sample collection pipe (802) and a collection unit cold trap cup (805) for containing the test sample collection pipe (801) and the backup sample collection pipe (802), the gas inlet end of the collection pipeline is the gas inlet end of the collection unit (8), the gas outlet end of the collection pipeline is the gas outlet end of the collection unit (8), the number of the test sample collection pipe (801) and the backup sample collection pipe (802) is consistent, the gas inlet end of the test sample collection pipe (801) is communicated with the collection pipeline, a test sample collection valve (803) is arranged between the test sample collection pipe (801) and the collection pipeline, the gas inlet end of the backup sample collection pipe (802) is communicated with the collection pipeline, and a backup sample collection valve (804) is arranged between the backup sample collection pipe (802) and the collection pipeline. ​ The vacuum control unit (20) comprises a first vacuum gauge (10), a second vacuum gauge (13), a molecular pump (11) and a primary pump (14), the gas outlet end of the collection unit (8) is connected to the gas inlet end of the fifth valve (9) and the gas inlet end of the seventh valve (15) respectively, the gas outlet end of the fifth valve (9) is connected to the gas inlet end of the first vacuum gauge (10), the gas outlet end of the first vacuum gauge (10) is connected to the gas inlet end of the ninth valve (19), the gas outlet end of the second vacuum gauge (13) is connected to the gas inlet end of the primary pump (14), the gas outlet end of the primary pump (14) is connected to the gas inlet end of the eighth valve (16), and the gas outlet end of the eighth valve (16) is connected to the gas inlet end of the molecular pump (11); The gas outlet end of the atmospheric sample supply unit (1) is connected to the gas inlet end of the first valve (2), the gas outlet end of the first valve (2) is connected to the gas inlet end of the second valve (3), the gas outlet end of the second valve (3) is connected to the gas inlet end of the enrichment and purification unit (4), the gas outlet end of the enrichment and purification unit (4) is connected to the gas inlet end of the third valve (5), the gas outlet end of the third valve (5) is connected to the gas inlet end of the quantitative unit (6), the gas outlet end of the quantitative unit (6) is connected to the gas inlet end of the fourth valve (7), the gas outlet end of the fourth valve (7) is connected to the gas inlet end of the collection unit (8), the gas outlet end of the collection unit (8) is connected to the gas inlet end of the vacuum control unit (20) having the independent on-off air flow function, and the gas outlet end of the first valve (2) is also connected to the gas inlet end of the sixth valve (12), and the gas outlet end of the sixth valve (12) is connected to the gas inlet end of the vacuum control unit (20); The control monitoring system (21) comprises a computer (22) and a control box (23), the computer (22) is used for receiving data information from the enrichment and purification unit (4), the quantitative unit (6), the collection unit (8) and the vacuum control unit (20) in real time, and sending working step instructions to the control box (23), the control box (23) converts the instructions into action instructions, and controls the enrichment and purification unit (4), the quantitative unit (6), the collection unit (8) and the vacuum control unit (20), and the control box (23) also controls the opening and closing states of the first valve (2), the second valve (3), the third valve (5), the fourth valve (7), the fifth valve (9), the sixth valve (12), the seventh valve (15), the eighth valve (16), the ninth valve (19), the gas supply valve (103), the collection valve (410), the test sample collection valve (803) and the backup sample collection valve (804); The control monitoring system (21) further comprises a cold trap cup automatic lifting unit directly controlled by the control box (23).

2. The use according to claim 1, wherein the compound is a compound of formula (I) as defined in claim 1. 14 C An automated enrichment device for atmospheric samples of CO2, characterized in that: The first valve (2), the second valve (3), the third valve (5), the fourth valve (7), the fifth valve (9), the sixth valve (12), the seventh valve (15), the eighth valve (16), the ninth valve (19), the gas supply valve (103), the test sample collection valve (803) and the backup sample collection valve (804) are electromagnetic valves.

3. The method according to claim 1, wherein the method is used for 14 An automated atmospheric sample CO2 enrichment device for C measurement, characterized by: The cold trap cup automatic lifting unit comprises a cold trap cup automatic lifting table (24) corresponding to the ethanol liquid nitrogen cold trap cup, the liquid nitrogen cold trap cup, the quantitative unit cold trap cup (604) and the collection unit cold trap cup (805); The cold trap cup automatic lifting table (24) comprises a support plate supporting the ethanol liquid nitrogen cold trap cup, the liquid nitrogen cold trap cup, the quantitative unit cold trap cup (604) or the collection unit cold trap cup (805) and a gas cylinder driving the support plate to lift.

4. The method according to claim 1, wherein the method is used for 14 An automatic enrichment device for measuring atmospheric samples of CO2, characterized by: The atmospheric sample supply unit (1) comprises 1-12 sample bottles (101), 1-12 gas supply pipes (102) and 1-12 gas supply valves (103), each group comprising one sample bottle (101), one gas supply pipe (102) and one gas supply valve (103), the gas outlet ends of the gas supply valves (103) being communicated on the same gas outlet pipeline, and the gas outlet end of the gas outlet pipeline serving as the gas outlet end of the atmospheric sample supply unit (1).

5. The method according to claim 1, wherein the method is used for 14 An automatic enrichment device for measuring atmospheric samples of CO2, characterized by: The collector comprises four collectors, i.e., a first-stage collector (402), a second-stage collector (403), a third-stage collector (404) and a fourth-stage collector (405), which are sequentially communicated in series, the collection valve (410) being controlled by the control box (23), and the collection valve (410) being an electromagnetic valve. The cold trap cup comprises four cold trap cups, i.e., a first-stage ethanol liquid nitrogen cold trap cup (406) for containing the first-stage collector (402), a first-stage liquid nitrogen cold trap cup (407) for containing the second-stage collector (403), a second-stage liquid nitrogen cold trap cup (408) for containing the third-stage collector (404) and a second-stage ethanol liquid nitrogen cold trap cup (409) for containing the fourth-stage collector (405).

6. The method for 14 An automated atmospheric sample CO2 enrichment device as claimed in claim 1, characterized by: The number of the test sample collection pipes (801) is 1-12, and the number of the backup sample collection pipes (802) is 1-12.

7. The method according to claim 1, wherein the method is used for 14 An automatic enrichment device for measuring atmospheric samples of CO2, characterized by: The gas outlet end of the collection unit (8), the gas inlet end of the fifth valve (9) and the gas inlet end of the seventh valve (15) are communicated through a three-way pipeline; The gas outlet end of the seventh valve (15), the gas inlet end of the second vacuum gauge (13) and the gas outlet end of the sixth valve (12) are communicated through a three-way pipeline; The gas outlet end of the eighth valve (16), the gas outlet end of the ninth valve (19) and the gas inlet end of the molecular pump (11) are communicated through a three-way pipeline; The gas outlet end of the first valve (2), the gas inlet end of the second valve (3) and the gas inlet end of the sixth valve (12) are communicated through a three-way pipeline.

8. A method for 14 A method for automated enrichment of atmospheric samples for CO2 measurement, characterized by: The use according to any one of claims 1 to 7, wherein the compound is used in combination with at least one additional therapeutic agent. 14 A device for automated enrichment of atmospheric samples for C02measurement by C02measurement, comprising the steps of: S1, system pumping, the gas inlet end of the gas delivery pipe (102) is sealed, the control box (23) sends an action instruction, the first valve (2), the second valve (3), the third valve (5), the fourth valve (7), the fifth valve (9), the sixth valve (12), the seventh valve (15), the eighth valve (16), the ninth valve (19), the gas valve (103), the collection valve (410), the test sample collection valve (803) and the backup sample collection valve (804) are opened, the molecular pump (11) and the primary pump (14) are started to pump out the gas in the system, the vacuum degree measurement value signals of the first vacuum gauge (10) and the second vacuum gauge (13) are fed back to the computer (22), until the vacuum degree measurement value is reduced to below the standard preset value, the computer (22) issues an instruction to the control box (23) to execute the next step; S2, sample loading, on the basis of step S1, the control box (23) sends an action instruction, the first valve (2), the second valve (3) and the gas valve (103) are closed first, then the sample bottle (101) is loaded and its bottle opening is kept closed, then the vacuum control unit (20) is disconnected from the collection unit (8) to avoid the reverse flow of gas, after the above steps are completed, the first valve (2) and the gas valve (103) are slowly opened, at this time, the vacuum control unit (20) starts to pump the atmospheric sample supply unit (1), so that the air entering the atmospheric sample supply unit (1) during the loading of the sample bottle (101) passes through the sixth valve (12) and is pumped out of the system by the vacuum control unit (20), until the vacuum degree measurement value of the vacuum control unit (20) is reduced to below the standard preset value; S3, enrichment and purification, on the basis of step S2, the control box (23) sends an action instruction, the second valve (3) is opened, the cold trap cup automatic lifting unit is started, the ethanol liquid nitrogen cold trap cup and the liquid nitrogen cold trap cup are slowly lifted until the corresponding collector is completely immersed in the ethanol liquid nitrogen cold trap cup or the liquid nitrogen cold trap cup, the sixth valve (12) is closed, the vacuum control unit (20) is connected with the collection unit (8), and the molecular pump (11) and the primary pump (14) are continuously pumped, then the port of the sample bottle (101) is unsealed, the collector cooled by the ethanol liquid nitrogen cold trap cup captures the water vapor in the atmospheric sample to condense it into ice, the collector cooled by the liquid nitrogen cold trap cup captures the CO2 in the atmospheric sample to condense it into dry ice, other gas components that cannot be condensed into solids will be pumped out of the system by the vacuum control unit (20), during which the flow rate of the gas delivered from the atmospheric sample supply unit (1) to the enrichment and purification unit (4) is observed by the flowmeter (401), the gas flow rate is controlled to be 200 mL / min by the gas valve (103), until the flowmeter (401) shows 0 mL / min, the atmospheric sample CO2 in the sample bottle (101) is enriched and purified, the computer (22) issues an instruction to the control box (23) to execute the next step; S4, carbon content determination, on the basis of step S3, the control box (23) sends an action instruction, the collection valve (410) and the third valve (5) are closed, the liquid nitrogen cold trap cup is slowly lowered, and it is separated from the collection tube containing dry ice. Then the collection tube is placed at room temperature, and the dry ice in it is naturally sublimed into CO2 gas. Then the quantitative unit cold trap cup (604) is raised until the quantitative tube (603) is completely immersed in the quantitative unit cold trap cup (604). The fourth valve (7) is closed, and then the third valve (5) is opened. The low-temperature quantitative tube (603) converts CO2 gas into dry ice. When the dry ice in the collection tube is completely transferred to the quantitative tube (603), the third valve (5) is closed. The quantitative unit cold trap cup (604) is lowered, so that the quantitative tube (603) is placed in a room temperature environment. The dry ice in the quantitative tube (603) is sublimed into CO2 gas. After the dry ice is completely sublimed, the pressure of the CO2 gas in the quantitative tube (603) is measured. According to the pre-calibrated CO2 gas pressure-mass P-M working curve, the carbon content of the enriched CO2 sample is calculated; S5, CO2 collection, on the basis of step S4, the control box (23) sends an action instruction, opens the fifth valve (9), and the vacuum degree measured value of the first vacuum gauge (10) is reduced to below the standard preset value. Then the fifth valve (9) and the seventh valve (15) are closed. Then a collection unit cold trap cup (805) is raised until the corresponding test sample collection tube (801) is completely immersed in the collection unit cold trap cup (805). Then the fourth valve (7) and the corresponding test sample collection valve (803) are opened. The CO2 gas in the quantitative tube (603) enters the low-temperature test sample collection tube (801). When the carbon content of CO2 in the test sample collection tube (801) reaches 1 mg, the fourth valve (7) and the corresponding test sample collection valve (803) are closed. Another collection unit cold trap cup (805) is raised until the corresponding backup sample collection tube (802) is completely immersed in the collection unit cold trap cup (805). Then the fourth valve (7) and the corresponding backup sample collection valve (804) are opened. The remaining CO2 gas in the quantitative tube (603) enters the low-temperature backup sample collection tube (802). Until the backup sample collection tube (802) collects the same amount of CO2 gas as the test sample collection tube (801), the fourth valve (7) and the corresponding backup sample collection valve (804) are closed. If the test sample collection tube (801) is collected, the quantitative tube (603) cannot provide enough CO2 gas, so the corresponding backup sample collection tube (802) will collect all the collectable CO2 gas. S6, system purification and vacuum state confirmation, on the basis of step S4 and at the same time of step S5, the control box (23) sends an action instruction to close the first valve (2), then let the ethanol liquid nitrogen cold trap cup drop, make the first collector (402) and the fourth collector (405) be in the room temperature environment, open the collection valve (410), keep the communication state of the gas inlet end of the enrichment purification unit (4) and the second vacuum gauge (13), until the vacuum degree detection value of the second vacuum gauge (13) is reduced below the standard preset value.

9. The method for 14 A method for automated enrichment of atmospheric samples of CO2 measured by C, characterized by: In step S1, step S2 and step S5, the vacuum degree standard preset value of the first vacuum gauge (10) is millibar, and the vacuum degree standard preset value of the second vacuum gauge (13) is millibar. In step S6, the vacuum degree standard preset value of the second vacuum gauge (13) is millibar.

10. The method for 14 A method for automated enrichment of atmospheric samples of CO2 measured by C, characterized by: In step S1, when the number of available gas delivery tubes (102) is more than one, all the gas delivery tubes (102) are pumped; In step S2, when the number of available sample bottles (101) is more than one, only one sample bottle (101) is used at the same time.

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