Online detection system and method for aerosol-amine collaborative escape heterogeneous reaction

Abstract

The invention belongs to the technical field of online detection of aerosol-amine collaborative escape heterogeneous reaction, and particularly relates to an online detection system and method for aerosol-amine collaborative escape heterogeneous reaction. The system comprises an aerosol particle generation device and a double-flow-tube reaction device which are communicated with each other, and further comprises an ozone generation and detection device which is communicated with the double-flow-tube reaction device, the double-flow-tube reaction device comprises a first flow tube reactor, an ozone decomposition agent container and a second flow tube reactor which are sequentially connected, and air outlets of the aerosol particle generation device and the ozone generation and detection device are respectively communicated with an air inlet of the first flow tube reactor. The method can be synchronously realized by combining the tandem type double-flow-tube reaction device with APPI-HRMS, the distribution characteristics of the SOZ particle multiphase reaction product can be obtained online in real time, and the effective absorption coefficient can be accurately measured by quantifying the SOZ multiphase reaction rate.

Description

Technical Field

[0001] The present invention belongs to the technical field of on-line detection of aerosol-amine synergistic escape multiphase reactions, and particularly relates to an on-line detection system and method for aerosol-amine synergistic escape multiphase reactions. Background Technique

[0002] Atmospheric particulate matter derived from behaviors such as fossil fuel combustion and biomass burning will continuously change its physical and chemical properties through complex atmospheric chemical reactions. Among them, amine compounds in the atmosphere play a key role in the formation and growth of new particulate matters such as secondary organic aerosols. These amine compounds can not only participate in new particle formation as key precursors, but also exacerbate particulate matter pollution through mechanisms such as acid-base neutralization and hygroscopicity regulation. Research shows that amine chemical processes have become a potential driving force for exceeding the standard of regional particulate matter pollution in the atmosphere (Nature. 2013; 502, 7471, 359-363). Therefore, clarifying the atmospheric amine chemical processes of particulate matter is of great scientific significance for revealing the evolution law of particulate matter and collaborative pollution control.

[0003] In terms of experimental methods, two newly developed on-line research systems are worthy of attention: 1) The flow tube reactor-infrared spectroscopy combined system. For example, Gao et al. constructed a stainless-steel flow tube reaction system combined with infrared spectroscopy technology, and in-situ quantified the heterogeneous surface reaction rate of crystalline succinic acid and n-butylamine by precisely controlling environmental condition parameters (such as temperature, humidity, and reactant conditions, etc.) (Phys. Chem. Chem. Phys. 2018, 20(22), 15464-15472); 2) The temperature-programmed Knudsen cell-mass spectrometry combined system. Li et al. used the Knudsen cell temperature-programmed desorption device combined with a quadrupole mass spectrometer to reveal the temperature dependence law of the gas-solid reaction absorption coefficient of solid acid / n-butylamine (ACS ES&T Air 2023, 1(1), 52-61).

[0004] In terms of experimental devices, the Knudsen cell temperature-programmed desorption device and the flow tube reactor are common experimental devices for studying particulate matter heterogeneous reaction kinetics. Among them, the former uses a large reaction cavity (about 5260 cm 3) is equipped with a liquid nitrogen temperature control system and a vacuum control module (ACS ES&T Air. 2023; 1(1), 52 - 61). Its operation process includes key pretreatment steps: 1) The reactor chamber is passivated with amine for 90 minutes before the experiment to establish a steady-state mass spectrometry signal (Environ Sci Technol. 2012; 46(20), 11112 - 11118); 2) Gaseous amine (such as n-butylamine) needs to go through three freeze-thaw cycles, be filled in a 5L vacuum bulb, and then be introduced into the reaction chamber (Phys. Chem. Chem. Phys. 2017, 19(6), 4827 - 4839). For the flow tube reactor, it has a simple structure and is easy to disassemble. The patented technology CN202410607412.5 expands the temperature control ability of the quartz flow tube by integrating a constant temperature water bath layer. Currently, by combining the particle coating method (ACS Earth Space Chem. 2018, 2(9), 904 - 914) and the integration method (Phys. Chem. Chem. Phys. 2018; 20(22), 15464 - 15472), the particulate matter is coated or fixed inside the flow tube, and the kinetic parameters of the particulate matter heterogeneous reaction can be measured online.

[0005] According to the above description of the technical background, the technical obstacles faced in in-situ analyzing the particulate matter-amine heterogeneous reaction mechanism are mainly: ① The limitation of the research object; ② The complexity of the experimental device.

[0006] 1) The limitation of the research object.

[0007] Existing research systems mainly focus on the reactions of stable crystal particles (such as crystalline organic acids) with simple amine compounds (such as n-butylamine) (Phys. Chem. Chem. Phys. 2017, 19(38), 26296 - 26309; Phys. Chem. Chem. Phys. 2017, 19(6), 4827 - 4839; Phys. Chem. Chem. Phys. 2018, 20(22), 15464 - 15472; ACS ES&T Air. 2023, 1(1), 52 - 61.). These particulate matters are mostly stable model compounds, which are easy to conduct heterogeneous reaction experimental investigations. However, for organic particles with active properties such as SOZ, it is difficult to stably generate, and the related heterogeneous reaction research is lacking. For example, Qiu et al. studied the heterogeneous reaction products of SOZ generated from the ozonation of pinene with ethylamine using a smog chamber (Atmospheric Chem. Phys. 2024, 24(1), 155 - 166.). However, this research process still relies on the offline links of sample collection - analysis, resulting in the loss of active intermediates and it is difficult to online monitor the complete reaction process. In addition, the amine chemistry research in the aldehyde system still focuses on the homogeneous system (gas phase: Phys. Chem. Chem. Phys. 2019, 21(29), 16170 - 16179; liquid phase: J. Am. Chem. Soc. 1972, 94(1), 190 - 194), lacking kinetic data on heterogeneous reactions at the particle interface.

[0008] 2) Complexity of the experimental setup.

[0009] There are many defects in the experimental exploration devices for the heterogeneous amine reactions of particulate matters in terms of system design and operation efficiency. For example, the Knudsen cell temperature programmed desorption device has a complex structure, including multiple control systems and a large reaction chamber (about 5260 cm 3)(ACS ES&T Air. 2023, 1(1), 52 - 61). In addition, the operation timeliness and flexibility of the device are insufficient. Not only does it require a long - time amine passivation pretreatment operation (90 minutes) before the experiment (Environ Sci Technol. 2012, 46(20), 11112 - 11118), but the introduction of gaseous amine also needs to go through multiple freeze - thaw cycles (Phys. Chem. Chem. Phys. 2017, 19(6), 4827 - 4839). Moreover, although the combination of a flow - through stainless - steel reactor and infrared spectroscopy has a simple structure, it highly relies on particle immobilization technology. The sample crystal is integrated into a multiple - reflection sampler and placed at a fixed position in the flow - through stainless - steel chamber. This not only increases the operation difficulty of particulate matter extraction during the experiment, but also there will be chemical behavior deviations between the immobilized particles and real suspended particles, which is not conducive to exploring the particle - amine chemical reaction mechanism in the real atmospheric environment. Summary of the Invention

[0010] In view of the above - mentioned disadvantages of the prior art, the purpose of the present invention is to provide an on - line detection system and method for aerosol - amine co - escape multiphase reactions, which are used to solve the problems that it is difficult to continuously and stably generate active secondary ozonated particles (SOZ) in situ in the prior art, and the collection process is complex; the coupling interference in the process of ozone oxidation and amine reaction; off - line sampling is prone to product loss, and it is difficult to accurately analyze the multiphase amine decomposition of SOZ and its co - escape process with gaseous amine.

[0011] The first aspect of the present invention provides a pretreatment system for aerosol - amine co - escape multiphase reactions, which includes a connected aerosol particle generation device and a dual - flow - tube reaction device, and also includes an ozone generation and detection device. The ozone generation and detection device is connected to the dual - flow - tube reaction device. The dual - flow - tube reaction device includes a first flow - tube reactor, an ozone decomposer container, and a second flow - tube reactor connected in sequence. The air outlets of the aerosol particle generation device and the ozone generation and detection device are respectively connected to the air inlet of the first flow - tube reactor.

[0012] In some embodiments of the present invention, the aerosol particle generation device includes a first mass flowmeter, a heating glass tube, and an activated carbon container connected in sequence. The air outlet of the activated carbon container is connected to the air inlet of the first flow - tube reactor.

[0013] In some embodiments of the present invention, the ozone generation and detection device includes a second mass flowmeter, an ozone generator, and an ozone detector connected in sequence. The air outlet of the ozone detector is connected to the air inlet of the first flow - tube reactor.

[0014] In some embodiments of the present invention, the inlet of the first flow tube reactor is connected to a first gas path, and a third mass flowmeter is provided on the first gas path.

[0015] In some embodiments of the present invention, the inlets of the second flow tube reactor are respectively connected to a second gas path and a third gas path. A fourth mass flowmeter is provided on the second gas path, and a fifth mass flowmeter is provided on the third gas path.

[0016] The second aspect of the present invention provides an on-line detection system for aerosol-amine co-escaping multiphase reactions, including the above-mentioned pre-treatment system for the on-line detection system for aerosol-amine co-escaping multiphase reactions, and further including an atmospheric pressure photoionization ultra-high resolution mass spectrometry on-line detection device. The inlet of the atmospheric pressure photoionization ultra-high resolution mass spectrometry on-line detection device is communicated with the outlet of the second flow tube reactor.

[0017] The present invention also provides an on-line detection method for aerosol-amine co-escaping multiphase reactions, including the following steps:

[0018] 1) Obtain aerosol particles with removed gaseous organic impurities through an aerosol particle generation device;

[0019] 2) Generate ozone through an ozone generation and detection device;

[0020] 3) React the aerosol particles in step 1) with the ozone in step 2) through the first flow tube reactor to generate secondary ozonated particulate matter;

[0021] 4) Introduce an amine compound into the second flow tube reactor and react it with the secondary ozonated particulate matter generated in step 3) to obtain a reaction product;

[0022] 5) Introduce the reaction product obtained in step 4) into an atmospheric pressure photoionization ultra-high resolution mass spectrometry on-line detection device for detection.

[0023] The third aspect of the present invention provides a method for detecting the components of an on-line detection system for aerosol-amine co-escaping multiphase reactions,

[0024] The detection object is: secondary ozonated particulate matter.

[0025] The mass spectrometry conditions are: ionization mode: atmospheric pressure photoionization (APPI); sheath gas flow rate: 2Arb; auxiliary gas flow rate: 2Arb; purge gas flow rate: 2Arb; ion transfer tube temperature: 300 - 350 °C; scanning mass range: 50 - 800 Da; mass resolution: 500000 @ m / z 200.

[0026] The present invention has the following beneficial effects:

[0027] 1) By means of a first flow tube reactor and a second flow tube reactor connected in sequence, the present invention can continuously generate in-situ various active secondary ozonation particles (SOZ) with adjustable concentrations, and precisely conduct the reaction kinetics study on the co-escaping process with amines.

[0028] 2) In combination with an atmospheric pressure photoionization ultra-high resolution mass spectrometry on-line detection device, the present invention can be synchronously realized to obtain in real time the distribution characteristics of the multi-phase reaction products of SOZ particles and accurately determine the effective absorption coefficient by quantifying the multi-phase reaction rate of SOZ. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a schematic diagram of the overall device structure of Embodiment 1 of the present invention.

[0030] Figure 2 It is the MS signal trend of C 35 SOZ (m / z 526) in Embodiment 1 of the present invention with the increase of ozone concentration (a) and at a fixed ozone concentration (0.57 ppm) (b).

[0031] Figure 3 It is the mass spectrometry diagrams before (a) and after (b) the reaction of secondary ozonide with ethylamine in Embodiment 1 of the present invention.

[0032] Figure 4 It is the kinetic curves of SOZ particles (a) and their amine-added products (b) with the increase of ethylamine exposure in Embodiment 1 of the present invention.

[0033] Figure 5 It is the distribution diagram of the effective absorption coefficient of SOZ particles with the increase of carbon number

[0034] Figure 6 It is the mass spectrometry diagram after the reaction of secondary ozonide with ethylamine in Embodiment 2 of the present invention ([EA]=2.17 ppm).

[0035] Figure 7 It is the mass spectrometry diagram after the reaction of secondary ozonide with ethylamine in Embodiment 3 of the present invention ([EA]=10.86 ppm).

[0036] Figure 8 It is the mass spectrometry diagram B) after the reaction of secondary ozonide with ammonia in Embodiment 4 of the present invention and the mass spectrometry diagram A) after the reaction of secondary ozonide with ammonia in the single flow tube experiment of Comparative Example 1.

[0037] DESCRIPTION OF REFERENCE NUMERALS

[0038] 1 aerosol particle generation device

[0039] 11 first mass flowmeter

[0040] 12 heated glass tube

[0041] 13 Activated carbon container

[0042] 2 Ozone generation and detection device

[0043] 21 Second mass flowmeter

[0044] 22 Ozone generator

[0045] 23 Ozone detector

[0046] 3 Dual-flow tube reaction device

[0047] 31 First flow tube reactor

[0048] 32 Ozone decomposer container

[0049] 33 Fourth mass flowmeter

[0050] 34 Fifth mass flowmeter

[0051] 35 Second flow tube reactor

[0052] 4 Third mass flowmeter

[0053] 5 Atmospheric pressure photoionization ultra-high resolution mass spectrometry on-line detection device Detailed implementation manners

[0054] Hereinafter, the implementation manners of the on-line detection system and method for aerosol-amine co-escaping multiphase reaction specifically disclosed will be described in detail.

[0055] Please refer to Figures 1 - 8 . It should be noted that the structures, ratios, sizes, etc. shown in the drawings of this specification are only used to cooperate with the content disclosed in the specification for those skilled in this technology to understand and read, and are not used to limit the implementation conditions of the present invention. Therefore, they do not have any technical substance. Any modification of the structure, change of the proportional relationship or adjustment of the size, without affecting the effects that the present invention can produce and the purposes that can be achieved, should still fall within the scope that the technical content disclosed by the present invention can cover. At the same time, the terms such as "upper", "lower", "left", "right", "middle" and "one" cited in this specification are only for the convenience of clear narration and are not used to limit the implementation scope of the present invention. The change or adjustment of their relative relationships, without substantial change of the technical content, should also be regarded as the scope that the present invention can implement.

[0056]

A pretreatment system for aerosol-amine co-escaping multiphase reaction

[0057] Please refer to Figure 1, in the first aspect of the present invention, a pretreatment system for aerosol-amine co-escaping multiphase reaction is provided, which includes a connected aerosol particle generation device 1 and a dual-flow tube reaction device 3, and also includes an ozone generation and detection device 2. The ozone generation and detection device 2 is connected to the dual-flow tube reaction device 3. The dual-flow tube reaction device 3 includes a first flow tube reactor 31, an ozone decomposing agent container 32, and a second flow tube reactor 35 connected in sequence. The air outlets of the aerosol particle generation device 1 and the ozone generation and detection device 2 are respectively connected to the air inlet of the first flow tube reactor 31. The present invention realizes precise separation of each reaction stage through physical isolation. The first flow tube reactor 31 is used to in-situ, continuously, stably, and adjustably generate active secondary ozonated particles SOZ without cumbersome sample preparation and secondary collection processes. The second flow tube reactor 35 is used to realize the multiphase reaction between active SOZ and amines. In a preferred embodiment, both the first flow tube reactor 31 and the second flow tube reactor 35 are quartz flow tubes, which can effectively reduce the wall loss of particles, help to construct a particle dynamic suspension system, and thus simulate the amine reaction state under real atmospheric conditions. Compared with the inherent defects of the single-tube system, the series-connected dual-tube system can effectively avoid the coupling interference between the ozone oxidation and amine reaction processes. In addition, by adding an ozone decomposing agent container 32 at the outlet of the first flow tube reactor 31, the formation of by-products due to the reaction between ozone or Criegee intermediates and amines can be effectively inhibited. When ozone molecules react with alkenes, a reactive intermediate, namely the Criegee intermediate, will be formed.

[0058] Continue to refer to Figure 1 , in the pretreatment system for aerosol-amine co-escaping multiphase reaction provided by the present invention, the aerosol particle generation device 1 includes a first mass flowmeter 11, a heating glass tube 12, and an activated carbon container 13 connected in sequence. The air outlet of the activated carbon container 13 is connected to the air inlet of the first flow tube reactor 31. In a preferred embodiment, the air inlet of the first mass flowmeter 11 is connected to a nitrogen gas source. In a preferred embodiment, the heating glass tube 12 is a three-section heating glass tube, which can focus the liquid for heating in the middle section of the tube to generate uniformly distributed aerosol particles; the inlet of the heating glass tube 12 is connected to a quartz tube joint through a flange groove for loading and unloading samples and cleaning the glass tube; the outlet of the heating glass tube 12 is connected to the activated carbon container 13 using a copper tube. In a preferred mode, the activated carbon container 13 is a stainless steel container, and both ends are sealed with stainless steel flanges to remove excess gaseous organic substances.

[0059] Continue to refer to Figure 1, in the pretreatment system for aerosol-amine co-escaping multiphase reaction provided by the present invention, the ozone generation and detection device 2 includes a second mass flowmeter 21, an ozone generator 22, and an ozone detector 23 that are connected in sequence. The outlet of the ozone detector 23 is connected to the inlet of the first flow tube reactor 31. In a preferred embodiment, the inlet of the second mass flowmeter 21 is connected to an oxygen gas source.

[0060] Continue to refer to Figure 1 , in the pretreatment system for aerosol particle multiphase oxidation reaction provided by the present invention, the ozone generator 22 ionizes oxygen into ozone molecules through intermediate frequency frequency modulation discharge. The ozone concentration generated in the experiment ranges from 0.075 - 0.678 ppm, and can be selected as 0.075 - 0.12 ppm, 0.12 - 0.16 ppm, 0.16 - 0.292 ppm, 0.292 - 0.4 ppm, 0.4 - 0.678 ppm.

[0061] Continue to refer to Figure 1 , in the pretreatment system for aerosol particle multiphase oxidation reaction provided by the present invention, the ozone detector 23 is a non-scattering ultraviolet detector with the manufacturer model: GM-6000-OEM, anseros, China. The measurement wavelength is set to 253.7 nm, and it can continuously measure the ozone concentration of the flowing gas in the monitoring pipeline.

[0062] Continue to refer to Figure 1 , in the pretreatment system for aerosol particle multiphase oxidation reaction provided by the present invention, the inlet of the first flow tube reactor 31 is connected to a first gas path, and a third mass flowmeter 4 is provided on the first gas path. The first gas path is used to transport nitrogen dilution gas.

[0063] Continue to refer to Figure 1 , in the pretreatment system for aerosol particle multiphase oxidation reaction provided by the present invention, the inlets of the second flow tube reactor 35 are respectively connected to a second gas path and a third gas path. A fourth mass flowmeter 33 is provided on the second gas path, and a fifth mass flowmeter 34 is provided on the third gas path. The second gas path is used to transport amine compounds, and the third gas path is used to transport supplementary nitrogen. In a preferred embodiment, the ozone decomposer container 32 is an organic glass container or a stainless steel container. In a preferred embodiment, the amine compound gas is directly introduced into the second flow tube reactor 35 through a stainless steel needle valve without a pretreatment process.

[0064]

An on-line detection system for aerosol-amine co-escaping multiphase reaction

[0065] Continue to refer to Figure 1, the on-line detection system for aerosol particle multiphase oxidation reaction provided by the present invention includes the pretreatment system of the on-line detection system for aerosol-amine synergistic escape multiphase reaction as described above, and further includes an atmospheric pressure photoionization high-resolution mass spectrometry on-line detection device 5. The air inlet of the atmospheric pressure photoionization high-resolution mass spectrometry on-line detection device 5 is communicated with the air outlet of the second flow tube reactor 35.

[0066] In the present invention, the construction of the atmospheric pressure photoionization high-resolution mass spectrometry on-line detection device 5 can specifically refer to the construction of the on-line detection device in paragraphs 0073-0077 of the specification of CN118329738A. This on-line detection device is a device that combines atmospheric pressure photoionization technology APPI and high-resolution mass spectrometry HRMS. By using the "direct inlet sampling" method and the soft ionization mode of APPI to capture aerosol particles and perform fragmentation-free ionization on them, when combined with a high-resolution mass spectrometer (manufacturer model: Orbitrap Fusion, Thermo scientific), its high resolution (mass resolution at m / z 200 is 500,000), high sensitivity and fast acquisition ability can realize the on-line characterization and accurate qualitative determination of products. Through the double flow tube reaction device 3 combined with the atmospheric pressure photoionization high-resolution mass spectrometry on-line detection device 5, the present invention can realize the on-line characterization of particulate phase products and monitor the multiphase reaction process in real time, thereby contributing to the accurate analysis of the multiphase amine decomposition of SOZ and its synergistic escape process with gaseous amines.

[0067] Please refer to Figure 1 , the usage process of the on-line detection system for aerosol particle multiphase oxidation reaction provided by the present invention:

[0068] Before the experiment starts, first, carrier gas 1 (nitrogen) is introduced through the first mass flowmeter 11. The liquid sample is placed in the heated glass tube 12 and heated to generate stable aerosol particles. These generated aerosol particles pass through the activated carbon container 13 filled with an activated carbon decomposer to remove gaseous organic impurities. Subsequently, carrier gas 2 (oxygen) is introduced through the second mass flowmeter 21, enters the ozone generator 22 to generate ozone, and the ozone concentration is detected in real time by the ozone detector 23. Next, carrier gas 3 (nitrogen diluent) is introduced through the third mass flowmeter 4, which enters the first flow tube reactor 31. In this reactor, the aerosol particles react with ozone to generate various active SOZ particles. The outlet of the first flow tube reactor 31 is connected to the ozone decomposer container 32 to remove excess ozone. An amine compound is introduced through the fourth mass flowmeter 33, and at the same time, carrier gas 4 (supplemental nitrogen) is introduced through the fifth mass flowmeter 34. In the second flow tube reactor 35, the secondary ozonide generated in the first flow tube reactor 31 reacts with nitrogen and the amine compound. After the reaction is completed, the reaction product is introduced into the atmospheric pressure photoionization ultra-high resolution mass spectrometry online detection device 5 for detection, and the composition and changes of the reaction product are monitored and analyzed in real time.

[0069]

An Online Detection Method for Aerosol-Amine Co-Escape Multiphase Reactions

[0070] Please refer to Figure 1 , the second aspect of the present invention provides a method for an online detection system for aerosol-amine co-escape multiphase reactions, including the following steps:

[0071] 1) Obtain aerosol particles with gaseous organic impurities removed through the aerosol particle generation device 1;

[0072] 2) Generate ozone through the ozone generation and detection device 2;

[0073] 3) React the aerosol particles in step 1) with the ozone in step 2) through the first flow tube reactor 31 to generate secondary ozonide particles;

[0074] 4) Introduce an amine compound into the second flow tube reactor 35 and react it with the secondary ozonide particles generated in step 3) to obtain a reaction product;

[0075] 5) Introduce the reaction product obtained in step 4) into the atmospheric pressure photoionization ultra-high resolution mass spectrometry online detection 5 system for detection.

[0076] In the method of the on-line detection system for aerosol-amine co-escaping multiphase reaction provided by the present invention, in step 1), aerosol particles free of gaseous organic impurities are obtained through the aerosol particle generating device 1. Specifically: the heating glass tube 12 of the aerosol particle generating device 1 is placed in a tube furnace to heat the sample at a constant temperature to generate aerosol particles. Nitrogen is introduced into one end of the first mass flowmeter 11, and the nitrogen flow rate is controlled so that the obtained aerosol particles pass through the activated carbon container 13 to obtain aerosol particles free of gaseous organic impurities.

[0077] In step 1) of the present invention, the sample is a liquid sample, for example, it can be a lipid liquid sample, preferably oleic acid or squalene.

[0078] In step 1) of the present invention, the nitrogen flow rate is 150 - 300 mL / min, and can be optionally 150 - 200 mL / min, 200 - 250 mL / min or 250 - 300 mL / min, etc.

[0079] In step 1) of the present invention, the heating temperature of the sample is 130 - 150 °C, and can be optionally 130 - 140 °C, 140 - 145 °C or 145 - 155 °C, etc. During the actual operation process, the heating temperature can be adjusted according to the different saturated vapor pressures of the samples to generate stable aerosol particles.

[0080] In the method of the on-line detection system for aerosol particle multiphase oxidation reaction provided by the present invention, in step 2), ozone is generated through the ozone generation and detection device 2. Specifically: oxygen is introduced into one end of the mass flowmeter 21, and the oxygen flow rate is controlled. After passing through the ozone generator 22, ozone is generated, and then the concentration of ozone in the pipeline is monitored by the ozone detector 23.

[0081] In step 2) of the present invention, the oxygen flow rate is 20 - 200 mL / min, and can be optionally 20 - 80 mL / min, 80 - 120 mL / min or 120 - 200 mL / min, etc.

[0082] In step 2) of the present invention, the concentration of ozone is 0.075 - 0.678 ppm, and can be optionally 0.075 - 0.12 ppm, 0.12 - 0.16 ppm, 0.16 - 0.292 ppm, 0.292 - 0.4 ppm, 0.4 - 0.678 ppm. By adjusting the ozone concentration, in-situ stable generation of active SOZ particles with different concentrations can be achieved.

[0083] In the method of the on-line detection system for the heterogeneous oxidation reaction of aerosol particles provided by the present invention, in step 3), the aerosol particles in step 1 and ozone in step 2 react through the first flow tube reactor 31 to generate secondary ozonated particles (SOZ). Specifically, one end of the third mass flowmeter 4 is introduced with a nitrogen dilution gas, and the flow rate of the nitrogen dilution gas is controlled so that the aerosol particles obtained by removing gaseous organic impurities in step 1 and the ozone obtained in step 2 react to generate secondary ozonated particles, and then the residual ozone in the generated secondary ozonated particles is removed through the ozone decomposer container 32.

[0084] In step 3) of the present invention, the flow rate of the nitrogen dilution gas is 80 - 730 mL / min, and can be optionally 80 - 130 mL / min, 130 - 180 mL / min, 180 - 230 mL / min, 230 - 400 mL / min, 400 - 600 mL / min or 400 - 730 mL / min, etc. In a preferred embodiment, when the amine compound is ethylamine, the flow rate of the nitrogen dilution gas is 400 - 730 mL / min; when the amine compound is ammonia, the flow rate of the nitrogen dilution gas is 80 - 130 mL / min.

[0085] In step 3) of the present invention, the reaction temperature is room temperature.

[0086] In the method of the on-line detection system for the heterogeneous oxidation reaction of aerosol particles provided by the present invention, in step 4), supplementary nitrogen and an amine compound are introduced into the second flow tube reactor 35 and react with the secondary ozonated particles generated in step 3) to obtain a reaction product. Specifically, the flow rate of the amine compound introduced into the second flow tube reactor 35 is controlled by the fourth mass flowmeter 33, the flow rate of the supplementary nitrogen introduced into the second flow tube reactor 35 is controlled by the fifth mass flowmeter 34, and they react with the secondary ozonated particles generated in step 3) in the second flow tube reactor 35 to obtain a reaction product.

[0087] In step 4) of the present invention, the amine compound includes ethylamine or ammonia.

[0088] In step 4) of the present invention, the flow rate of the supplementary nitrogen is 100 - 650 mL / min, and it can be optionally 100 - 160 mL / min, 160 - 170 mL / min, 170 - 190 mL / min, 190 - 198 mL / min, 198 - 300 mL / min, 300 - 500 mL / min, 500 - 600 mL / min, 160 - 198 mL / min, 170 - 198 mL / min or 170 - 650 mL / min, etc. In a preferred embodiment, when the amine compound is ethylamine, the flow rate of the supplementary nitrogen is 160 - 198 mL / min; when the amine compound is ammonia, the flow rate of the supplementary nitrogen is 100 - 650 mL / min.

[0089] In step 4) of the present invention, the flow rate of the amine compound is 2 - 600 mL / min, and it can be optionally 2 - 40 mL / min, 50 - 600 mL / min, 2 - 10 mL / min, 10 - 20 mL / min, 20 - 30 mL / min, 30 - 40 mL / min, 50 - 100 mL / min, 100 - 200 mL / min, 200 - 300 mL / min, 300 - 400 mL / min, 400 - 500 mL / min or 500 - 600 mL / min, etc. In a preferred embodiment, when the amine compound is ethylamine, its flow rate is 2 - 40 mL / min; when the amine compound is ammonia, its flow rate is 50 - 600 mL / min.

[0090] In step 4) of the present invention, when the amine compound is ethylamine, the concentration is 2.17 - 43.45 ppm, and it can be optionally 2.17 - 10.86 ppm, 10.86 - 32.59 ppm, 32.59 - 45.45 ppm or 2.17 - 32.59 ppm, etc.

[0091] In step 4) of the present invention, when the amine compound is ammonia, the concentration is 45.49 - 636.81 ppm, and it can be optionally 45.49 - 100 ppm, 100 - 300 ppm, 300 - 500 ppm or 500 - 636.81 ppm, etc.

[0092] In step 4) of the present invention, the reaction temperature is room temperature.

[0093] In the method of the on-line detection system for aerosol particle multiphase oxidation reaction provided by the present invention, in step 5), the reaction product obtained in step 4) is introduced into the atmospheric pressure photoionization ultra-high resolution mass spectrometry on-line detection device 5 for detection. Specifically: the reaction product obtained in step 4) enters the atmospheric pressure photoionization ultra-high resolution mass spectrometry on-line detection device 5, is first heated and vaporized, and after the vaporized product is in-situ ionized by an ultraviolet lamp, it enters the high resolution mass spectrometry through an ion transfer tube for detection. The atmospheric pressure photoionization ultra-high resolution mass spectrometry on-line detection device 5 of the present invention combines the atmospheric pressure photoionization technology APPI and the high resolution mass spectrometry HRMS, can capture the reaction dynamic process of SOZ-ethylamine in real time, effectively avoid the product loss caused by off-line sampling, realize the on-line non-destructive detection of active particulate matter, and avoid the secondary reaction of particles to the greatest extent. In addition, when combined with high resolution mass spectrometry analysis, it can not only track the whole process of amine chemical reaction on-line, but also realize the synchronous analysis of multiphase reaction kinetic parameters.

[0094] In step 4) of the present invention, the heating and vaporization temperature is controlled within the range of 120-180°C, and can be selected as intervals such as 120-140°C, 140-160°C or 160-180°C, etc., and preferably 180°C.

[0095] The third aspect of the present invention provides a method for detecting the components of an on-line detection system for aerosol-amine co-escaping multiphase reaction.

[0096] The detection object is: secondary ozonated particulate matter.

[0097] The mass spectrometry conditions are: ionization mode: atmospheric pressure photoionization (APPI); sheath gas flow rate: 2Arb; auxiliary gas flow rate: 2Arb; purge gas flow rate: 2Arb; ion transfer tube temperature: 300-350°C; scanning mass range: 50-800Da; mass resolution: 500000@m / z 200.

[0098] In order to make the technical means, creative features, achieved purposes and effects of the present invention easy to understand, the present invention will be specifically described below in conjunction with embodiments and drawings.

[0099] In the following embodiments, unless otherwise specified, each reaction raw material is a commercially available product.

[0100] Unless otherwise specified, the purity of each product in the embodiments of the present invention exceeds 98%.

[0101] Example 1

[0102] The use process of an on-line detection system for aerosol-amine co-escaping multiphase reaction

[0103] As Figure 1As shown, before the experiment started, the flow rate of carrier gas 1 (nitrogen) was controlled at 300 mL / min by the first mass flowmeter 11. The squalene liquid sample was placed in the heating glass tube 12 and heated to 145 °C to generate stable aerosol particles. The generated aerosol particles passed through the activated carbon container 13 filled with activated carbon decomposer to remove the gaseous organic impurities. The flow rate of carrier gas 2 (oxygen) was controlled at 200 mL / min by the second mass flowmeter 21, entered the ozone generator 22 to generate ozone and the real-time concentration was detected by the ozone detector 22, and the ozone concentration was 0.678 ppm. The flow rate of carrier gas 3 (nitrogen diluent) was controlled at 400 mL / min by the third mass flowmeter 4 to ensure that the total gas flow rate entering the dual-flow tube reaction device 3 was 900 mL / min (corresponding to a reaction time of about 45 s). The first flow tube reactor 31 was used to react squalene with ozone to generate various active SOZ particles, and its outlet was connected to the ozone decomposer container 32 to remove the excess ozone. The flow rate of carrier gas 5 (ethylamine standard gas with a concentration of 32.59 ppm) was controlled at 30 mL / min by the fourth mass flowmeter 33. The flow rate of carrier gas 4 (supplemental nitrogen) was controlled at 170 mL / min by the fifth mass flowmeter 34. The secondary ozonide generated in the first flow tube reactor 31 reacted with nitrogen and ethylamine in the second flow tube reactor 35, and the total flow rate in the second flow tube reactor 35 was controlled at 1100 mL / min (corresponding to a reaction time of about 37 s). After splitting, 500 mL / min of aerosol particles were introduced for on-line detection by the atmospheric pressure photoionization ultra-high resolution mass spectrometry on-line detection device 5.

[0104] As Figure 2 shown, with the increase of ozone concentration (a) and at a fixed ozone concentration (0.57 ppm) (b), the MS signal trend diagram of C 35 SOZ (m / z526). Taking C 35 SOZ as an example, Figure 2 a shows its mass spectrometry signal change trend at different stages of the reaction, that is, with the increase of ozone concentration. It can be seen that at different ozone concentrations, the tandem dual-flow tube reactor can achieve the generation of SOZ particles with different concentrations. At a fixed ozone concentration (0.57 ppm), Figure 2 b shows the continuous and stable generation of C 35 SOZ over a long reaction time.

[0105] As Figure 3As shown, the online mass spectrometry of secondary ozonides (SOZs) from the oxidation of squalene particles and the products of their reaction with ethylamine. (a) is the mass spectrometry before the reaction of secondary ozonides with ethylamine, and (b) is the mass spectrometry after the reaction of secondary ozonides with ethylamine. At this time, the ozone concentration in both the first flow tube reactor 31 and the second flow tube reactor 35 is 0.678 ppm, the ethylamine concentration in the first flow tube reactor 31 is 0 ppm, and the ethylamine concentration in the second flow tube reactor 35 is 32.588 ppm. Figure 3 In a, various SOZs with different carbon numbers can be seen, such as C 16 SOZ (m / z 267), C 20 SOZ (m / z 321), C 21 SOZ (m / z 335), C 25 SOZ (m / z 390), C 26 SOZ (m / z 403), C 30 SOZ (m / z 458), C 34 SOZ (m / z 512), C 35 SOZ (m / z526), C 39 SOZ (m / z 580), C 40 SOZ (m / z 594), C 44 SOZ (m / z 648) and C 49 SOZ (m / z715). Figure 3 In b, the direct amine addition products (m / z 314, 368, 380, 436, 504, 558, 572, 640, 694 and 762) corresponding to various SOZs and some amine addition dehydration products (m / z 296, 350, 364, 418 and 486) can be seen.

[0106] To quantitatively determine the heterogeneous reaction rate of secondary ozonides with ethylamine, following the method of Smith et al. (Aerosol Sci. Technol. 2023, 58(4), 356 - 373), the decay rate (denoted as k) and the effective absorption coefficient (denoted as γ) of SOZ particles are derived from equations E1 and E2. By monitoring the exposure of ethylamine, that is, the ethylamine concentration × reaction time (37 s), the decay data is fitted to an exponential function (1) to determine k. Equation (2) is used to calculate γ, which quantifies the reaction rate of the collision between SOZ particles and ethylamine molecules. In equation (2), D is the particle diameter, ρ0 is the reactant density, N A is Avogadro's constant, c is the average velocity of ethylamine gas molecules, and M is the molar mass of the reactant molecules.

[0107]

[0108] According to the above equations, the kinetic curves of SOZ particles (a) and their aminated products (b) with increasing ethylamine exposure are shown as Figure 4 follows. Figure 4 a shows the kinetic curves of five main secondary ozonides (C 40 , C 35 , C 30 , C 25 and C 20 SOZ) with increasing ethylamine exposure, and the kinetic evolution information of their aminated products is shown as Figure 4 b. Among them, C 20 and C 30 SOZ (m / z 322 and 458) exhibit faster reaction rates, corresponding to faster formation rates of aminated products (m / z 368 and 504).

[0109] As Figure 5 shown, when considering the influence of the relative molecular masses of SOZ particles with different carbon numbers, it can be found that the effective absorption coefficient of C 30 SOZ is the largest, indicating that it has the fastest heterogeneous reaction rate with ethylamine.

[0110] Example 2

[0111] The difference from Example 1 is only that the ethylamine concentration is 2.17 ppm, the flow rate is 2 mL / min, and the supplementary nitrogen flow rate is 198 mL / min.

[0112] Example 3

[0113] The difference from Example 1 is only that the ethylamine concentration is 10.86 ppm, the flow rate is 10 mL / min, and the supplementary nitrogen flow rate is 190 mL / min.

[0114] Example 4

[0115] Before the experiment started, the carrier gas 1 (nitrogen) was controlled by the first mass flowmeter 11 to have a flow rate of 200 mL / min. The squalene liquid sample was placed in the heating glass tube 12 and heated at a temperature of 145 °C to generate stable aerosol particles. The generated aerosol particles passed through the activated carbon container 13 filled with an activated carbon decomposer to remove gaseous organic impurities. The carrier gas 2 (oxygen) was controlled by the second mass flowmeter 21 to have a flow rate of 20 mL / min, entered the ozone generator 22 to generate ozone and was detected for its real-time concentration by the ozone detector 22, and the ozone concentration was 0.16 ppm. The carrier gas 3 (nitrogen diluent) had a flow rate of 180 mL / min controlled by the third mass flowmeter 4 to ensure that the total gas flow rate entering the dual-flow tube reaction device 3 was 400 mL / min (corresponding to a reaction time of about 103 s). The first flow tube reactor 31 was used to react squalene with ozone to generate various active SOZ particles, and its outlet was connected to the ozone decomposer container 32 to remove excess ozone. The carrier gas 5 (ammonia standard gas with a concentration of 636 ppm) had a flow rate of 600 mL / min controlled by the fourth mass flowmeter 33. The carrier gas 4 (supplemental nitrogen) had a flow rate of 100 mL / min controlled by the fifth mass flowmeter 34. The secondary ozonides generated in the first flow tube reactor 31 reacted with nitrogen and ammonia in the second flow tube reactor 35, and the total flow rate in the second flow tube reactor 35 was controlled to be 1100 mL / min (corresponding to a reaction time of about 37 s).

[0116] Comparative Example 1

[0117] In the comparative experiment of ammonia in a single flow tube, squalene (200 mL / min), ozone (20 mL / min), and supplemental nitrogen (880 mL / min) were introduced into the single flow tube to react first to generate aldehydes, acids, and secondary ozonide particles (the total flow rate in the single flow tube was controlled to be 1100 mL / min). Subsequently, under the condition of a fixed ozone concentration, ammonia (with a concentration of 636 ppm and a flow rate of 600 mL / min) was introduced into the system, the supplemental nitrogen was adjusted (280 mL / min), and the total flow rate in the single flow tube was also controlled to be 1100 mL / min.

[0118] As Figure 8 shown are the mass spectra of the products in the comparative experiment of a single flow tube A) and a series flow tube B) at an ammonia concentration of 636 ppm. Under the interference of the Criegee intermediates (CIs) in the single flow tube, Figure 8 A and 8B exhibit different product distribution patterns. Figure 6Zhongyou first generated various reaction products of CIs with ammonia and dehydration secondary products, such as m / z 124, 142, 194, 210, 334 and 402. This is because compared with aldehydes and SOZs in the system, CIs have a faster reaction rate with ammonia. Due to the extremely short lifespan of CIs (in the microsecond level), using a tandem flow tube is more helpful to eliminate the interference of CI side reactions on the study of heterogeneous ammonia chemical reactions. In addition, according to the reported ammonia-ozone reaction mechanism in the literature (Appl Energy CombustSci. 2023; 14, 100137-100143.), the side reaction between ozone and ammonia cannot be excluded in the particle-ammonia heterogeneous reaction carried out in a single flow tube, and a large amount of NO and NO2 will be generated by the oxidation of ammonia. Therefore, the tandem flow tube can effectively exclude the interference of ozone on the ammonia chemical reaction products by introducing an ozone adsorbent.

[0119] The above embodiments are preferred cases of the present invention and are not used to limit the protection scope of the present invention. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept scope of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0120] In addition, it should be noted that, in the case of no contradiction, the various specific technical features described in the above specific embodiments can be combined in any appropriate way. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

Claims

1. A pretreatment system for aerosol-amine co-escaping multiphase reactions, characterized in that, It includes a connected aerosol particle generation device (1) and a dual-flow tube reaction device (3), and also includes an ozone generation and detection device (2). The ozone generation and detection device (2) is connected to the dual-flow tube reaction device (3). The dual-flow tube reaction device (3) includes a first flow tube reactor (31), an ozone decomposing agent container (32), and a second flow tube reactor (35) connected in sequence. The air outlets of the aerosol particle generation device (1) and the ozone generation and detection device (2) are respectively connected to the air inlet of the first flow tube reactor (31).

2. The pretreatment system for aerosol-amine co-escaping multiphase reaction according to claim 1, characterized in that, The aerosol particle generation device (1) includes a first mass flowmeter (11), a heating glass tube (12), and an activated carbon container (13) connected in sequence. The air outlet of the activated carbon container (13) is connected to the air inlet of the first flow tube reactor (31).

3. The pretreatment system for aerosol-amine co-escaping multiphase reaction according to claim 1, wherein, The ozone generation and detection device (2) includes a second mass flowmeter (21), an ozone generator (22), and an ozone detector (23) connected in sequence. The air outlet of the ozone detector (23) is connected to the air inlet of the first flow tube reactor (31).

4. The pretreatment system for aerosol-amine collaborative escape multiphase reaction according to claim 1, wherein The air inlet of the first flow tube reactor (31) is connected to a first gas path, and a third mass flowmeter (4) is provided on the first gas path.

5. The on-line detection system for aerosol-amine co-escaping multiphase reaction according to claim 1, characterized in that The air inlets of the second flow tube reactor (35) are respectively connected to a second gas path and a third gas path. A fourth mass flowmeter (33) is provided on the second gas path, and a fifth mass flowmeter (34) is provided on the third gas path.

6. An on-line detection system for aerosol-amine co-escaping multiphase reaction, comprising the pre-treatment system of the on-line detection system for aerosol-amine co-escaping multiphase reaction according to any one of claims 1-5, characterized in that, It also includes an atmospheric pressure photoionization ultra-high resolution mass spectrometry online detection device (5). The air inlet of the atmospheric pressure photoionization ultra-high resolution mass spectrometry online detection device (5) is connected to the air outlet of the second flow tube reactor (35).

7. An on-line detection method for aerosol-amine co-escaping multiphase reaction, which uses the on-line detection system for aerosol-amine co-escaping multiphase reaction as described in claim 6, and is characterized in that, It includes the following steps: 1) Obtain aerosol particles with gaseous organic impurities removed through the aerosol particle generation device; 2) Generate ozone through the ozone generation and detection device; 3) React the aerosol particles in step 1) and the ozone in step 2) through the first flow tube reactor to generate secondary ozonated particles; 4) Introduce an amine compound into the second flow tube reactor and react it with the secondary ozonated particles generated in step 3) to obtain a reaction product; 5) Introduce the reaction product obtained in step 4) into the atmospheric pressure photoionization ultra-high resolution mass spectrometry online detection device for detection.

8. The on-line detection method for aerosol-amine co-escaping multiphase reaction according to claim 7, characterized in that, It includes any one or more of the following features: A1) In step 1), nitrogen is introduced into the aerosol particle generation device, and the nitrogen flow rate is 150 - 300 mL / min; A2) In step 1), the aerosol particle generation device is heated, and the heating temperature is 130 - 150 °C; A3) In step 2), oxygen is introduced into the ozone generation and detection device, and the oxygen flow rate is 20 - 200 mL / min; A4) In step 3), the concentration of the ozone is 0.075 - 0.678 ppm; A5) In step 3), nitrogen dilution gas is introduced into the first flow tube reactor, and the nitrogen dilution gas flow rate is 80 - 730 mL / min; A6) In step 3), the temperature of the reaction is room temperature; A7) In step 4), supplementary nitrogen is introduced into the second flow tube reactor, and the flow rate of the nitrogen is 100 - 650 mL / min; A8) In step 4), an amine compound is introduced into the second flow tube reactor, and the flow rate of the amine compound is 2 - 600 mL / min; A9) In step 4), the amine compound is ethylamine or ammonia; A10) In step 4), the temperature of the reaction is room temperature; A11) In step 5), the introduction amount of the reaction product is 400 - 600 mL / min; A12) In step 5), the reaction product is heated and vaporized before detection, and the temperature of the heating and vaporization is 120 - 180 °C.

9. The on-line detection method for aerosol-amine collaborative escape multiphase reaction according to claim 8, characterized in that, Comprising any one or more of the following features: A91) In step (4), the concentration of ethylamine is 2.17 - 43.45 ppm; A92) In step (4), the concentration of ammonia is 45.49 - 636.81 ppm.

10. A method for detecting the components of an on-line detection system for aerosol-amine co-escaping multiphase reactions, using the on-line detection system for aerosol-amine co-escaping multiphase reactions as described in claim 6, and performing ultra-high resolution mass spectrometry detection according to the detection method described in any one of claims 7 - 9.

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