Device and method for monitoring ozone depletion substances and hydrofluorocarbon in atmosphere

Abstract

The invention relates to a device and a method for monitoring ozone depletion substances and hydrofluorocarbon in atmosphere, and belongs to the technical field of chromatography-mass spectrometry. According to the scheme, the device mainly comprises a target object trapping pipeline which comprises a trapping module, and the target object trapping pipeline is used for trapping target objects in sample gas through the trapping module and removing interferents; the multi-stage analysis pipeline comprises an analysis carrier gas inlet and a temporary storage column switching module; the focusing analysis module is used for carrying out focusing and chromatographic separation on the target object and then carrying out detection; the analysis carrier gas inlet is connected with the focusing analysis module through the trapping switching module and the temporary storage column switching module in sequence, and the multi-stage analysis pipeline is used for conveying target objects analyzed in batches to the focusing analysis module.

Description

Technical Field

[0001] The invention belongs to the technical field of chromatography-mass spectrometry analysis, and specifically relates to a device and method for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere. Background Art

[0002] Ozone (O3) is concentrated in the stratosphere of the atmosphere, with the highest concentration at 15km to 30km above the ground. This part is called the ozone layer. It can absorb most of the ultraviolet rays in sunlight, especially UVB ultraviolet rays that are harmful to organisms, thus preventing humans and other organisms from being harmed by these ultraviolet rays. Scientists have discovered that there are gas components in the air that destroy the ozone layer. These substances mainly include ozone-depleting substances and fluorinated greenhouse gases. Ozone-depleting substances, also known as Ozone-Depleting Substances, or ODS for short, include six major types of halogenated hydrocarbons, such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), halons, carbon tetrachloride (CCl4), methyl chloroform (CH3CCl3), and methyl bromide (CH3Br). Fluorinated greenhouse gases, referred to as F-gas, include four of the seven types of greenhouse gases included in the Kyoto Protocol of the United Nations Framework Convention on Climate Change (UNFCCC), namely hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), sulfur hexafluoride (SF6) and nitrogen trifluoride (NF3). Especially in the face of multi-item and multi-sample testing, there are generally problems such as low dosing efficiency, large dosing errors and even dosing errors.

[0003] At present, these compounds that destroy the ozone layer are mainly produced by industry and used and produced in the fields of refrigeration, cleaning and foaming. In order to protect the human living environment, countries around the world signed the Montreal Protocol in 1987 to restrict the use and emission of ozone-depleting substances and chlorofluorocarbons on a global scale. Therefore, it is necessary to monitor the concentrations of ozone-depleting substances and fluorinated greenhouse gases in the atmospheric environment mentioned in the Montreal Protocol. However, the content of these substances in the atmospheric environment is at the ppt (parts per trillion) level, and the concentration of some substances is less than 1ppt, so the detection limit and accuracy of the monitoring system are extremely high. At present, this type of equipment covers fewer components, and it is difficult to accurately separate the target from the sample, resulting in a large deviation in the test results.

[0004] The patent with the publication number CN113834884A discloses an online monitoring system for ozone depletion substances, and the technical solution adopted is "a semiconductor refrigeration combined with a super-strong adsorbent cold trap online sampling pre-concentration system, and an online low-temperature Nafion membrane dehydration device is connected to the sample injection end, and the sampling pre-concentration system is connected to the gas chromatograph and the quadrupole mass spectrometer in turn, and the pre-concentration and gas chromatograph and quadrupole mass spectrometer workstation computer are respectively connected." However, this detection system is only equipped with a nafion membrane dehydration device at the sample, and the water at the carrier gas end cannot be removed, and the ambient air needs to be pressurized to complete continuous sampling, and this system only covers the monitoring of 21 ozone depletion substances. The patent with the publication number CN116577446A discloses a detection method, device and storage medium for ozone depletion substances in the air; in this set of devices, since the Nafion tube dehydration technology is used at the front end, pressurized sampling is required, making the sampling structure more complicated. The patent with publication number CN116465993A discloses a method for identifying and evaluating the ecological environmental damage of controlled ozone-depleting substances; this method is only for identifying and evaluating the ecological environmental damage of ozone-depleting substances and is not applicable to qualitative and quantitative analysis and detection of ozone-depleting substances and hydrofluorocarbons in ambient air. The patent with publication number CN115494172A discloses a method and device for determining ozone-depleting substances and fluorinated greenhouse gases in the atmosphere. This method and device can only analyze and measure high-concentration samples and do not have a concentration effect. Therefore, it is impossible to accurately analyze low-concentration samples qualitatively and quantitatively.

[0005] In summary, it is difficult for the detection equipment in the prior art to accurately separate the target object from the sample, resulting in a large deviation in the detection results. Summary of the invention

[0006] In view of the above analysis, in order to solve the above problems, the first aspect of the present invention provides a monitoring device for ozone depleting substances and hydrofluorocarbons in the atmosphere, comprising:

[0007] A target object capture pipeline, including a capture module, the target object capture pipeline is used to capture the target object in the sample gas and remove interfering substances through the capture module;

[0008] A multi-stage analytical pipeline, including an analytical carrier gas inlet and a temporary column switching module; and

[0009] Focusing analysis module, used to focus and chromatographically separate the target for detection;

[0010] The analytical carrier gas inlet is connected to the focusing analysis module through the capture switching module and the temporary column switching module in sequence, and the multi-stage analytical pipeline is used to transport the target objects to be analyzed in batches to the focusing analysis module;

[0011] The temporary storage column switching module has a first state and a second state. When in the first state, the capture module is connected to the focusing analysis module through the temporary storage column. When in the second state, the capture module is directly connected to the focusing analysis module without passing through the temporary storage column. The temporary storage column has a chromatographic separation capability.

[0012] The capture switching module has a first state and a second state. When in the first state, the analytical carrier gas inlet is connected to the temporary storage column switching module through the capture module. When in the second state, the analytical carrier gas inlet is directly connected to the temporary storage column switching module without passing through the capture module.

[0013] In some embodiments, a dehydration module is further included. The dehydration module is disposed on the target object capture pipeline, and the dehydration module is used to dehydrate the sample gas before the sample gas enters the capture module.

[0014] In some embodiments, the dehydration module includes a first dehydration module and a second dehydration module;

[0015] The target object capture pipeline further includes an automatic sampler, a pump and a first flow meter, wherein the automatic sampler is used to be connected to the Suma tank, the pump is arranged at one end close to the outlet of the target object capture pipeline, and the automatic sampler is connected to the pump through the first dehydration module, the second dehydration module, the capture module and the first flow meter in sequence;

[0016] The focusing analysis module includes a focusing module, a chromatographic separation module and a detection unit connected in sequence. The focusing module is used to focus on the target object and input the target object into the chromatographic separation module. The chromatographic separation module is used to perform chromatographic separation on the target object and then input it into the detection unit. The inlet of the focusing module is connected to the multi-stage analysis pipeline.

[0017] In some embodiments, it further includes a pair of multiple selector valves, a first switching valve, and a second switching valve;

[0018] The one-to-many selection valve has a fixed interface and a plurality of selection interfaces, and the one-to-many selection valve is configured to enable one of the fixed interfaces to communicate with one of the selection interfaces;

[0019] The automatic sampler is connected to the selection interface S7 of the one-to-many selection valve through the first dehydration module, the fixed interface is connected to the interface P1 of the first switching valve, the two ends of the second dehydration module are respectively connected to the interfaces P2 and P8 of the first switching valve, the two ends of the capture module are respectively connected to the interfaces P3 and P6 of the first switching valve, the interface P7 of the first switching valve is connected to the pump through the first flow meter, the interface P5 of the first switching valve is connected to the analytical carrier gas inlet, the interface P4 of the first switching valve is connected to the interface P5 of the second switching valve, the two ends of the temporary storage column are respectively connected to the interfaces P6 and P7 of the second switching valve, and the interface P8 of the second switching valve is connected to the focusing module;

[0020] The first switching valve has an A state and a B state. When the first switching valve is in the A state, only its interfaces P1 and P8 are connected, interfaces P2 and P3 are connected, interfaces P4 and P5 are connected, and interfaces P6 and P7 are connected. When the first switching valve is in the B state, only its interfaces P1 and P2 are connected, interfaces P3 and P4 are connected, interfaces P5 and P6 are connected, and interfaces P7 and P8 are connected.

[0021] The second switching valve has an A state and a B state. When the second switching valve is in the A state, only its interfaces P6 and P7 are connected, and interfaces P5 and P8 are connected. When the second switching valve is in the B state, only its interfaces P5 and P6 are connected, and interfaces P7 and P8 are connected.

[0022] In some embodiments, it further includes a forward and reverse flushing pipeline, which is connected to the target object capture pipeline and is used to introduce inert gas into the target object capture pipeline from two directions, so that the capture module captures the target object remaining in the target object capture pipeline;

[0023] The forward and reverse flushing pipeline has a first state and a second state. When in the first state, the inert gas passes through the second dehydration module and the capture module in sequence; when in the second state, the inert gas passes through the capture module and the second dehydration module in sequence.

[0024] In some embodiments, the forward and reverse flushing pipeline includes an inert gas inlet, a first three-way valve and a second three-way valve;

[0025] One end of the first three-way valve is connected to one end of the second three-way valve, the other two ends of the first three-way valve are respectively connected to the inert gas inlet and the selection interface S5 of the one-to-many selection valve, and the other two ends of the second three-way valve are respectively connected to the interface P7 of the first switching valve and the first flow meter;

[0026] The first three-way valve is configured to connect the inert gas inlet to the one-to-multiple selector valves or to connect the inert gas inlet to the second three-way valve;

[0027] The second three-way valve is configured to connect the first three-way valve to the first switching valve or to connect the first switching valve to the first flow meter.

[0028] An embodiment of the present invention further provides a method for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere, using the device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere described in any embodiment of the first aspect, the method comprising the following steps:

[0029] S1. Pass the sample gas into the capture pipeline, and capture the target in the sample gas through the capture module;

[0030] S2, the temporary storage column switching module is switched to the first state, the capture switching module is switched to the first state, the capture module is set to a first given temperature to parse out the first part of the target, the carrier gas is introduced into the carrier gas inlet and flows into the capture module and the temporary storage column in sequence, wherein the temperature of the temporary storage column is set to a second given temperature, so that the first part of the target remains in the temporary storage column, and the first part of the target is chromatographed by the temporary storage column;

[0031] S3, the temporary column switching module is switched to the second state, the capture switching module is switched to the first state, the capture module is set to a third given temperature to parse out the second part of the target, a carrier gas is introduced into the carrier gas inlet to flow through the capture module and the second part of the target is transported to the focusing analysis module;

[0032] S4, the temporary storage column switching module is switched to the first state, the capture switching module is switched to the second state, a carrier gas is introduced into the carrier gas inlet to flow through the temporary storage column and the first part of the target is transported to the focusing analysis module;

[0033] The first given temperature is lower than the third given temperature.

[0034] The second embodiment of the present invention provides a device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere, comprising:

[0035] A target object capture pipeline, comprising a capture module, wherein the capture module is used to capture the target object in the sample gas;

[0036] Focusing analysis module, used to focus and chromatographically separate the target for detection;

[0037] An analytical pipeline, comprising an analytical carrier gas inlet and a capture switching module, wherein the capture switching module is used to connect two ends of the capture module to the analytical carrier gas inlet and the focusing analysis module respectively;

[0038] A purification pipeline, wherein the purification pipeline is used to remove interfering substances of the target object in the capture module, and the purification pipeline includes a capillary chromatographic column purification module, wherein the capillary chromatographic column purification module is used to remove interfering substances in the target object, and the purification pipeline has a first state and a second state. When in the first state, the inert gas passes through the capture module and the capillary chromatographic column purification module in sequence; when in the second state, the inert gas passes through the capillary chromatographic column purification module and the capture module in sequence.

[0039] In some embodiments, a dehydration module is further included. The dehydration module is disposed on the target object capture pipeline, and the dehydration module is used to dehydrate the sample gas before the sample gas enters the capture module.

[0040] In some embodiments, the dehydration module includes a first dehydration module and a second dehydration module;

[0041] The target object capture pipeline also includes an automatic sampler, a pump and a first flow meter. The automatic sampler is used to be connected to the Summa tank. The pump is arranged at one end close to the outlet of the target object capture pipeline. The automatic sampler is connected to the pump through the first dehydration module, the second dehydration module, the capture module and the first flow meter in sequence.

[0042] The focusing analysis module includes a focusing module, a chromatographic separation module and a detection unit connected in sequence. The focusing module is used to focus on the target object and input the target object into the chromatographic separation module. The chromatographic separation module is used to perform chromatographic separation on the target object and then input it into the detection unit. The inlet of the focusing module is connected to the multi-stage analysis pipeline.

[0043] In some embodiments, it further includes a pair of multiple selector valves, a first switching valve, and a second switching valve;

[0044] The one-to-many selection valve has a fixed interface and a plurality of selection interfaces, and the one-to-many selection valve is configured to enable one of the fixed interfaces to communicate with one of the selection interfaces;

[0045] The automatic sampler is connected to the selection interface S7 of the one-to-many selection valve through the first dehydration module, the fixed interface is connected to the interface P1 of the first switching valve, the interface P2 of the first switching valve is connected to the interface P5 of the second switching valve, the two ends of the capture module are respectively connected to the interfaces P3 and P6 of the first switching valve, the interface P4 of the first switching valve is connected to the focusing module, the interface P5 of the first switching valve is connected to the analytical carrier gas inlet, the interface P7 of the first switching valve is connected to the pump through the first flowmeter, the interface P8 of the first switching valve is connected to the interface P2 of the second switching valve, the two ends of the second dehydration module are respectively connected to the interfaces P3 and P4 of the second switching valve, and the two ends of the capillary column purification module are respectively connected to the interfaces P6 and P1 of the second switching valve;

[0046] The first switching valve has an A state and a B state. When the first switching valve is in the A state, only its interfaces P1 and P8 are connected, interfaces P2 and P3 are connected, interfaces P4 and P5 are connected, and interfaces P6 and P7 are connected. When the first switching valve is in the B state, only its interfaces P1 and P2 are connected, interfaces P3 and P4 are connected, interfaces P5 and P6 are connected, and interfaces P7 and P8 are connected.

[0047] The second switching valve has an A state and a B state. When the second switching valve is in the A state, only its interfaces P1 and P6 are connected, interfaces P2 and P3 are connected, and interfaces P4 and P5 are connected. When the second switching valve is in the B state, only its interfaces P1 and P2 are connected, interfaces P4 and P5 are connected, and interfaces P5 and P6 are connected.

[0048] In some embodiments, the purge line includes an inert gas inlet, a first three-way valve, and a second three-way valve;

[0049] One end of the first three-way valve is connected to one end of the second three-way valve, the other two ends of the first three-way valve are respectively connected to the inert gas inlet and the selection interface S5 of the one-to-many selection valve, and the other two ends of the second three-way valve are respectively connected to the interface P7 of the first switching valve and the first flow meter;

[0050] The first three-way valve is configured to connect the inert gas inlet to the one-to-multiple selector valves or to connect the inert gas inlet to the second three-way valve;

[0051] The second three-way valve is configured to connect the first three-way valve to the first switching valve or to connect the first switching valve to the first flow meter.

[0052] An embodiment of the present invention further provides a method for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere, using the device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere described in any embodiment of the second aspect, and the method comprises the following steps:

[0053] S1. Pass the sample gas into the capture pipeline, and capture the target in the sample gas through the capture module;

[0054] S2, the purification pipeline is switched to the first state, the temperature of the capillary column purification module is set to the fourth given temperature, the temperature of the capture module is set to the fifth given temperature to resolve the interfering substances and part of the target substances with a boiling point below the fifth given temperature, an inert gas is introduced into the purification pipeline to flow into the capture module and the capillary column purification module in sequence, the resolved interfering substances and part of the target substances are brought into the capillary column purification module, chromatographic separation is performed through the capillary column purification module until the interfering substances are eliminated, and the introduction of the inert gas is stopped;

[0055] S3, the purification pipeline is switched to the second state, the temperature of the capillary column purification module is set to the sixth given temperature to resolve the part of the target, the temperature of the capture module is set to the seventh given temperature, and an inert gas is introduced into the purification pipeline to bring the part of the target back to the capture module to complete the recovery of the part of the target, wherein the seventh given temperature is lower than the fifth given temperature;

[0056] S4, the capture switching module is switched to the capture module connected to the analysis pipeline, the temperature of the capture module is set to the eighth given temperature, the carrier gas is introduced into the carrier gas inlet to flow through the capture module and transport the target object to the focusing analysis module. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] In order to more clearly illustrate the embodiments of this specification or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the embodiments of this specification. For ordinary technicians in this field, other drawings can also be obtained based on these drawings.

[0058] Figure 1 A schematic diagram of the structure of a device for monitoring ozone-depleting substances and hydrofluorocarbons in the atmosphere provided in Example 1 of the present invention;

[0059] Figure 2 A schematic diagram of the structure of a device for monitoring ozone-depleting substances and hydrofluorocarbons in the atmosphere provided in Embodiment 3 of the present invention;

[0060] Figure 3 This is a chromatogram of steps SC1 to SC8 of Example 4 of the present invention;

[0061] Figure 4 This is a chromatographic analysis diagram of steps SD1 to SD10 in Example 4 of the present invention. DETAILED DESCRIPTION

[0062] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0063] Embodiment 1

[0064] The embodiment of the present invention provides a monitoring device 100 for ozone depleting substances and hydrofluorocarbons in the atmosphere, such as Figure 1 As shown, including:

[0065] The target capture pipeline, the multi-stage analysis pipeline and the focusing analysis module, the target capture pipeline includes the capture module 203, and the target capture pipeline is used to capture the target in the sample gas and remove interferences through the capture module 203. The capture module 203 is used to remove other interferences such as carbon dioxide, oxygen, xenon, argon, etc. in the gas. The multi-stage analysis pipeline includes an analysis carrier gas inlet 304 and a temporary column switching module. The focusing analysis module is used to focus and chromatographically separate the target and then detect it. The analysis carrier gas inlet 304 is, for example, an electronic pressure controller EPC.

[0066] The analytical carrier gas inlet is connected to the focusing analysis module through the capture switching module and the temporary column switching module in sequence, and the multi-stage analytical pipeline is used to transport the target objects to be analyzed in batches to the focusing analysis module;

[0067] The temporary storage column switching module has a first state and a second state. When in the first state, the capture module is connected to the focusing analysis module through the temporary storage column 301. When in the second state, the capture module is directly connected to the focusing analysis module without passing through the temporary storage column 301, wherein the temporary storage column 301 has chromatographic separation capability. The temporary storage column is used to temporarily store the target object and transport the target object to the focusing analysis module, wherein the target object refers to the target gas.

[0068] The capture switching module has a first state and a second state. In the first state, the analytical carrier gas inlet 304 is connected to the temporary storage column switching module through the capture module 203. In the second state, the analytical carrier gas inlet is directly connected to the temporary storage column switching module without passing through the capture module 203.

[0069] In some embodiments, a dehydration module is further included. The dehydration module is disposed on the target object capture pipeline, and the dehydration module is used to dehydrate the sample gas before the sample gas enters the capture module.

[0070] In some embodiments, the dehydration module includes a first dehydration module 201 and a second dehydration module 202. The primary dehydration module 201 and the secondary dehydration module 202 are used to dehydrate the collected gas. Through the dehydration module 201, the secondary dehydration module 202 and the capture module 203, the sample gas is dehydrated, enriched, and carbon dioxide is removed. Compared with the three-stage cold trap pre-concentrator, there is an additional first-stage dehydration cold trap, which has better water removal efficiency, higher target compound recovery rate, and better peak shape. Optionally, the multi-stage analysis pipeline in some embodiments is equipped with a nafion tube, and the carrier gas and the sample can be dehydrated again to ensure that the interference of water is removed to the maximum extent while avoiding the need for a pressurizing device to collect ambient air, so that the peak time and peak shape are more stable, and the structure can be relatively simpler.

[0071] The target object capture pipeline also includes an automatic sampler 101, a pump 109 and a first flowmeter 105. The automatic sampler 101 is used to connect to the Summa tank. The pump 109 is arranged at one end close to the outlet of the target object capture pipeline. The automatic sampler 101 is connected to the pump 109 through the first dehydration module 201, the second dehydration module 202, the capture module 203, and the first flowmeter 105 in sequence. The automatic sampler 101 is used to collect sample gases from different Suma tanks according to demand, wherein the Suma tanks are pre-loaded with sample gases; the automatic sampler 101 can provide two ways for sampling. First, the Suma tank can be directly connected to different sample positions provided by the pre-concentration valve body, and the gas in the Suma tanks connected to these sample positions can be collected according to demand. Alternatively, the automatic sampler 101 can be connected through pre-concentration, and the automatic sampler 101 can be connected to more Suma tanks at the same time. The Suma tanks containing the gas can be hung on the automatic sampler 101 according to demand, and then the gas can be collected from the Suma tanks corresponding to the sample position of the sampler, so as to improve the monitoring and analysis efficiency and meet the demand for continuous sampling of gases from different Suma tanks. Optionally, the first flowmeter 105 is, for example, a nitrogen sampling flowmeter.

[0072] Optionally, the primary dehydration module 201 uses a polytetrafluoroethylene empty tube, the secondary dehydration module 202 uses a polytetrafluoroethylene empty tube, and the capture module 203 is a stainless steel liner filled with tenax and carbon molecular sieve composite filler.

[0073] The focusing analysis module includes a focusing module 302, a chromatographic separation module and a detection unit 501 connected in sequence. The focusing module 302 is used to focus the target and input the target into the chromatographic separation module. The chromatographic separation module includes a chromatographic column 401, a condenser and a heat exchanger; wherein the condenser and the heat exchanger 403 are connected to the chromatographic column 401, one end of the chromatographic column 401 is connected to the detection unit, and the other end of the chromatographic column 401 is connected to the focusing module 302 through an inert two-way. The chromatographic separation module inputs the detection unit 501 after chromatographic separation of the target, and the inlet of the focusing module 302 is connected to the multi-stage analysis pipeline. Specifically, the focusing analysis module is used to focus the target at low temperature through the focusing module 302, and at the same time control the program temperature rise so that the target flows into the detection unit 501 one by one; it should be noted that the low temperature here refers to an environment of -15℃ to 15℃. The detection unit 501 includes an ion source and an ion multiplier. The ion source fragments the target molecule into ions; the ion fragments enter the ion multiplier to form a current signal, and the ion multiplier is used to receive and amplify the current signal to form a chromatogram, which facilitates qualitative and quantitative analysis.

[0074] Optionally, in some embodiments, the embodiments of the present invention further include a signal acquisition and processing control unit, which is connected to other units and is used to acquire, process and reverse control the temperature, pressure, analog signals, etc. of other units. (It should be noted that reverse control refers to sending instructions to other units through the control unit to control them. These instructions can be automatic control based on the collected data, or they can be control instructions manually input by the operator. Through reverse control, the control unit can realize real-time monitoring and adjustment of the system to ensure the normal operation and stability of the system. For example, the temperature of each module such as the capture module 203 is controlled through reverse control.)

[0075] The embodiment of the present invention realizes step-by-step temperature analysis of the target through the combination of the capture switching module and the temporary column switching module. The collected gas is cooled and then heated to analyze the target with different boiling points through step-by-step temperature analysis. In view of the difficulty of separating the target, step-by-step temperature analysis and temporary column design are adopted here. The refrigeration method adopts the deep freezing mode, and the heating adopts the hot nitrogen chamber mode to quickly heat up. According to the difference in boiling point of the target, it is divided into two stages of analysis, and the full volume enters the chromatographic separation module in batches, so as to obtain higher separation degree and better peak shape between the target.

[0076] It should be understood that the two-stage analysis is performed, that is, the low-boiling target is first analyzed and temporarily stored in the temporary storage column 301, and then the high-boiling target is analyzed and entered into the chromatographic separation module, and then the target in the temporary storage column 301 enters the chromatographic separation module. Since the temporary storage column 301 also uses a chromatographic column with chromatographic separation capability, it is equivalent to pre-treating the low-boiling target, and the low-boiling target passes through the temporary storage column and the chromatographic column 401 of the chromatographic separation module. The total length of the chromatographic column is longer, which is conducive to separating the difficult-to-remove interfering substances mixed in the low-boiling target, thereby making the overall separation effect better.

[0077] In some embodiments, the present invention further includes a pair of multiple selector valves 102 , a first switching valve 103 , and a second switching valve 104 ;

[0078] The one-to-many selector valve 102 has a fixed interface and multiple selector interfaces, and the one-to-many selector valve 102 is configured to enable one of the fixed interfaces to be connected to one of the selector interfaces. Specifically, the one-to-many selector valve 102 is, for example, an eight-input and one-output selector valve, and the multiple selector interfaces include, for example, S1 to S8 flow paths, S1 and S8 are dead plugs, S2 is an exhaust port, S3 is a spare interface, and can also be used to directly connect to a Suma tank, S4 is an internal standard gas, S5 is an input interface for blank helium, S6 is an environmental standard gas, and S7 is an interface for connecting a target object capture pipeline.

[0079] The automatic sampler 101 is connected to the selection interface S7 of the one-to-many selection valve through the first dehydration module 201, the fixed interface S0 is connected to the interface P1 of the first switching valve, the two ends of the second dehydration module 202 are respectively connected to the interfaces P2 and P8 of the first switching valve, the two ends of the capture module 203 are respectively connected to the interfaces P3 and P6 of the first switching valve, the interface P7 of the first switching valve is connected to the pump 109 through the first flowmeter 105, the interface P5 of the first switching valve is connected to the analytical carrier gas inlet 304, the interface P4 of the first switching valve is connected to the interface P5 of the second switching valve, the two ends of the temporary storage column 301 are respectively connected to the interfaces P6 and P7 of the second switching valve, and the interface P8 of the second switching valve is connected to the focusing module. Optionally, in some embodiments, the Nafion tube is arranged between the interface P4 of the first switching valve and the interface P5 of the second switching valve.

[0080] The first switching valve 103 has an A state and a B state. When the first switching valve is in the A state, only its interfaces P1 and P8 are connected, interfaces P2 and P3 are connected, interfaces P4 and P5 are connected, and interfaces P6 and P7 are connected. When the first switching valve is in the B state, only its interfaces P1 and P2 are connected, interfaces P3 and P4 are connected, interfaces P5 and P6 are connected, and interfaces P7 and P8 are connected. Optionally, the first switching valve 103 adopts an eight-position switching valve.

[0081] The second switching valve 104 has an A state and a B state. When the second switching valve is in the A state, only its interfaces P6 and P7 are connected, and interfaces P5 and P8 are connected. When the second switching valve is in the B state, only its interfaces P5 and P6 are connected, and interfaces P7 and P8 are connected. Optionally, the second switching valve 104 can be a four-position switching valve, a six-position switching valve, or an eight-position switching valve. Figure 1 An eight-position switching valve is used in the illustrated embodiment.

[0082] Alternatively, if Figure 1 As shown, H1 and H2 areas are constant temperature areas, which are electrically heated and PID temperature controlled. T1~T5 are variable temperature control areas, T1~T2 are cooled by semiconductor elements, electrically heated, and PID temperature controlled. T3 is cooled by Stirling elements, electrically heated, and PID temperature controlled. T4 is cooled by Stirling elements, electrically heated nitrogen, and then heated with hot nitrogen. T5 is a variable temperature control area in the chromatographic column oven, the temporary column 301 and the chromatographic separation module are arranged in the chromatographic column oven, and the heat exchanger 403 is installed in the chromatographic column oven; the variable temperature control area of ​​T5 also includes a condenser 402, the refrigerant is driven by the compressor of the condenser 402, and evaporates and cools in the heat exchanger 403; it is heated by the heater in the column oven, and the PID temperature is controlled to -10~10 degrees as the initial temperature of the chromatogram.

[0083] In some embodiments, a forward and reverse flushing pipeline is further included, and the forward and reverse flushing pipeline is connected to the target object capturing pipeline, and is used to introduce inert gas into the target object capturing pipeline from two directions, so that the capturing module 203 captures the target object remaining in the target object capturing pipeline;

[0084] The forward and reverse flushing pipeline has a first state and a second state. When in the first state, the inert gas passes through the second dehydration module 202 and the capture module 203 in sequence; when in the second state, the inert gas passes through the capture module 203 and the second dehydration module 202 in sequence.

[0085] In some embodiments, the forward and reverse flushing pipeline includes an inert gas inlet, a first three-way valve 107 and a second three-way valve 112;

[0086] One end of the first three-way valve 107 is connected to one end of the second three-way valve 112, the other two ends of the first three-way valve 107 are respectively connected to the inert gas inlet and the selection interface S5 of the one-to-many selection valve, and the other two ends of the second three-way valve 112 are respectively connected to the interface P7 of the first switching valve and the first flow meter 105;

[0087] The first three-way valve 107 has a first state and a second state. In the first state, the inert gas inlet is connected to the one-to-many selector valve 102, and in the second state, the inert gas inlet is connected to the second three-way valve 112.

[0088] The second three-way valve 112 has a first state and a second state. In the first state, the first three-way valve 107 is connected to the first switching valve 103 , and in the second state, the first switching valve 103 is connected to the first flow meter 105 .

[0089] Optionally, the inert gas inlet is connected to the first three-way valve 107 via a second flowmeter 108. Optionally, the inert gas inlet is used to introduce high-pressure helium, and the second flowmeter 108 is a helium sampling flowmeter.

[0090] Embodiment 2

[0091] The embodiment of the present invention further provides a method for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere, using the device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere described in any one of the embodiments in the first embodiment, and the method comprises the following steps:

[0092] S1. Pass the sample gas into the capture pipeline, and capture the target in the sample gas through the capture module;

[0093] S2, the temporary storage column switching module is switched to the first state, the capture switching module is switched to the first state, the capture module is set to a first given temperature to parse out the first part of the target, the carrier gas is introduced into the carrier gas inlet and flows into the capture module and the temporary storage column in sequence, wherein the temperature of the temporary storage column is set to a second given temperature, so that the first part of the target remains in the temporary storage column, and the first part of the target is chromatographed by the temporary storage column;

[0094] S3, the temporary column switching module is switched to the second state, the capture switching module is switched to the first state, the capture module is set to a third given temperature to parse out the second part of the target, a carrier gas is introduced into the carrier gas inlet to flow through the capture module and the second part of the target is transported to the focusing analysis module;

[0095] S4, the temporary storage column switching module is switched to the first state, the capture switching module is switched to the second state, a carrier gas is introduced into the carrier gas inlet to flow through the temporary storage column and the first part of the target is transported to the focusing analysis module;

[0096] The first given temperature is lower than the third given temperature.

[0097] In some embodiments, a method for monitoring ozone-depleting substances and hydrofluorocarbons in the atmosphere comprises: using the device for monitoring ozone-depleting substances and hydrofluorocarbons in the atmosphere described in the first aspect of the embodiment, and further comprising the following steps:

[0098] S1. The system is ready for standby and the temperature and gas pressure of each unit are adjusted. This step is used to complete various pre-sampling preparations, including the temperature of each temperature control module, gas pressure, etc.

[0099] S2, collecting gas samples, passing the sample gas into the capture pipeline, and capturing the target in the sample gas through the capture module;

[0100] Specifically, the automatic sampler 101 collects the sample gas in the Summa tank, the one-to-many selection valve is connected to the selection interface S7, and the first switching valve is switched to state A, so that the sample gas flows out through the first dehydration module 201, the first switching valve 103, the second dehydration module 202, the capture module 203, the first flowmeter 105 and the pump 109 in sequence.

[0101] S3, dehydration and enrichment, first dehydration treatment is performed on the collected gas samples at a temperature of -45℃~25℃ by the first dehydration module 201 and the second dehydration module 202, and then the dehydrated gas is subjected to adsorption enrichment treatment at a temperature of -100℃~-30℃ by the capture module 203; specifically, according to the set flow rate, volume, pre-concentration sample position or different sample positions of the automatic sampler 101, gas samples of different Suma tanks are collected, including diluted standard gas, internal standard gas, blank gas, actual sample gas, etc. And the collected gas samples are subjected to low-temperature bipolar dehydration treatment and low-temperature adsorption enrichment treatment. The temperature is maintained at -45℃~25℃ during low-temperature bipolar dehydration treatment; the temperature is maintained at -45℃~-2℃ during low-temperature adsorption enrichment treatment.

[0102] S4, dry blowing recovery and purification, the first three-way valve 107 is switched to the first state, the one-to-many selection valve is connected to the selection interface S5, and the target remaining in the dehydration module is first recovered to the capture module 203 by forward blowing the dehydration module with high purity helium at low temperature. Then the first three-way valve 107 is switched to the second state, and the second three-way valve 112 is switched to the second state, and the capture module 203 is reversely purged with high purity helium to recover the target that is difficult to enrich in the capture module 203 and gather them in the capture module 203; specifically, the dehydration tube is first forwardly purged with helium at low temperature of -5 to 10°C to recover the target in it to the adsorption tube in the capture module 203, and the adsorption tube is purified to remove interfering substances such as carbon dioxide, and then the target that is difficult to enrich in the capture module 203 is recovered to the capture module 203 by reverse blowing.

[0103] S5, one-stage analysis, the first switching valve switches to state B, the second switching valve switches to state B, the capture module 203 is controlled to heat up to a first given temperature to parse out a first portion of low-boiling-point target substances, the first given temperature is, for example, 0-50°C, a carrier gas is introduced into the analysis carrier gas inlet 304, the carrier gas passes through the capture module 203 to bring the parsed first portion of target substances into the temporary storage column 301, the temporary storage column 301 controls the temperature at -20-10°C to temporarily store the first portion of target substances; specifically, in the first stage, the adsorption tube of the capture module 203 is heated to 0-50°C to parse out part of the low-boiling-point target substances, which are brought into the temporary storage column 301 by the carrier gas.

[0104] S6, two-stage analysis, the first switching valve switches to state B, the second switching valve switches to state A, the capture module 203 is controlled to heat up to 180-280°C to analyze the second part of the target with a high boiling point, and is directly brought into the focusing module 302 by the carrier gas.

[0105] S7, first stage injection, firstly, the focusing module 302 is rapidly heated to 120-200° C. by means of a hot nitrogen chamber for analysis, so that the second part of the target material of the focusing module 302 enters the chromatographic column 401 in its entirety;

[0106] S8, second stage injection, switching the second switching valve 104 to B to pass the first part of the target retained in the temporary storage column 301 into the focusing module 302, and then inject it into the chromatographic column 401.

[0107] S9, low temperature chromatography separation and detection, all target objects are chromatographically separated and processed in a chromatographic column 401 incubator at -15 to 15°C, the separated target objects are detected, and the results are analyzed and processed.

[0108] In a preferred embodiment, when the system steps S7 to S8 are injected, the primary dehydration module 201 and the secondary dehydration module 202 are heated to 160 to 210°C, and the capture module 203 is heated to 180 to 250°C. Nitrogen is introduced by controlling the first flowmeter 105 to set the flow rate to 80 to 160 mL / min to clean the dehydration module and the capture module 203.

[0109] In a preferred embodiment, in the process of dehydrating the carrier gas end using a nanotube, according to the dehydration principle of the nanotube itself, it is necessary to always maintain a certain nitrogen flow rate in the nanotube, and introduce 20 to 80 ml / min of nitrogen by setting an auxiliary nitrogen sampling flowmeter to remove moisture from the carrier gas.

[0110] In some embodiments, a method for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere comprises:

[0111] SA1, the system is ready for standby, and various pre-sampling preparations are completed: H1, H2, control the temperature to 140°C, the first dehydration module 201 and the second dehydration module 202 are controlled to -30°C, the capture module 203 is controlled to -60°C, the first switching valve 103 and the second switching valve 104 are switched to state A, and the remaining components are in the default state.

[0112] SA2. Collect gas samples: according to the gas type, flow rate and volume to be collected, switch the selection valve to the designated position to connect the interface, start the sampling pump 109, and limit the collection flow rate with the nitrogen mass flow meter. After reaching the specified sampling volume, turn off the nitrogen mass flow meter; and switch different sample channels and injector sample channels in turn, and perform adsorption enrichment treatment on the injector sample, injector ambient air, internal standard gas, blank nitrogen, etc.

[0113] SA3, dry-blow recovery: heat the dehydration module to 5°C, set the one-to-many selection valve to the selection interface S7, switch the automatic sampler 101 interface to interface No. 1, set the nitrogen mass flow meter to 4ml / min, purge the dehydration module with nitrogen for 2min, recover the target object to the capture module 203, and purify the adsorption tube to remove interfering substances such as carbon dioxide.

[0114] SA4, helium reverse dry blowing: turn the one-to-many selection valve to the selection interface S5, the helium mass flow meter is 20 ml / min, and the helium is used to reversely purge the capture module 203 for 30 seconds to collect the blown target objects into the capture module 203.

[0115] SA5, first-stage analysis to temporary storage column: Start the low-temperature column oven T5 for refrigeration, and the compressor circulates the refrigerant in the heat exchanger 403 and the condenser 402 to maintain the low-temperature column oven at -5°C. The focusing module 302 is cooled to -30°C, the first switching valve 103 is in state B, and the second switching valve 104 is in state B. At this time, the capture module 203 is connected to the temporary storage column 301 module, and the capture module 203 is heated to 0°C to analyze part of the target, which is brought into the temporary storage column 301 for storage by the carrier gas 80kPa and the non-divided mode;

[0116] SA6, second stage analysis to focusing module: the first switching valve 103 is in state B, the second switching valve 104 is in state A. At this time, the capture module 203 is connected with the focusing module 302, the capture module 203 is heated to 200°C to analyze the remaining target, and the carrier gas is 80 kPa, and the non-dividing mode is brought into the focusing module 302 for storage;

[0117] SA7, first-stage full-volume injection: the focusing module 302 is rapidly heated to 200°C for analysis, and the full volume enters the chromatographic column 401 through the silanized two-way connection to start chromatographic separation;

[0118] SA8, second-stage full-volume injection: the second switching valve 104 is switched back to state B, and the full volume enters the chromatographic column 401 under the silanized two-way connection to start chromatographic separation;

[0119] SA9, thermal cleaning: Injection is carried out in parallel, the valve is switched to state A, the temperature of the dehydration module, dehydration module, and capture module 203 is raised to 200°C and 250°C respectively, a one-to-many selection valve is set to the selection interface S7, the automatic sampler 101 valve is switched to position 1, and the solenoid valve and nitrogen mass flow meter are turned on in turn to 100ml / min, and maintained for 8min. Thermal cleaning flow system, thermal cleaning of the dehydration module, dehydration module capture module 203.

[0120] SA10, low temperature chromatography separation and detection: low temperature column oven T5, maintain -5℃, 7min, 10℃ / min to 35℃, 7min; 10℃ / min to 120℃, maintain 10min, 5℃ / min to 182℃, maintain 0min, 48℃ / min to 230℃, maintain 2.3min, chromatographic separation. The detector is MS detector, the separated target is detected, and the results are analyzed and processed.

[0121] In some embodiments, a method for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere comprises:

[0122] SB1, the system is ready for standby, and various pre-sampling preparations are completed: H1, H2, control the temperature to 140°C, the dehydration module controls the temperature to -30°C, the capture module 203 controls the temperature to -60°C, the first switching valve 103 and the second switching valve are both in state A, and the remaining components are in default state.

[0123] SB2. Collect gas samples: According to the gas type, flow rate, and volume to be collected, switch the one-to-many selection valve to the designated position to connect the interface, start the sampling pump, and limit the collection flow rate with a nitrogen mass flow meter. After reaching the specified sampling volume, turn off the nitrogen mass flow meter; and switch different sample channels and injector sample channels in turn, and perform adsorption enrichment treatment on the injector sample, injector ambient air, internal standard gas, blank nitrogen, etc.

[0124] SB3, dry-blow recovery: heat the dehydration module to 5°C, set the one-to-many selection valve to the selection interface S7, switch the automatic sampler interface to interface No. 1, set the nitrogen mass flow meter to 4ml / min, purge the dehydration module with nitrogen for 1.5min, recover the target object to the capture module 203, and purify the adsorption tube to remove interfering substances such as carbon dioxide.

[0125] SB4, helium reverse dry blowing: set a one-to-many selection valve to the selection interface S5, the helium mass flow meter is 20ml / min, and the capture module 203 is purged with helium in reverse for 30s to collect the blown target into the capture module 203;

[0126] SB5, first-stage analysis to temporary storage column: start the low-temperature column oven T5 refrigeration, the compressor makes the refrigerant circulate in the heat exchanger 403 and the condenser 402 to maintain the -5℃ low-temperature column oven. The focusing module 302 is cooled to -30℃, the first switching valve 103 is in the B state, and the second switching valve 104 is in the B state. At this time, the capture module 203 is connected to the temporary storage column 301 module, and the capture module 203 is heated to 0℃ to analyze part of the target, which is brought into the temporary storage column 301 module for storage by the carrier gas 80kPa and the non-divided mode;

[0127] SB6, second stage analysis to focusing module 302: eight-position switching valve 103 to B state, six-position switching valve 104 to A state. At this time, the capture module 203 is connected with the focusing module 302, and the capture module 203 is heated to 200°C to analyze the remaining target, which is brought into the focusing module 302 for storage by the carrier gas 80kPa and non-dividing mode;

[0128] SB7, first-stage full-volume injection: the focusing module 302 is quickly heated to 200°C for analysis, and the full volume enters the chromatographic column 401 under the silanized two-way connection to start chromatographic separation. SB8, second-stage full-volume injection: the second switching valve 104 is switched back to state B, and the full volume enters the chromatographic column 401 under the silanized two-way connection to start chromatographic separation;

[0129] SB9, thermal cleaning: Injection is carried out in parallel, the first switching valve 103 is switched to state A, the first dehydration module 201, the second dehydration module 202, and the capture module 203 are controlled and heated to 200°C, 200°C, and 250°C respectively, a one-to-many selection valve is set to the selection interface S7, the automatic sampler 101 valve is switched to position 1, and the solenoid valve and nitrogen mass flow meter are turned on in sequence to 100ml / min, and maintained for 8 minutes. Thermal cleaning of the flow path system, thermal cleaning of the first dehydration module 201, the second dehydration module 202, and the capture module 203.

[0130] SB10, low temperature chromatography separation and detection: low temperature column oven T5, maintain -5℃, 7min, 10℃ / min to 35℃, 7min; 10℃ / min to 120℃, maintain 10min, 5℃ / min to 182℃, maintain 0min, 48℃ / min to 230℃, maintain 2.3min, chromatographic separation. The detector is MS detector, the separated target is detected, and the results are analyzed and processed.

[0131] Embodiment 3

[0132] After purification by the primary dehydration module, the secondary dehydration module and the capture module, there are still some difficult-to-remove interferents in the enriched target, and these interferents have a large interference with the quantitative detection of some medium and low boiling point targets. In order to solve this problem, the first embodiment of the present invention adopts staged analysis. However, since the boiling point division boundary of the two stages in the staged analysis is difficult to grasp, the separation results of some targets in the two stages overlap, that is, some targets have two peaks, one large and one small. In order to solve this problem, this embodiment provides a monitoring device for ozone depleting substances and hydrofluorocarbons in the atmosphere, such as Figure 2 As shown, including:

[0133] The target object capturing pipeline includes a capturing module 203, and the capturing module 203 is used to capture the target object in the sample gas;

[0134] Focusing analysis module, used to focus and chromatographically separate the target for detection;

[0135] An analysis pipeline, comprising an analysis carrier gas inlet 402 and a capture switching module, wherein the capture switching module is used to connect two ends of the capture module 203 to the analysis carrier gas inlet 402 and the focusing analysis module respectively;

[0136] A purification pipeline, wherein the purification pipeline is used to remove interfering substances of the target object in the capture module, and the purification pipeline includes a capillary chromatographic column purification module 204, wherein the capillary chromatographic column purification module 204 is used to remove interfering substances in the target object, and the purification pipeline has a first state and a second state. When in the first state, the inert gas passes through the capture module 203 and the capillary chromatographic column purification module 204 in sequence; when in the second state, the inert gas passes through the capillary chromatographic column purification module 204 and the capture module 203 in sequence.

[0137] In some embodiments, a dehydration module is further included. The dehydration module is disposed on the target object capture pipeline, and the dehydration module is used to dehydrate the sample gas before the sample gas enters the capture module.

[0138] In some embodiments, the dehydration module includes a first dehydration module 201 and a second dehydration module 202;

[0139] The target object capture pipeline also includes an automatic sampler 101, a pump 109 and a first flowmeter 105. The automatic sampler 101 is used to connect to the Summa tank. The pump 109 is arranged at one end close to the outlet of the target object capture pipeline. The automatic sampler 101 is connected to the pump 109 through the first dehydration module 201, the second dehydration module 202, the capture module 203, and the first flowmeter 105 in sequence.

[0140] The focusing analysis module includes a focusing module 302, a chromatographic separation module and a detection unit 405 which are connected in sequence. The focusing module 302 is used to focus on the target object and input the target object into the chromatographic separation module. The chromatographic separation module is used to perform chromatographic separation on the target object and then input it into the detection unit. The inlet of the focusing module is connected to the multi-stage analysis pipeline.

[0141] The chromatographic separation module includes a chromatographic column 401, a condenser 404 and a heat exchanger 403; wherein the condenser 404 and the heat exchanger 403 are connected to the chromatographic column 401, one end of the chromatographic column 401 is connected to the detection unit, and the other end of the chromatographic column 401 is connected to the focusing module 302 through an inert two-way. The chromatographic separation module inputs the detection unit 501 after chromatographic separation of the target, and the inlet of the focusing module 302 is connected to the multi-stage analysis pipeline. Specifically, the focusing analysis module is used to focus the target at low temperature through the focusing module 302, and at the same time control the program temperature rise, so that the target flows into the detection unit 501 one by one; it should be noted that the low temperature here refers to an environment of -15°C to 15°C. The detection unit 501 includes an ion source and an ion multiplier, and the ion source part fragments the target molecule ions; the ion fragments enter the ion multiplier to form a current signal, and the ion multiplier is used to receive, amplify and form a chromatogram of the current signal; it is convenient for qualitative and quantitative analysis.

[0142] In some embodiments, it further includes a pair of multiple selector valves 102 , a first switching valve 103 , and a second switching valve 104 ;

[0143] The one-to-many selection valve 102 has a fixed interface and multiple selection interfaces, and the one-to-many selection valve 102 is configured to enable one of the fixed interfaces to communicate with one of the selection interfaces;

[0144] The automatic sample injector 101 is connected to the selection interface S7 of the one-to-many selection valve through the first dehydration module 201, the fixed interface is connected to the interface P1 of the first switching valve, the interface P2 of the first switching valve is connected to the interface P5 of the second switching valve, the two ends of the capture module 203 are respectively connected to the interfaces P3 and P6 of the first switching valve, the interface P4 of the first switching valve is connected to the focusing module, the interface P5 of the first switching valve is connected to the analytical carrier gas inlet, the interface P7 of the first switching valve is connected to the pump through the first flow meter, the interface P8 of the first switching valve is connected to the interface P2 of the second switching valve, the two ends of the second dehydration module 202 are respectively connected to the interfaces P3 and P4 of the second switching valve, and the two ends of the capillary column purification module 204 are respectively connected to the interfaces P6 and P1 of the second switching valve;

[0145] The first switching valve 103 has an A state and a B state. When the first switching valve is in the A state, only its interfaces P1 and P8 are connected, interfaces P2 and P3 are connected, interfaces P4 and P5 are connected, and interfaces P6 and P7 are connected. When the first switching valve is in the B state, only its interfaces P1 and P2 are connected, interfaces P3 and P4 are connected, interfaces P5 and P6 are connected, and interfaces P7 and P8 are connected.

[0146] The second switching valve 104 has an A state and a B state. When the second switching valve is in the A state, only its interfaces P1 and P6 are connected, interfaces P2 and P3 are connected, and interfaces P4 and P5 are connected. When the second switching valve is in the B state, only its interfaces P1 and P2 are connected, interfaces P4 and P5 are connected, and interfaces P5 and P6 are connected.

[0147] Optionally, the one-to-many selector valve 102 may be an eight-in-one-out selector valve, the first switching valve 103 may be, for example, an eight-position switching valve, and the second switching valve 104 may be, for example, a six-position switching valve.

[0148] In some embodiments, the purification pipeline includes an inert gas inlet, a first three-way valve 110 and a second three-way valve 112; the first three-way valve 110 is, for example, a two-position three-way solenoid valve, and the second three-way valve 112 is, for example, a two-position three-way solenoid valve.

[0149] One end of the first three-way valve 110 is connected to one end of the second three-way valve 112, the other two ends of the first three-way valve 110 are respectively connected to the inert gas inlet and the selection interface S5 of the one-to-many selection valve, and the other two ends of the second three-way valve 112 are respectively connected to the interface P7 of the first switching valve and the first flow meter;

[0150] The first three-way valve 110 is configured to connect the inert gas inlet to the one-to-many selector valve 102 or to connect the inert gas inlet to the second three-way valve 112;

[0151] The second three-way valve 112 is configured to connect the first three-way valve 110 to the first switching valve 103 or to connect the first switching valve 103 to the first flow meter 105 .

[0152] In some embodiments, it also includes a signal acquisition and processing control unit, including temperature and pressure sensors and PID control loops of each temperature control zone, as well as a high-temperature constant temperature zone and a variable temperature control zone; the high-temperature constant temperature zone is specifically H1 to H3, which are high-temperature constant temperature zones, wherein: the one-to-many selection valve 102, the first switching valve 103, the second switching valve 104, and the second three-way valve 112 are located in the H2 high-temperature constant temperature zone, the S1-7 position and both ends of the first-stage low-temperature empty pipe dehydration module are located in the H1 high-temperature constant temperature zone, and the Nafion tube dehydration module is the H3 high-temperature constant temperature zone;

[0153] The variable temperature control zones are specifically T1 to T6, which all adopt PID temperature control and the temperature change rate is controllable; the first dehydration module 201 is located in the T1 variable temperature control zone, with a temperature range of -45°C to 250°C; the second dehydration module 202 is located in the T2 variable temperature control zone, with a temperature range of -45°C to 250°C; the capture module 203 is located in the T3 variable temperature control zone, with a temperature range of -160°C to 300°C, and is cooled by a deep-cold compressor; the focusing module 302 is located in the T4 variable temperature control zone, with a temperature range of -160°C to 200°C, and is cooled by a deep-cold compressor; the chromatographic column 401 is located in the T5 variable temperature control zone, with a temperature range of -5°C to 300°C; the capillary chromatographic column purification module 204 is located in the T6 variable temperature control zone, with a temperature range of 35°C to 300°C.

[0154] In some embodiments, the first dehydration module 201 and the second dehydration module 202 both use empty polytetrafluoroethylene tubes with an inner diameter of 2 to 4 mm and a length of 20 to 40 cm for freezing and dehydration, so that sample collection can be achieved under positive pressure, normal pressure and negative pressure; the capture module 203 is a silanized stainless steel tube with an inner diameter of 2 to 4 mm and a length of 20 to 40 cm, filled with tenax and carbon molecular sieve composite fillers, which enriches the target under ultra-low temperature conditions; the capillary column purification module 204 is a 30m capillary column with a stationary phase coating, which is used to separate interfering substances and purify the target.

[0155] In some embodiments, the focusing module 302 is a capillary chromatographic column with an outer diameter of 0.53 mm, a length of 20 to 40 cm, and a stationary phase coating, which is used to focus the target object into an extremely small volume for injection to ensure sharp chromatographic peaks; a Nafion online dehydration module with a length of 2 to 4 m continuously removes moisture from the carrier gas and the analytical gas to ensure that the chromatographic peaks do not drift.

[0156] An embodiment of the present invention further provides a method for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere, using the device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere described in any embodiment of the second aspect, and the method comprises the following steps:

[0157] S1. Pass the sample gas into the capture pipeline, and capture the target in the sample gas through the capture module;

[0158] S2, the purification pipeline is switched to the first state, the temperature of the capillary column purification module is set to the fourth given temperature, the temperature of the capture module is set to the fifth given temperature to resolve the interfering substances and part of the target substances with a boiling point below the fifth given temperature, an inert gas is introduced into the purification pipeline to flow into the capture module and the capillary column purification module in sequence, the resolved interfering substances and part of the target substances are brought into the capillary column purification module, chromatographic separation is performed through the capillary column purification module until the interfering substances are eliminated, and the introduction of the inert gas is stopped;

[0159] S3, the purification pipeline is switched to the second state, the temperature of the capillary column purification module is set to the sixth given temperature to resolve the part of the target, the temperature of the capture module is set to the seventh given temperature, and an inert gas is introduced into the purification pipeline to bring the part of the target back to the capture module to complete the recovery of the part of the target, wherein the seventh given temperature is lower than the fifth given temperature;

[0160] S4, the capture switching module is switched to the capture module connected to the analysis pipeline, the temperature of the capture module is set to the eighth given temperature, the carrier gas is introduced into the carrier gas inlet to flow through the capture module and transport the target object to the focusing analysis module.

[0161] The capillary column purification module 204 of the embodiment of the present invention can separate and purify impurities in the sample, including gases such as nitrogen, argon, krypton, and xenon, so that low-boiling point substances such as NF3 and CF4 that are difficult to detect can also be accurately qualitatively and quantitatively analyzed.

[0162] The first dehydration module 201, the second dehydration module 202, and the online Nafion tube dehydration module 303 of the embodiment of the present invention can fully remove a large amount of water in the sample and the carrier gas, ensure the stability of the retention time of each target component in the chromatographic mass spectrum formed by the detection unit, and facilitate accurate qualitative and quantitative determination.

[0163] The ultra-low temperature conditions of the capture module 203 and the focusing module 302 of the present invention do not require the use of any cold medium, and can be reduced to below -160°C by using a compressor refrigeration method, so there is no need to consider the site environment and the economic cost of the refrigerant, and they can be started and used as soon as possible.

[0164] The refrigerator 404 and the heat exchanger 403 in the low-temperature chromatographic separation unit of the present invention work together to control the initial column density of the chromatographic separation unit to be 35°C below room temperature, and refocus after injection to optimize the peak shape, improve the separation degree, and improve the accuracy and reliability of the analysis.

[0165] In the present invention, the nafion online dehydration device 303 is located between the focusing module 302 and the eight-position switching valve, and the pressure provided by the EPC carrier gas pressure controller is cleverly used to achieve the third dehydration treatment of the carrier gas and the target, thereby minimizing the interference of water removal on the entire analysis.

[0166] The whole system of the present invention has high sensitivity and low detection limit, and can effectively detect some components with ppt (parts per billion) concentration in ozone depleting substances (ODS) and hydrofluorocarbons (HFCS).

[0167] Optionally, the sample gas in the present invention is: 40 kinds of ODS and controlled halogenated hydrocarbon gas mixed standard gas: concentration is 100nmol·mol-1. Ultrapure helium: ≥99.9999%; high-purity nitrogen: ≥99.999%. Standard use gas: 5, 50, 500pmol·mol-1 and 1nmol·mol-1, using a high-precision static diluter to dilute and prepare step by step.

[0168] In some embodiments, a method for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere comprises:

[0169] SC1, system standby preparation: adjust the temperature and gas pressure of each unit; the temperature of H1 and H2 areas rises to 120℃~160℃, H3 rises to 40~60℃, and the auxiliary nitrogen mass flowmeter adjusts the flow rate to 30~60ml / min; the first-level dehydration module and the second-level dehydration module are cooled to 0℃~-40℃, and the capture module is cooled to -60~-80℃. The eight-position switching valve and the six-position switching valve are both in state A, and the other components are in the default state.

[0170] SC2, collect gas samples: collect gas samples from different Suma tanks through the sampling unit and transport them to the concentration and purification unit; turn on the mechanical pump, set the flow rate of the nitrogen mass flow meter at 50-100ml / min, and reach the set volume.

[0171] SC3, freeze dehydration, adsorption capture: remove moisture from the primary dehydration module and the secondary dehydration module at a temperature of -45℃ to -10℃, set the temperature of the capture module to -60~-80℃, and enrich the target.

[0172] SC4, forward dry-blow recovery: raise the temperature of the two dehydration modules to 2°C to 20°C, set the nitrogen mass flow meter flow rate to 50ml / min to 100ml / min, switch the eight-position selector valve to position 7, switch the autosampler selector valve to the nitrogen position, introduce nitrogen to purge the two dehydration modules for 10 to 45 seconds, and recover the target in the dehydration module to the capture module;

[0173] SC5, capture and analysis, ultra-low temperature capillary column focusing: adjust the focusing module temperature to -120℃~-130℃, the capture module temperature to 180℃~220℃, switch the eight-position switching valve to state B, and bring the enriched target into the focusing module through the carrier gas for ultra-low temperature focusing;

[0174] SC6, full volume injection: control the temperature of the hot nitrogen chamber to 300°C, open the two-way solenoid valve, use the high-temperature nitrogen in the hot nitrogen chamber to quickly heat the focusing module to 180-220°C, and let the full volume of the target in the focusing module enter the low-temperature chromatographic column in the low-temperature chromatographic separation unit for secondary focusing;

[0175] SC7, low temperature chromatography separation, through a suitable temperature program and a certain pressure, the target in the chromatographic column is chromatographically separated and processed, and flows into the detector one by one in batches to form a chromatographic mass spectrum for qualitative and quantitative analysis;

[0176] SC8, thermal cleaning, the primary dehydration module and the secondary dehydration module are heated to 180-220°C, the capture module is heated to 200-260°C, the flow rate is set to 80-100 mL / min by controlling the nitrogen mass flow meter, the mechanical pump is turned on, and the cleaning is carried out for 240s-480s.

[0177] Figure 3 In steps SC1 to SC8: the sampling unit collects 1000 ml of 1 nmol·mol-1 standard gas, which is concentrated and purified, and the whole volume is focused and sent into the low-temperature chromatography separation and detection unit for processing to obtain a chromatographic mass spectrum. There are 38 peaks of target objects in the figure, and the peak tops are digitally marked. The target object represented by each digital mark is explained below.

[0178] Table 1 shows the low, medium and high linear relationships, detection limits and background values ​​of some target compounds obtained by analyzing a series of standard samples in the atmospheric ozone depleting substances and hydrofluorocarbon monitoring and analysis system in steps SC1 to SC8. In this case, the reverse dry-blowing capillary column was not used for purification, and the NF3 and CF4 targets were not identified due to interference, and could not be qualitatively and quantitatively analyzed.

[0179] Table 1

[0180]

[0181]

[0182]

[0183] In some embodiments, a method for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere comprises:

[0184] SD1, system standby preparation: adjust the temperature and gas pressure of each unit; H1 and H2 control temperature to 120℃~160℃, H3 control temperature to 50℃, auxiliary nitrogen mass flow meter adjusts flow rate to 40~60ml / min; the primary dehydration module and secondary dehydration module control temperature are both 0℃~-40℃, the capture module control temperature is -135~-160℃, the eight-position switching valve and the six-position switching valve are both in A state, and the rest of the components are in default state;

[0185] SD2. Collect gas samples: switch the eight-position selector valve to sample position 6 according to the gas to be collected, open the two-way solenoid valve, start the mechanical pump, and use the nitrogen mass flow meter to limit the collection flow rate to 50-100 ml / min, and collect the set volume;

[0186] SD3, cryo-dehydration, adsorption capture: The collected gas samples are dehydrated in a two-stage dehydration module at a temperature of -45℃ to 0℃, and then the dehydrated gas is enriched in a capture module at -160℃ to -135℃ through a concentration and purification unit;

[0187] SD4, one-time forward dry-purge recovery: raise the temperature of the two dehydration modules to 5℃~10℃, adjust the nitrogen mass flow meter flow rate to 50ml / min~100ml / min, switch the eight-position selection valve to position 7, switch the automatic sampler selection valve to the nitrogen position to introduce nitrogen to forward purge the dehydration module for 10~30s, and recover the retained target substances in the two dehydration modules to the capture module;

[0188] SD5, helium reverse dry purge purification: adjust the temperature of the capture module to -120~-100℃, raise the temperature of the capillary column purification module to 35℃~45℃, switch the six-position switching valve to state B, adjust the helium mass flow meter flow rate to 4ml / min~10ml / min, open the three-way solenoid valve to introduce helium from the silanized three-way purge capture module for 15s~60s;

[0189] SD6, secondary forward dry blowing in-situ collection, adjust the temperature of the capillary column purification module to 100℃~150℃, cool the collection module to -160℃~-135℃, adjust the helium mass flow meter flow rate to 4ml / min~10ml / min, close the three-way solenoid valve, switch the eight-position selector valve to position 5, and introduce helium to purge the capillary column purification module;

[0190] SD7, capture and analysis, ultra-low temperature capillary column focusing: adjust the focusing module temperature to -135℃~-160℃, the capture module temperature to 180℃~250℃, switch the eight-position switching valve to state B, and bring the captured target gas into the focusing module through the carrier gas for ultra-low temperature focusing;

[0191] SD8, full volume injection, control the temperature of the hot nitrogen chamber to 300°C, open the two-way solenoid valve, use the high-temperature nitrogen in the hot nitrogen chamber to quickly heat the focusing module to 180-220°C, and let the full volume of the target gas in the focusing module enter the low-temperature chromatographic column in the low-temperature chromatographic analysis unit for secondary focusing;

[0192] SD9, low temperature chromatographic separation, through the appropriate carrier gas pressure and the appropriate temperature program, the target in the chromatographic column is chromatographically separated and processed, and flows into the detector one by one in batches to form a chromatographic mass spectrum for qualitative and quantitative analysis;

[0193] SD10, thermal cleaning, the primary dehydration module and the secondary dehydration module are heated to 180-210°C, the capture module is heated to 180-250°C, the capillary column purification module is heated to 80-150°C, the flow rate is set to 80-160 mL / min by controlling the nitrogen mass flow meter, the pump is turned on, and cleaning is performed for 240s-480s.

[0194] Figure 4 In steps SD1 to SD10: the sampling unit collects 1000 ml of 1 nmol·mol-1 standard gas, which is concentrated and purified, and then focused by an ultra-low temperature capillary column and introduced into a low temperature chromatography separation and detection unit for analysis to obtain a chromatographic mass spectrum. There are 40 peaks of target objects in the figure, and the peak tops are digitally marked, and the target object represented by each digital mark is explained below.

[0195] Table 2 is a comparison of the low, medium and high correlation coefficients, detection limits and background values ​​of the target objects obtained by analyzing a series of standard samples in steps SD1 to SD10 through the atmospheric ozone depleting substances and hydrofluorocarbon monitoring and analysis system; in steps SD1 to SD10, after reverse dry-blowing capillary column purification, two forward dry-blowing recovery, NF3 and CF4 are captured, and the response is significant in the spectrum, which can be qualitatively and quantitatively analyzed.

[0196] Table 2

[0197]

[0198]

[0199]

[0200] In the description of the present invention, it is necessary to understand that the terms "coaxial", "bottom", "one end", "top", "middle", "the other end", "upper", "one side", "top", "inside", "front", "center", "two ends", etc., indicating the orientation or position relationship are based on the orientation or position relationship shown in the drawings, which are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operate in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0201] In the present invention, unless otherwise clearly stipulated and limited, the terms such as "installation", "setting", "connection", "fixation" and "screw-on" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integrated connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium; it can be the internal connection of two elements or the interaction relationship between two elements. Unless otherwise clearly defined, ordinary technicians in this field can understand the specific meanings of the above terms in the present invention according to the specific circumstances.

[0202] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere, characterized in that: include: A target object capture pipeline, including a capture module, the target object capture pipeline is used to capture the target object in the sample gas and remove interfering substances through the capture module; Multi-stage analytical pipeline, including analytical carrier gas inlet and temporary column switching module; and Focusing analysis module, used to focus and chromatographically separate the target for detection; The analytical carrier gas inlet is connected to the focusing analysis module through the capture switching module and the temporary column switching module in sequence, and the multi-stage analytical pipeline is used to transport the target objects to be analyzed in batches to the focusing analysis module; The temporary storage column switching module has a first state and a second state. When in the first state, the capture module is connected to the focusing analysis module through the temporary storage column. When in the second state, the capture module is directly connected to the focusing analysis module without passing through the temporary storage column. The temporary storage column has a chromatographic separation capability. The capture switching module has a first state and a second state. When in the first state, the analytical carrier gas inlet is connected to the temporary storage column switching module through the capture module. When in the second state, the analytical carrier gas inlet is directly connected to the temporary storage column switching module without passing through the capture module.

2. The device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere according to claim 1, characterized in that: It also includes a dehydration module, which is arranged on the target object capture pipeline and is used to dehydrate the sample gas before the sample gas enters the capture module.

3. The device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere according to claim 2, characterized in that: The dehydration module comprises a first dehydration module and a second dehydration module; The target object capture pipeline further includes an automatic sampler, a pump and a first flow meter, wherein the automatic sampler is used to be connected to the Suma tank, the pump is arranged at one end close to the outlet of the target object capture pipeline, and the automatic sampler is connected to the pump through the first dehydration module, the second dehydration module, the capture module and the first flow meter in sequence; The focusing analysis module includes a focusing module, a chromatographic separation module and a detection unit connected in sequence. The focusing module is used to focus on the target object and input the target object into the chromatographic separation module. The chromatographic separation module is used to perform chromatographic separation on the target object and then input it into the detection unit. The inlet of the focusing module is connected to the multi-stage analysis pipeline.

4. The device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere according to claim 3, characterized in that: Also includes a pair of multiple selection valves, a first switching valve and a second switching valve; The one-to-many selection valve has a fixed interface and a plurality of selection interfaces, and the one-to-many selection valve is configured to enable one of the fixed interfaces to communicate with one of the selection interfaces; The automatic sampler is connected to the selection interface S7 of the one-to-many selection valve through the first dehydration module, the fixed interface is connected to the interface P1 of the first switching valve, the two ends of the second dehydration module are respectively connected to the interfaces P2 and P8 of the first switching valve, the two ends of the capture module are respectively connected to the interfaces P3 and P6 of the first switching valve, the interface P7 of the first switching valve is connected to the pump through the first flow meter, the interface P5 of the first switching valve is connected to the analytical carrier gas inlet, the interface P4 of the first switching valve is connected to the interface P5 of the second switching valve, the two ends of the temporary storage column are respectively connected to the interfaces P6 and P7 of the second switching valve, and the interface P8 of the second switching valve is connected to the focusing module; The first switching valve has an A state and a B state. When the first switching valve is in the A state, only its interfaces P1 and P8 are connected, interfaces P2 and P3 are connected, interfaces P4 and P5 are connected, and interfaces P6 and P7 are connected. When the first switching valve is in the B state, only its interfaces P1 and P2 are connected, interfaces P3 and P4 are connected, interfaces P5 and P6 are connected, and interfaces P7 and P8 are connected. The second switching valve has an A state and a B state. When the second switching valve is in the A state, only its interfaces P6 and P7 are connected, and interfaces P5 and P8 are connected. When the second switching valve is in the B state, only its interfaces P5 and P6 are connected, and interfaces P7 and P8 are connected.

5. The device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere according to claim 4, characterized in that: It also includes a forward and reverse flushing pipeline, which is connected to the target object capturing pipeline and is used to introduce inert gas into the target object capturing pipeline from two directions, so that the capturing module can capture the target object remaining in the target object capturing pipeline; The forward and reverse flushing pipeline has a first state and a second state. When in the first state, the inert gas passes through the second dehydration module and the capture module in sequence; when in the second state, the inert gas passes through the capture module and the second dehydration module in sequence.

6. The device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere according to claim 5, characterized in that: The forward and reverse flushing pipeline includes an inert gas inlet, a first three-way valve and a second three-way valve; One end of the first three-way valve is connected to one end of the second three-way valve, the other two ends of the first three-way valve are respectively connected to the inert gas inlet and the selection interface S5 of the one-to-many selection valve, and the other two ends of the second three-way valve are respectively connected to the interface P7 of the first switching valve and the first flow meter; The first three-way valve is configured to connect the inert gas inlet to the one-to-many selector valve or to connect the Susonghu inert gas inlet to the second three-way valve; The second three-way valve is configured to connect the first three-way valve to the first switching valve or to connect the first switching valve to the first flow meter.

7. A method for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere, characterized in that: Using the device for monitoring ozone-depleting substances and hydrofluorocarbons in the atmosphere as described in any one of claims 1 to 6, the method comprises the following steps: S1. Pass the sample gas into the capture pipeline, and capture the target in the sample gas through the capture module; S2, the temporary storage column switching module is switched to the first state, the capture switching module is switched to the first state, the capture module is set to a first given temperature to parse out the first part of the target, the carrier gas is introduced into the carrier gas inlet and flows into the capture module and the temporary storage column in sequence, wherein the temperature of the temporary storage column is set to a second given temperature, so that the first part of the target remains in the temporary storage column, and the first part of the target is chromatographed by the temporary storage column; S3, the temporary column switching module is switched to the second state, the capture switching module is switched to the first state, the capture module is set to a third given temperature to parse out the second part of the target, a carrier gas is introduced into the carrier gas inlet to flow through the capture module and the second part of the target is transported to the focusing analysis module; S4, the temporary storage column switching module is switched to the first state, the capture switching module is switched to the second state, a carrier gas is introduced into the carrier gas inlet to flow through the temporary storage column and the first part of the target is transported to the focusing analysis module; The first given temperature is lower than the third given temperature.

8. A device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere, characterized in that: include: A target object capture pipeline, comprising a capture module, wherein the capture module is used to capture the target object in the sample gas; Focusing analysis module, used to focus and chromatographically separate the target for detection; An analytical pipeline, comprising an analytical carrier gas inlet and a capture switching module, wherein the capture switching module is used to connect two ends of the capture module to the analytical carrier gas inlet and the focusing analysis module respectively; A purification pipeline, wherein the purification pipeline is used to remove interfering substances of the target object in the capture module, and the purification pipeline includes a capillary chromatographic column purification module, wherein the capillary chromatographic column purification module is used to remove interfering substances in the target object, and the purification pipeline has a first state and a second state. When in the first state, the inert gas passes through the capture module and the capillary chromatographic column purification module in sequence; when in the second state, the inert gas passes through the capillary chromatographic column purification module and the capture module in sequence.

9. The device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere according to claim 8, characterized in that: It also includes a dehydration module, which is arranged on the target object capture pipeline and is used to dehydrate the sample gas before the sample gas enters the capture module.

10. The device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere according to claim 9, characterized in that: The dehydration module comprises a first dehydration module and a second dehydration module; The target object capture pipeline further includes an automatic sampler, a pump and a first flow meter, wherein the automatic sampler is used to be connected to the Suma tank, the pump is arranged at one end close to the outlet of the target object capture pipeline, and the automatic sampler is connected to the pump through the first dehydration module, the second dehydration module, the capture module and the first flow meter in sequence; The focusing analysis module includes a focusing module, a chromatographic separation module and a detection unit connected in sequence. The focusing module is used to focus on the target object and input the target object into the chromatographic separation module. The chromatographic separation module is used to perform chromatographic separation on the target object and then input it into the detection unit. The inlet of the focusing module is connected to the multi-stage analysis pipeline.

11. The device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere according to claim 10, characterized in that: Also includes a pair of multiple selection valves, a first switching valve and a second switching valve; The one-to-many selection valve has a fixed interface and a plurality of selection interfaces, and the one-to-many selection valve is configured to enable one of the fixed interfaces to communicate with one of the selection interfaces; The automatic sampler is connected to the selection interface S7 of the one-to-many selection valve through the first dehydration module, the fixed interface is connected to the interface P1 of the first switching valve, the interface P2 of the first switching valve is connected to the interface P5 of the second switching valve, the two ends of the capture module are respectively connected to the interfaces P3 and P6 of the first switching valve, the interface P4 of the first switching valve is connected to the focusing module, the interface P5 of the first switching valve is connected to the analytical carrier gas inlet, the interface P7 of the first switching valve is connected to the pump through the first flowmeter, the interface P8 of the first switching valve is connected to the interface P2 of the second switching valve, the two ends of the second dehydration module are respectively connected to the interfaces P3 and P4 of the second switching valve, and the two ends of the capillary column purification module are respectively connected to the interfaces P6 and P1 of the second switching valve; The first switching valve has an A state and a B state. When the first switching valve is in the A state, only its interfaces P1 and P8 are connected, interfaces P2 and P3 are connected, interfaces P4 and P5 are connected, and interfaces P6 and P7 are connected. When the first switching valve is in the B state, only its interfaces P1 and P2 are connected, interfaces P3 and P4 are connected, interfaces P5 and P6 are connected, and interfaces P7 and P8 are connected. The second switching valve has an A state and a B state. When the second switching valve is in the A state, only its interfaces P1 and P6 are connected, interfaces P2 and P3 are connected, and interfaces P4 and P5 are connected. When the second switching valve is in the B state, only its interfaces P1 and P2 are connected, interfaces P4 and P5 are connected, and interfaces P5 and P6 are connected.

12. The device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere according to claim 11, characterized in that: The purification pipeline includes an inert gas inlet, a first three-way valve and a second three-way valve; One end of the first three-way valve is connected to one end of the second three-way valve, the other two ends of the first three-way valve are respectively connected to the inert gas inlet and the selection interface S5 of the one-to-many selection valve, and the other two ends of the second three-way valve are respectively connected to the interface P7 of the first switching valve and the first flow meter; The first three-way valve is configured to connect the inert gas inlet to the one-to-multiple selector valves or to connect the inert gas inlet to the second three-way valve; The second three-way valve is configured to connect the first three-way valve to the first switching valve or to connect the first switching valve to the first flow meter.

13. A method for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere, characterized in that: Using the device for monitoring ozone depleting substances and hydrofluorocarbons in the atmosphere as described in any one of claims 8 to 12, the method comprises the following steps: S1. Pass the sample gas into the capture pipeline, and capture the target in the sample gas through the capture module; S2, the purification pipeline is switched to the first state, the temperature of the capillary column purification module is set to the fourth given temperature, the temperature of the capture module is set to the fifth given temperature to resolve the interfering substances and part of the target substances with a boiling point below the fifth given temperature, an inert gas is introduced into the purification pipeline to flow into the capture module and the capillary column purification module in sequence, the resolved interfering substances and part of the target substances are brought into the capillary column purification module, chromatographic separation is performed through the capillary column purification module until the interfering substances are eliminated, and the introduction of the inert gas is stopped; S3, the purification pipeline is switched to the second state, the temperature of the capillary column purification module is set to the sixth given temperature to resolve the part of the target, the temperature of the capture module is set to the seventh given temperature, and an inert gas is introduced into the purification pipeline to bring the part of the target back to the capture module to complete the recovery of the part of the target, wherein the seventh given temperature is lower than the fifth given temperature; S4, the capture switching module is switched to the capture module connected to the analysis pipeline, the temperature of the capture module is set to the eighth given temperature, the carrier gas is introduced into the carrier gas inlet to flow through the capture module and transport the target object to the focusing analysis module.

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