Gas sample injection device, detection device and detection method containing ammonia and / or amine substances

Abstract

The present invention relates to a gas sample injection device containing ammonia and / or amine substances, a detection device and a detection method, comprising a first injection tube, a first outer sleeve, a first particle collection component and an exhaust device; at least a portion of the first injection tube is arranged in the first outer sleeve, a gas flow channel is formed between the first outer sleeve and the first injection tube, the first injection tube has an air inlet and an air outlet, and the air outlet of the first injection tube is located in the first outer sleeve; the first outer sleeve has an air inlet for introducing a barrier agent of a test object, a first air outlet and a second air outlet connected to the exhaust device to inhale a gas sample and a standard sample, a first particle collection component is arranged at the first air outlet, the air outlet of the first injection tube faces the first particle collection component, and the distance between the second air outlet and the first particle collection component is greater than the distance between the air outlet of the first injection tube and the first particle collection component. The injection device can eliminate interference and make the detection result more accurate.

Description

Technical Field

[0001] The present invention belongs to the technical field of analysis and detection, and in particular relates to a gas sample injection device, a detection device and a detection method containing ammonia and / or amine substances. Background Art

[0002] Ammonia (NH3) in the atmosphere plays an extremely important role in the formation and growth of atmospheric particulate matter. Ammonia / amine pollutants are considered to be PM 2.5 The concentration level is continuously pushed up by the important factors, ammonia / amine is PM 2.5 Amines are derivatives of ammonia in which one or more hydrogen atoms are replaced by hydrocarbon groups. Amines can be divided into fatty amines, alcohol amines, amides, aromatic amines and heterocyclic amines according to the different substituents. Ammonia / amines have a wide range of sources, including natural sources, including oceans, forest fires, vegetation and soil, as well as artificial sources, including animal husbandry, industrial emissions, composting and motor vehicle exhaust. Most organic amines are toxic and allergenic, irritating to the eyes, nose, skin and respiratory tract, and damaging to the liver and kidneys. Ammonia / amines can also react with nitrites to form nitrosamines with strong carcinogenicity, which have a great impact on human health. Ammonia / amines mainly undergo three reactions in the atmosphere: acid-base reaction with acidic substances (such as sulfuric acid, nitric acid, etc.); organic amines react with carbonyl compounds to form imines, enamines and amine polymers; organic amines react with oxidants such as ozone and OH. Amines can promote the formation of new particles and the growth of submicron particles, and participate in the formation of secondary organic aerosols, directly or indirectly affecting ambient air quality and regional climate change.

[0003] There are many unfavorable factors in the detection of substances to be tested in the atmosphere. First, particulate matter in the atmosphere often interferes with the analysis and detection of substances to be tested. Second, online continuous detection is difficult. Third, it is difficult to detect the concentrations of multiple substances to be tested with high time resolution. Taking the analysis and detection of ammonia / amines as an example, the most commonly used detection methods are gas chromatography, high performance liquid chromatography, and ion chromatography. However, these methods are cumbersome to operate, slow, lack efficient and simple methods to eliminate the interference of particulate matter, and are not easy to achieve online continuous detection. Therefore, establishing a fast, simple to operate, and labor-saving method for determining substances to be tested in the atmosphere, such as ammonia / amines, has become an urgent need for conducting atmospheric research. Summary of the invention

[0004] In order to solve at least one of the above technical problems, according to a first aspect of the present invention, an embodiment of the present invention provides a gas sample injection device containing ammonia and / or amine substances.

[0005] <1> A gas sample injection device containing ammonia and / or amine substances, comprising a first injection tube, a first outer sleeve, a first particle collecting component and a gas extraction device;

[0006] At least a portion of the first injection tube is disposed in the first outer sleeve, a gas flow channel is formed between the first outer sleeve and the first injection tube, the first injection tube has an air inlet and an air outlet, and the air outlet of the first injection tube is located in the first outer sleeve;

[0007] The first outer sleeve has an air inlet for introducing a barrier agent for the object to be tested, a first air outlet for connecting to the exhaust device to inhale gas samples and standard samples, and a second air outlet for the circulation of gas samples and standard samples. A first particle collecting component is arranged at the first air outlet, the air outlet of the first injection tube is arranged toward the first particle collecting component, and the distance between the second air outlet and the first particle collecting component is greater than the distance between the air outlet of the first injection tube and the first particle collecting component.

[0008] <2> like <1> In the gas sample injection device, the inner diameter of the first injection tube decreases continuously or discontinuously in the direction from the gas inlet to the gas outlet; and / or,

[0009] The distance between the gas outlet of the first sample inlet tube and the first particle collecting component is adjustable; and / or,

[0010] The air inlet and the second air outlet of the first outer sleeve are arranged at one end of the first outer sleeve, and the first air outlet is arranged at the other end of the first outer sleeve; and / or,

[0011] The gas sampling device further comprises a power device for passing the analyte barrier agent into the first outer sleeve through the gas inlet of the first outer sleeve; and / or,

[0012] The first particle collecting component is a particle collecting component with a rough and sticky surface, preferably a quartz glass plate with a rough and sticky surface, or a rubber plate; and / or,

[0013] A flow channel for gas samples and standard samples to flow into the detection device is formed between the first outer sleeve and the first sample inlet tube, and the second gas outlet of the first outer sleeve is used to communicate with the detection device; and / or,

[0014] The sampling device also has a first air inlet pipe for gas sample intake and a second air inlet pipe for standard sample intake in parallel, and the first air inlet pipe and the second air inlet pipe are connected to the air inlet of the first sampling pipe.

[0015] <3> like <2> The gas sample injection device, the power device is a nitrogen generating device, a nitrogen bottle or a helium bottle.

[0016] <4> like <2> In the gas sample injection device, the first injection tube has an air inlet, and the first and second air inlet tubes are connected to the air inlet of the first injection tube through a first tee.

[0017] <5> like <1> The gas sample injection device further comprises a second injection tube, a second outer sleeve, and a second particle collecting component;

[0018] At least a portion of the second injection tube is disposed in the second outer sleeve, a gas flow channel is formed between the second outer sleeve and the second injection tube, the second injection tube has an air inlet and an air outlet, and the air outlet of the second injection tube is located in the second outer sleeve;

[0019] The second outer sleeve has an air inlet for introducing a barrier agent for the object to be tested, a first air outlet for connecting to the exhaust device to inhale gas samples and standard samples, and a second air outlet for the circulation of gas samples and standard samples. A second particle collecting component is arranged at the first air outlet, and the air outlet of the second sampling tube is arranged toward the second particle collecting component. The distance between the second air outlet and the second particle collecting component is greater than the distance between the air outlet of the second sampling tube and the second particle collecting component.

[0020] <6> like <5> The gas sample injection device, the second outer sleeve and the second injection tube form a flow channel for the gas sample and the standard sample to flow into the detection device, and the second gas outlet of the second outer sleeve is used to communicate with the detection device; and / or,

[0021] The gas sampling device further comprises a power device for passing the analyte barrier agent into the second outer sleeve through the gas inlet of the second outer sleeve; and / or,

[0022] The inner diameter of the second injection tube decreases continuously or discontinuously in the direction from the gas inlet to the gas outlet.

[0023] According to a second aspect of the present invention, an embodiment of the present invention provides a detection device for detecting ammonia / amine substances in the atmosphere.

[0024] <7> A detection device for detecting ammonia / amine substances in the atmosphere, comprising: <1> to <6> The gas sample injection device and the proton transfer reaction mass spectrometer or the proton transfer reaction time-of-flight mass spectrometer as described in one of the above, wherein the proton transfer reaction mass spectrometer or the proton transfer reaction time-of-flight mass spectrometer has a sampling device that provides flow power for gas samples and standard samples to enter the mass spectrometer.

[0025] <8> like <7> In the detection device, the air extraction capacity of the air extraction device is greater than that of the sampling device.

[0026] According to a third aspect of the present invention, an embodiment of the present invention provides a method for detecting ammonia / amine substances in the atmosphere.

[0027] <9> A use of <7> or <8> The method for detecting ammonia / amine substances in the atmosphere by using the detection device comprises the following steps:

[0028] Passing barrier agent;

[0029] Atmospheric samples and standard samples are introduced alternately;

[0030] Proton transfer reaction mass spectrometer or proton transfer reaction time-of-flight mass spectrometer detects the content of ammonia / amine substances in the atmosphere.

[0031] <10> like <9> In the detection method, the barrier agent is 1H,1H-perfluorooctylamine.

[0032] The beneficial effects of the embodiments of the present invention are as follows:

[0033] The gas sample injection device proposed in the embodiment of the present invention utilizes the difference in gas / particle inertia to separate gas and particulate matter, efficiently and simply remove particulate matter, avoid the interference of particulate matter on analysis and detection, and improve the precision and accuracy of ammonia / amine substances in the atmosphere.

[0034] The sampling device adopts a double-layer sleeve structure, which can be used to pass the barrier agent of the object to be tested, block the contact between ammonia / amine and the tube wall, avoid the sample loss (wall effect loss) in the traditional online / offline analysis process, and use a hydrophilic barrier agent to absorb moisture in the gas sample to eliminate moisture interference. In addition, the barrier agent of the present invention is introduced through the outer sleeve instead of the sampling tube, which can prevent the barrier agent from being hydrophilic in the air sample during the gas-particle separation process, resulting in the hydrolysis equilibrium being broken, and the ammonium in the granular state being converted into ammonia gas, affecting the observation accuracy.

[0035] By using the sampling device, combined with a controller and a detection device, the sampling and analysis of various substances to be tested in the atmosphere (such as various ammonia / amine substances) can be completed unattended, and continuous and uninterrupted sampling and analysis of substances to be tested in the atmosphere over a period of time can also be achieved.

[0036] The sampling device is combined with a proton transfer reaction mass spectrometer or a proton transfer reaction time-of-flight mass spectrometer to analyze the concentrations of various ammonia / amine substances in the atmosphere with high time resolution.

[0037] When the sampling device includes multiple parallel sampling tubes and outer sleeves, they can be enabled at the same time for cross-sampling. If one sampling channel fails, the other sampling channels can operate normally to prevent data loss caused by the failure. The detection values ​​of multiple sampling channels can also be used for data processing and correction. When the data deviation is within the allowable range, the average value of the multi-channel data can be calculated. When the data deviation is too large, it means that the device is unstable or there is a failure. The data in this period can be deleted or the detection data of a certain sampling channel in this period can be deleted. In this way, uninterrupted detection is guaranteed and more accurate detection results can be obtained.

[0038] The detection device includes both a vacuum device and a sampling device, and the gas is affected by both of them at the same time. In particular, the vacuum capacity of the vacuum device is set to be greater than that of the sampling device, that is, the power of the vacuum device is greater than that of the sampling device, or the vacuum degree of the vacuum device is greater than that of the sampling device, which helps to better eliminate the interference of particulate matter on detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is a schematic diagram of a gas sample injection device with two injection channels proposed in an embodiment of the present invention. DETAILED DESCRIPTION

[0040] To make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings. However, those skilled in the art will appreciate that the present invention is not limited to the accompanying drawings and the following embodiments.

[0041] Example 1 Gas sample injection device

[0042] Reference Figure 1 This embodiment proposes a gas sample injection device that can be used for detecting ammonia / amine pollutants in the atmosphere, including a first injection tube 10, a first outer sleeve 20, a first particle collection component 30, a power device 40 and a suction device 50.

[0043] The first injection tube 10 is used for gas sample injection. At least a part of the first injection tube 10 is arranged in the first outer sleeve 20. The first injection tube 10 has an air inlet 11 and an air outlet 12. The air outlet 12 is located in the first outer sleeve. The first injection tube 10 is made of quartz glass, for example, and can be integrally formed or composed of a plurality of parts. The first injection tube 10 has one or more air inlets 11. When it has one air inlet 11, both the gas sample and the standard sample are inletted from the air inlet. When it has multiple air inlets (not shown in the figure), the gas sample and the standard sample can be inletted from different air inlets respectively.

[0044] The gas sample injection device also has a first air inlet pipe and a second air inlet pipe in parallel (not shown in the figure), the first air inlet pipe and the second air inlet pipe are connected to the air inlet of the first injection pipe, the first air inlet pipe serves as the gas sample air inlet pipe, and the second air inlet pipe serves as the standard sample air inlet pipe. In a preferred embodiment, the first injection pipe 10 has an air inlet 11, the air inlet 11 is connected to one end of the first tee 13, and the other two ends of the first tee 13 are respectively connected to the first air inlet pipe and the second air inlet pipe. By using an air inlet 11 and connecting two air inlet pipes through the first tee 13, the gas sample and the standard sample can be allocated and switched more quickly, reasonably and accurately under the control of the controller, and the air intake is more convenient, making the quantification more accurate.

[0045] Preferably, the inner diameter of the first injection tube 10 decreases continuously or discontinuously in the direction from the air inlet to the air outlet. In one embodiment, the inner diameter of the first injection tube 10 gradually decreases in the direction from the air inlet to the air outlet; in another embodiment, the first injection tube 10 has two or more different inner diameters, and the two or more inner diameters generally decrease in the direction from the air inlet to the air outlet, for example, Figure 1 As shown, the first injection tube 10 has three different inner diameters, namely the first inner diameter R1, the second inner diameter R2, and the third inner diameter R3. In the direction from the air inlet to the air outlet, the first inner diameter> the second inner diameter> the third inner diameter. By reducing the inner diameter of the first injection tube continuously or discontinuously in the direction from the air inlet to the air outlet, the speed of the air flow in the first injection tube can be increased. Since the gas sample will be affected by the combined action of the exhaust device and the sampling device for providing power for the detection device when the sample is injected through the injection device, the use of multi-stage acceleration can use a lower power exhaust device, thereby effectively avoiding the interference of the exhaust device on the injection, which is conducive to the smooth injection of the sample.

[0046] The first outer sleeve 20 is used for passing the barrier agent of the object to be tested and forming a gas flow channel. The first outer sleeve 20 is sleeved on at least a portion of the first sampling tube 10. The inner diameter of the first outer sleeve 20 is larger than the outer diameter of the first sampling tube 10. A gas flow channel is formed between the first outer sleeve 20 and the first sampling tube 10. Under the action of the sampling device, the gas sample and the standard sample can flow into the detection device along the flow channel.

[0047] The first outer sleeve 20 has an air inlet 21, a first air outlet 22 and a second air outlet 23. The air inlet 21 and the second air outlet 22 of the first outer sleeve 20 are arranged at one end of the first outer sleeve 20, and the first air outlet 22 is arranged at the other end of the first outer sleeve.

[0048] The air inlet 21 of the first outer sleeve 20 is used to pass the barrier agent of the object to be detected, and the power device 40 is used to pass the barrier agent of the object to be detected into the first outer sleeve 20 through the air inlet 21 of the first outer sleeve 20. The power device 40 is, for example, a gas generating device (such as a nitrogen generating device), a nitrogen cylinder, a helium cylinder, etc., which can output gas as a carrier gas, heat and gasify the barrier agent of the object to be detected pre-placed in the barrier agent container C, and then bring it into the first outer sleeve 20 by the carrier gas. The barrier agent of the object to be detected is adsorbed on the inner wall of the first outer sleeve 20, which can prevent the object to be detected from contacting with the inner wall of the first outer sleeve 20, thereby preventing the wall effect loss of the object to be detected, and making the detection result more accurate. The barrier agent for the object to be tested is preferably 1H,1H-perfluorooctylamine. After the barrier agent is heated and vaporized, it is brought into the first outer sleeve 20 by the carrier gas output by the power device 40, and adsorbed on the inner wall of the first outer sleeve 20 after being cooled. It can not only prevent the object to be tested from contacting the inner wall of the first outer sleeve 20, but also because its hydrophilicity is higher than other ammonia / amine substances, it can eliminate the interference of moisture on the detection.

[0049] A first particle collecting component 30 is provided at the first gas outlet 22 of the first outer sleeve 20. The first particle collecting component 30 is used to collect particles in the gas. The first particle collecting component 30 is opposite to the gas outlet of the first injection tube 10, that is, the gas outlet 12 of the first injection tube 10 is arranged toward the first particle collecting component 30. There is a gap between the first particle collecting component 30 and the gas outlet 12 of the first injection tube 10. The first particle collecting component 30 can absorb particles and eliminate the rebound effect of particles. For example, it is a particle collecting component with a rough and sticky surface, preferably a quartz glass plate with a rough and sticky surface, or a rubber plate, and the rubber plate refers to a plate coated with sticky substances such as glue, glycerin, lipids, vaseline, etc. The suction device 50 is connected to the first gas outlet 22 and is used to inhale gas samples and standard samples. There may be a variety of ways of connecting the exhaust device 50 to the first air outlet 22. In one embodiment, the first particle collecting component 30 covers the first air outlet 22, and the first particle collecting component 30 is provided with an air vent. The air vent and the air outlet 22 of the first sampling tube 10 are offset (i.e., the two are not opposite), and the exhaust device 50 exhausts air through the air vent.

[0050] During detection, the gas sample is injected through the sampling device, and the gas sample will be acted upon by the exhaust device 50 and the sampling device used to provide power for the detection device. Gas samples, such as atmospheric samples, are often mixed with particulate matter. After the gas sample is sucked into the first injection tube 10 by the exhaust device 50, it is accelerated in the first injection tube 10 with a reduced inner diameter, and the particulate matter is also accelerated accordingly. The gas sample can flow into the detection device from the gas flow channel between the first outer sleeve 20 and the first injection tube 10 under the action of the sampling device. Since the particulate matter has a large mass and a greater inertia than the gas molecules, the movement path of the particulate matter cannot be turned back, and can be discharged from the gas outlet 12 of the first injection tube 10 and adsorbed by the first particle collection component 30. The present invention adopts the first particle collecting component 30 to collect particles instead of discharging the particles through a pipeline, which can avoid the pipeline discharge method that the pipeline is prone to accumulation of particles after a period of time, thereby causing blockage. The surface of the first particle collecting component 30 is rough and sticky, and the accelerated particles quickly hit the collection plate without affecting the gas diversion. After a period of time, the particle collecting component is replaced or cleaned.

[0051] The second gas outlet 23 of the first outer sleeve 20 is used as the gas outlet of the gas sample and the standard sample. The second gas outlet 23 of the first outer sleeve 20 is connected to the sample inlet of the detection device through the first gas guide channel. The detection device is, for example, a proton transfer reaction mass spectrometer (PTR-MS) or a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). The detection device has a sampling device, such as an air pump, to provide flow power for the gas sample and the standard sample to enter the detection device. The distance between the second gas outlet 23 of the first outer sleeve 20 and the first particle collection component 30 is greater than the distance between the gas outlet 12 of the first injection tube 10 and the first particle collection component (as shown in the figure, the gas outlet of the first outer sleeve is lower than the gas outlet of the first injection tube). Preferably, the distance between the gas outlet 12 of the first injection tube 10 and the first particle collection component 30 is adjustable. In one embodiment, the direction of the second gas outlet 23 of the first outer sleeve 20 is perpendicular to the direction of the gas outlet 12 of the first injection tube 10. In this case, the distance between the second gas outlet 23 of the first outer sleeve 10 and the first particle collecting component 30 refers to the distance between the uppermost part of the second gas outlet 23 of the first outer sleeve 20 and the first particle collecting component 30. Through the above arrangement, the gas sample or the standard sample enters the first injection tube 10 through the gas inlet 11 of the first injection tube 10, flows out from the gas outlet 12 of the first injection tube 10, and enters the first outer sleeve 20. Since the distance between the second gas outlet 23 of the first outer sleeve 20 and the first particle collecting component 30 is relatively large, the flow direction of the gas sample and the standard sample is changed. After turning back, the gas sample and the standard sample flow out through the second gas outlet 23 of the first outer sleeve 20 and enter the detection device. As mentioned above, during detection, the gas sample is acted upon by the exhaust device 50 and the sampling device. The distance between the gas outlet 12 of the first sampling tube 10 and the first particle collecting component 30 is adjustable, and the distance between the two can be adjusted according to actual conditions, thereby changing the effect of the exhaust device 50 and the sampling device on the gas sample, which can not only ensure smooth sampling of the detection device, but also achieve the effect of effective separation of gas-particle distribution.

[0052] The gas sampling device of this embodiment is connected to a proton transfer reaction mass spectrometer or a proton transfer reaction time-of-flight mass spectrometer, and can be used as a sampling device for detecting ammonia / amine substances in the atmosphere using a proton transfer reaction mass spectrometry method.

[0053] Next, a working mode of the gas sample injection device of the preferred embodiment is exemplified by taking the detection of ammonia / amine substances in the atmosphere by proton transfer reaction mass spectrometry as an example.

[0054] The power device and the exhaust device are turned on. The power device introduces gasified perfluorooctylamine, a barrier agent for the test object, into the first outer sleeve. The perfluorooctylamine condenses on the tube wall of the first outer sleeve when it is cold, and is used to block the ammonia / amine test substances in the atmosphere, and can also eliminate the interference of moisture in the gas sample. The exhaust device alternately inhales the atmospheric sample and the standard sample (the standard sample is, for example, ammonia, methyleneamine, methylamine, ethylamine, 1-butylamine, 1-pentylamine, neopentylamine, aniline, 2-methylaniline, etc., and a single standard sample or a mixture of standard samples can be used as the standard sample). The atmospheric sample is introduced into the sample tube, and the particles in the sample are accelerated by the sample tube, hit the particle collecting component, and are adsorbed by the particle collecting component. A part of the gas can change its flow direction under the action of the sampling device of the proton transfer reaction mass spectrometer or the proton transfer reaction time-of-flight mass spectrometer, and then return to the proton transfer reaction mass spectrometer or the proton transfer reaction time-of-flight mass spectrometer to detect the ammonia / amine analyte in the atmosphere. The gas sample and the standard sample are alternately introduced, and the external standard method can be used for quantitative detection. Figure 1 As shown, the solid arrow F0 represents the barrier agent flow path, the solid arrow F1 represents the standard sample flow path, the solid arrow F2 represents the gas sample flow path, and the dotted arrow F3 represents the particle flow path.

[0055] Further preferably, the gas sampling device of this embodiment further comprises a second sampling tube 10', a second outer sleeve 20' and a second particle collecting component 30'.

[0056] The second injection tube 10' is used for gas sample injection. At least a part of the second injection tube 10' is arranged in the second outer sleeve 20'. The second injection tube 10' has an air inlet 11' and an air outlet 12'. The air outlet 12' is located in the second outer sleeve 20'. The second injection tube 10' is made of quartz glass, for example, and can be integrally formed or composed of a plurality of parts. The second injection tube 10' has one or more air inlets. When it has one air inlet 11', the gas sample and the standard sample are both inletted from the air inlet. When it has multiple air inlets, the gas sample and the standard sample can be inletted from different air inlets respectively.

[0057] The gas sample injection device also has a third air inlet pipe and a fourth air inlet pipe in parallel (not shown in the figure), and the third air inlet pipe and the fourth air inlet pipe are connected to the air inlet 11' of the second injection pipe 10', and the third air inlet pipe serves as the gas sample air inlet pipe, and the fourth air inlet pipe serves as the standard sample air inlet pipe. In a preferred embodiment, the second injection pipe has an air inlet, and the air inlet 11' is connected to one end of the second tee 13', and the other two ends of the second tee 13' are respectively connected to the third air inlet pipe and the fourth air inlet pipe. By using an air inlet 11' and connecting two air inlet pipes through the second tee 13', the gas sample and the standard sample can be allocated and switched more quickly, reasonably and accurately under the control of the controller, and the air intake is more convenient, making the quantification more accurate.

[0058] Preferably, the inner diameter of the second injection tube 10' decreases continuously or discontinuously in the direction from the air inlet to the air outlet. In one embodiment, the inner diameter of the second injection tube 10' tapers in the direction from the air inlet to the air outlet; in another embodiment, the second injection tube 10' has two or more different inner diameters, and the two or more inner diameters generally show a decreasing trend in the direction from the air inlet to the air outlet. For example, the second injection tube 10' has three different inner diameters, namely the first inner diameter R1, the second inner diameter R2, and the third inner diameter R3. In the direction from the air inlet to the air outlet, the first inner diameter> the second inner diameter> the third inner diameter. By reducing the inner diameter of the second injection tube 10' continuously or discontinuously in the direction from the air inlet to the air outlet, the speed of the airflow in the second injection tube 10' can be increased. When the gas sample is injected through the injection device, it will be affected by the combined action of the exhaust device and the sampling device used to provide power for the detection device. The use of multi-stage acceleration can use a lower power exhaust device, thereby effectively avoiding the interference of the exhaust device on the injection, which helps to smoothly inject the sample.

[0059] The second outer sleeve 20′ is used for passing the barrier agent of the object to be tested and forming a gas flow channel. The second outer sleeve 20′ is sleeved on at least a portion of the second sampling tube 10′. The inner diameter of the second outer sleeve 20′ is larger than the outer diameter of the second sampling tube 10′. A gas flow channel is formed between the second outer sleeve 20′ and the second sampling tube 10′. Under the action of the sampling device, the gas sample and the standard sample can flow into the detection device along the flow channel.

[0060] The second outer sleeve 20' has an air inlet 21', a first air outlet 22' and a second air outlet 23'. The air inlet 21' and the second air outlet 23' of the second outer sleeve 20' are arranged at one end of the second outer sleeve 20', and the first air outlet 22 is arranged at the other end of the second outer sleeve 20'.

[0061] The air inlet 21' of the second outer sleeve 20' is used to introduce the barrier agent of the object to be tested, and the power device (not shown in the figure) is used to introduce the barrier agent of the object to be tested into the second outer sleeve 20' through the air inlet 21' of the second outer sleeve 20'. The power device is, for example, a gas generating device (such as a nitrogen generating device), a nitrogen cylinder, a helium cylinder, etc., which can output gas as a carrier gas to bring the gasified barrier agent of the object to be tested into the second outer sleeve 20'. The barrier agent of the object to be tested is adsorbed on the inner wall of the second outer sleeve, which can prevent the contact between the object to be tested and the inner wall of the second outer sleeve, thereby preventing the loss of the wall effect of the object to be tested and making the detection result more accurate. The barrier agent for the object to be tested is preferably 1H,1H-perfluorooctylamine. After the barrier agent is heated and vaporized, it is carried into the second outer sleeve by the carrier gas output by the power device, and adsorbed on the inner wall of the second outer sleeve after being cooled. It can not only prevent the object to be tested from contacting the inner wall of the second outer sleeve, but also because its hydrophilicity is higher than other ammonia / amine substances, it can eliminate the interference of moisture on the detection.

[0062] A second particle collecting component 30' is provided at the first gas outlet 21' of the second outer sleeve 20'. The second particle collecting component 30' is used to collect particles in the gas. The second particle collecting component is opposite to the gas outlet 12' of the second sampling tube 10', that is, the gas outlet 12' of the second sampling tube 10' is arranged toward the second particle collecting component 30'. There is a gap between the second particle collecting component 30' and the gas outlet 12' of the second sampling tube 10'. The second particle collecting component 30' can absorb particles and eliminate the rebound effect of particles. For example, it is a particle collecting component with a rough and sticky surface, preferably a quartz glass plate with a rough and sticky surface, or a rubber plate, which refers to a plate coated with sticky substances such as glue, glycerin, lipids, vaseline, etc. The suction device 50 is connected to the first gas outlet 12' and is used to inhale gas samples and standard samples. There may be a variety of ways of connecting the exhaust device 50 with the first air outlet 12′. In one embodiment, the second particle collecting component 30′ covers the first air outlet 12′, and the second particle collecting component 30′ is provided with an air vent, which is offset from the air outlet 12′ of the second sampling tube 10′ (i.e., the two are not opposite), and the exhaust device 50 exhausts air through the air vent.

[0063] During detection, the gas sample is injected through the sampling device, and the gas sample will be acted upon by the exhaust device and the sampling device used to provide power for the detection device. Gas samples, such as atmospheric samples, are often mixed with particles. After the gas sample is sucked into the second injection tube by the exhaust device, it is accelerated in the second injection tube with a reduced inner diameter, and the particles are also accelerated accordingly. The gas sample can flow into the detection device from the gas flow channel between the second outer sleeve and the second injection tube under the action of the sampling device. Since the particles have a large mass and a greater inertia than gas molecules, the movement path of the particles cannot be turned back, and they can be discharged from the gas outlet of the second injection tube and adsorbed by the first particle collection component.

[0064] The second gas outlet 23' of the second outer sleeve 20' is used as the gas outlet for the gas sample and the standard sample, and the second gas outlet 23' of the second outer sleeve 20' is connected to the sample inlet of the detection device through the first air guide tube. The detection device is, for example, a proton transfer reaction mass spectrometer (PTR-MS) or a proton transfer reaction time-of-flight mass spectrometer, and the detection device has a sampling device, such as an air pump, to provide flow power for the gas sample and the standard sample to enter the detection device. The distance between the second gas outlet 23' of the second outer sleeve 20' and the second particle collection component 30' is greater than the distance between the gas outlet 12' of the second injection tube 10' and the second particle collection component 30' (as shown in the figure, the second gas outlet 23' of the second outer sleeve 20' is lower than the gas outlet 12' of the second injection tube 10'). Preferably, the distance between the gas outlet 12' of the second injection tube 10' and the second particle collection component 30' is adjustable. In one embodiment, the direction of the second gas outlet 23' of the second outer sleeve 20' is perpendicular to the direction of the gas outlet 12' of the second injection tube 10'. In this case, the distance between the second gas outlet 23' of the second outer sleeve 20' and the second particle collecting component 30' refers to the distance between the uppermost part of the second gas outlet 23' of the second outer sleeve 20' and the second particle collecting component 30'. With the above arrangement, the gas sample or the standard sample enters the second injection tube 10' through the gas inlet 11' of the second injection tube 10', flows out from the gas outlet 12' of the second injection tube 10', and enters the second outer sleeve 20'. Since the distance between the second gas outlet 23' of the second outer sleeve 20' and the second particle collecting component 30' is large, the flow direction of the gas sample and the standard sample is changed. After turning back, the gas sample and the standard sample flow out through the second gas outlet 23' of the second outer sleeve 20' and enter the detection device. As mentioned above, during detection, the gas sample is acted upon by the exhaust device and the sampling device. The distance between the gas outlet 12' of the first sampling tube 10' and the second particle collecting component 30' is adjustable, and the distance between the two can be adjusted according to actual conditions, thereby changing the effect of the exhaust device and the sampling device on the gas sample, which can not only ensure smooth sampling of the detection device, but also achieve the effect of effective separation of gas-particle distribution.

[0065] Those skilled in the art will appreciate that the gas sample injection device of this embodiment may also include more than two injection tubes and outer sleeves connected in parallel, and their structures and arrangements are the same as those described above and need not be elaborated.

[0066] When the gas sampling device includes two or more parallel sampling tubes and outer sleeves, they can be enabled at the same time, share a detection device, and perform cross-sampling. If one sampling channel fails, the other sampling channels can operate normally, preventing data loss caused by failures, which is beneficial to continuous monitoring of air quality. The detection values ​​of multiple sampling channels can also be used for data processing and correction. When the data deviation is within the allowable range, the average value of multi-channel data can be calculated. When the data deviation is too large, it means that the device is unstable or there is a fault. The data for this period can be deleted or the detection data of a certain sampling channel within this period can be deleted. In this way, uninterrupted detection is guaranteed and more accurate detection results can be obtained.

[0067] The gas sampling device of this embodiment can realize automatic operation by controlling the solenoid valve (two-way valve, three-way valve) and the like provided in the flow path through a controller.

[0068] Example 2 Gas sample detection device

[0069] This embodiment proposes a gas sample detection device for detecting ammonia / amine substances in the atmosphere, comprising the gas sample injection device and a proton transfer reaction mass spectrometer (PTR-MS) or a proton transfer reaction time-of-flight mass spectrometer described in Embodiment 1, wherein the proton transfer reaction mass spectrometer (PTR-MS) has a sampling device (not shown in the figure), such as a vacuum pump, to provide flow power for gas samples and standard samples to enter the detection device. The atmospheric sample and the standard sample alternately enter the proton transfer reaction mass spectrometer or the proton transfer reaction time-of-flight mass spectrometer through the gas sample injection device to detect the content of ammonia / amine substances in the atmosphere.

[0070] Further preferably, the air extraction capacity of the air extraction device is greater than that of the sampling device, that is, the power of the air extraction device is greater than that of the sampling device, or the vacuum degree of the air extraction device is greater than that of the sampling device. This helps to better eliminate the interference of particulate matter on the detection.

[0071] Example 3 Detection method of ammonia / amine substances in the atmosphere

[0072] This embodiment proposes a detection method for detecting ammonia / amine substances in the atmosphere using the gas sample detection device of embodiment 2, comprising the following steps:

[0073] Passing barrier agent;

[0074] Atmospheric samples and standard samples are introduced alternately;

[0075] Proton transfer reaction mass spectrometer or proton transfer reaction time-of-flight mass spectrometer detects the content of ammonia / amine substances in the atmosphere.

[0076] Preferably, the barrier is 1H,1H-perfluorooctylamine. After the analyte barrier is heated and gasified, it is carried into the first outer sleeve by the carrier gas output by the power device, and adsorbed on the inner wall of the first outer sleeve after being cooled, which can not only prevent the analyte from contacting the inner wall of the first outer sleeve, but also eliminate the interference of moisture on the detection because its hydrophilicity is higher than other ammonia / amine substances.

[0077] It should be noted that, in this embodiment, the barrier agent can be introduced before the atmospheric sample / standard sample is introduced, or can be introduced at the same time as the atmospheric sample / standard sample is introduced.

[0078] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A gas sample injection device containing ammonia and / or amine substances, characterized in that: It includes a first sample inlet tube, a first outer sleeve, a first particle collecting component and an air extraction device; At least a portion of the first injection tube is disposed in the first outer sleeve, a gas flow channel is formed between the first outer sleeve and the first injection tube, the first injection tube has an air inlet and an air outlet, and the air outlet of the first injection tube is located in the first outer sleeve; The first outer sleeve has an air inlet for introducing a barrier agent for the object to be tested, a first air outlet for connecting the air extraction device to inhale a gas sample and a standard sample, and a second air outlet for the circulation of the gas sample and the standard sample, a first particle collecting component is arranged at the first air outlet, the air outlet of the first injection tube is arranged toward the first particle collecting component, and the distance between the second air outlet and the first particle collecting component is greater than the distance between the air outlet of the first injection tube and the first particle collecting component; The gas sample injection device also includes a power device for passing the analyte barrier agent into the first outer sleeve through the gas inlet of the first outer sleeve; The power device is a nitrogen generator, a nitrogen cylinder or a helium cylinder; The gas sample injection device also has a first air inlet pipe for gas sample injection and a second air inlet pipe for standard sample injection in parallel, wherein the first air inlet pipe and the second air inlet pipe are connected to the air inlet of the first injection pipe; The first inlet tube has an air inlet, and the first inlet tube and the second inlet tube are connected to the air inlet of the first inlet tube through a first tee.

2. The gas sample injection device according to claim 1, characterized in that: The inner diameter of the first injection tube decreases continuously or discontinuously in the direction from the air inlet to the air outlet; and / or, The distance between the gas outlet of the first sample inlet tube and the first particle collecting component is adjustable; and / or, The air inlet and the second air outlet of the first outer sleeve are arranged at one end of the first outer sleeve, and the first air outlet is arranged at the other end of the first outer sleeve; and / or, The first particle collecting component is a particle collecting component with a rough and sticky surface, or is a rubber sheet; and / or, A flow channel for gas samples and standard samples to flow into the detection device is formed between the first outer sleeve and the first sample inlet tube, and the second gas outlet of the first outer sleeve is used to communicate with the detection device.

3. The gas sample injection device according to claim 2, characterized in that: The first particle collecting component is a quartz glass plate with a rough surface and adhesiveness.

4. The gas sample injection device according to claim 1, characterized in that: The gas sample injection device also includes a second injection tube, a second outer sleeve, and a second particle collection component; At least a portion of the second injection tube is disposed in the second outer sleeve, a gas flow channel is formed between the second outer sleeve and the second injection tube, the second injection tube has an air inlet and an air outlet, and the air outlet of the second injection tube is located in the second outer sleeve; The second outer sleeve has an air inlet for introducing a barrier agent for the object to be tested, a first air outlet for connecting to the exhaust device to inhale gas samples and standard samples, and a second air outlet for the circulation of gas samples and standard samples. A second particle collecting component is arranged at the first air outlet, and the air outlet of the second sampling tube is arranged toward the second particle collecting component. The distance between the second air outlet and the second particle collecting component is greater than the distance between the air outlet of the second sampling tube and the second particle collecting component.

5. The gas sample injection device according to claim 4, characterized in that: A flow channel for gas samples and standard samples to flow into the detection device is formed between the second outer sleeve and the second sample inlet tube, and the second gas outlet of the second outer sleeve is used to communicate with the detection device; and / or, The gas sample injection device further comprises a power device for passing the analyte barrier agent into the second outer sleeve through the gas inlet of the second outer sleeve; and / or, The inner diameter of the second injection tube decreases continuously or discontinuously in the direction from the gas inlet to the gas outlet.

6. A detection device for detecting ammonia / amine substances in the atmosphere, characterized in that: It comprises the gas sample injection device as described in any one of claims 1 to 5 and a proton transfer reaction mass spectrometer or a proton transfer reaction time-of-flight mass spectrometer, wherein the proton transfer reaction mass spectrometer or the proton transfer reaction time-of-flight mass spectrometer has a sampling device for providing flow power for gas samples and standard samples to enter the mass spectrometer.

7. The detection device according to claim 6, characterized in that: The air extraction capacity of the air extraction device is greater than that of the sampling device.

8. A method for detecting ammonia / amine substances in the atmosphere using the detection device as claimed in claim 6 or 7, characterized in that: The following steps are involved: Passing barrier agent; Atmospheric samples and standard samples are introduced alternately; Proton transfer reaction mass spectrometer or proton transfer reaction time-of-flight mass spectrometer detects the content of ammonia / amine substances in the atmosphere.

9. The detection method according to claim 8, characterized in that: The barrier agent is 1H,1H-perfluorooctylamine.

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