A method and system for the controllable generation of highly stable amine nanoparticles and the detection of their CO2 gas-solid reaction.

Abstract

The application belongs to the field of controllable generation method of amine aerosol particles and CO2 gas-solid reaction research, and relates to a controllable generation method of high-stability amine nanoparticles and application of the method in CO2 gas-solid reaction research, which comprises the following steps: 1) putting amine compounds and samples into an amine aerosol generation device for heating, and removing gas-phase organic impurities by an activated carbon decomposition agent to obtain amine aerosol mixed particles; 2) passing the amine aerosol mixed particles obtained in step S1 into a double-layer flow tube reaction device to perform a multiphase reaction with CO2, and after the reaction, part of the products is passed into an amine particle size concentration online detection device for detection, and the other part of the products is passed into a CO2 adsorbent to remove residual CO2 to obtain product amine aerosol particles; 3) the product amine aerosol particles obtained in step S2 are extracted into a solvent electrospray, ionized, introduced into an HRMS online detection unit by an ion transmission tube, and detected.

Description

Technical Field

[0001] This invention belongs to the field of controllable generation methods of amine aerosol particles and research on CO2 gas-solid reaction, and in particular relates to a controllable generation method and system for high-stability amine nanoparticles and detection of their CO2 gas-solid reaction. Background Technology

[0002] Amine-based CO2 absorption technology is the mainstream post-combustion carbon capture scheme in my country, and its core lies in the efficient reaction between amine absorbents and CO2. In industrial absorption towers, amines coexist in three forms: gaseous, droplets, and aerosol particles. Among them, the formation and evolution of aerosols directly affect the system's operating efficiency and emission control. Studies have shown that when there are heterogeneous nuclei such as carbon soot in the inlet flue gas of a CO2 chemical absorption system, gaseous amines will undergo condensation and mass transfer on the particle surface and react with CO2 to significantly promote the growth of large-sized aerosols (Environ. Sci. Technol. 2021, 55 (8), 5152-5160). This process is also subject to the complex operating conditions such as temperature, humidity, and gas phase composition within the tower. For example, Yu et al. found that the generation of aerosols in the absorber tower is mainly attributed to the heterogeneous reaction between CO2 or H2O and gaseous amines, and that the aerosol concentration increases significantly with increasing CO2 load (Energy Fuels. 2024, 38 (7), 6230-6237). Furthermore, the temperature of the flue gas and absorbent also promotes the increase in aerosol concentration. However, existing studies mostly focus on macroscopic emission characteristics, lacking quantitative analysis of the multiphase reaction network and kinetic parameters of amine aerosols with CO2.

[0003] Quantitative formation of amine aerosols is a prerequisite for studying their reaction kinetics, but existing methods have significant limitations. There are two main modes of amine aerosol particle formation: homogeneous nucleation and heterogeneous nucleation. Zahardis et al. reported the formation of homogeneous aerosol particles of octadecylamine and hexadecylamine using a glass concentric pneumatic sprayer, but this process uses ethanol as a solvent and cannot completely remove it; residual ethanol in the system may interfere with subsequent reactions (Atmos. Chem. Phys. 2008, 8 (5), 1181-1194.). Heterogeneous nucleation can be achieved using inert nuclei such as SiO2 and NaCl, but related studies are rare. Furthermore, the correlation between the formation mechanism of amine aerosols (such as nucleation mode and particle size distribution) and CO2 reactivity has not been systematically studied, making it difficult to quantitatively analyze the influence of particle characteristics on the heterogeneous reaction rate.

[0004] Furthermore, current research on the heterogeneous reaction mechanism of organic amines with CO2 mainly focuses on amine droplet systems. For example, Huang et al. investigated the process of primary amine droplets reacting with CO2 to form carbamates, confirming that trace amounts of water can significantly increase the amount of carbamate produced (Chem. Sci. 2020, 12 (6), 2242-2250.). Feng et al. confirmed that ammonium bicarbonate present in ESI droplets can significantly improve the conversion rate of organic amine compounds. Ammonium bicarbonate can decompose into CO2 and form microbubbles within the ESI droplets, significantly increasing the specific surface area of ​​the droplets and promoting the interfacial reaction between amines and CO2 (Anal Chem2021, 93 (47), 15775-15784.). However, these studies mostly infer interfacial effects indirectly through product analysis or conversion rates, lacking direct measurement of kinetic parameters (such as rate constants).

[0005] Current research on the heterogeneous reactions of organic amines with CO2 under the amine-based carbon capture method mainly focuses on product identification and exploring the influence of operating conditions, lacking quantitative analysis of the heterogeneous reaction network between amine aerosols and CO2. The main reasons for this are as follows:

[0006] (1) Limitations of methods for generating amine aerosol particles. Existing methods for the quantitative generation of amine aerosol particles have significant shortcomings. For example, homogeneous nucleation methods typically rely on concentric glass pneumatic sprayers, but require solvents such as ethanol. Residual solvents may interfere with subsequent reaction kinetic studies and mechanism analysis (Atmos. Chem. Phys. 2008, 8 (5), 1181-1194). Furthermore, while tubular furnace heating has been successfully applied to the quantitative generation of some long-chain carbon particles with low saturated vapor pressure, its application to the generation of particles in organic amine systems has not been reported. Although heterogeneous nucleation methods can promote the generation of amine particles through inert nuclei (such as SiO2 and NaCl), related studies are extremely limited, and there is a lack of systematic investigation into the relationship between nucleation mechanisms and CO2 reactivity.

[0007] (2) Insufficient information dimensions in detection methods. Traditional offline analyses, such as gas chromatography (GC) and liquid chromatography (LC) combined with mass spectrometry (MS), lack sufficient time resolution, often focusing only on the characteristics of the final product or raw materials while neglecting the analysis of intermediate products. Online detection technologies, such as the electrical low-voltage impactor (ELPI)... + It can monitor aerosol concentration and particle size distribution online (Energy Fuels. 2024, 38 (7), 6230-6237), but it can only provide macroscopic changes in aerosol particles and cannot analyze the reaction process at the molecular level. In situ 13 C nuclear magnetic resonance spectrometer ( 13While C10 NMR can track the reaction process of amines with CO2 in solution in real time (Energy Fuels. 2016, 30, 1221-3236), it is limited by insufficient spatiotemporal resolution (limited to the study of bulk solutions and unable to capture millisecond-level reactions) and can only obtain information on the functional groups of the products, making it difficult to directly study the surface and interface reactions of aerosol particles. Online characterization techniques, represented by electron electrospray ionization (EESI) or ESI-HRMS, have been applied to the in-situ monitoring of the interface reaction between amine droplets and CO2 (Chem. Sci. 2020, 12 (6), 2242-2250.) (Anal Chem 2021, 93 (47), 15775-15784.), but mainly focus on product identification and interface effect verification. As a result, although the existing ESI-HRMS technology has online detection capabilities, it has failed to promote the quantitative study of the multiphase reaction mechanism of amine particles. Summary of the Invention

[0008] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide a controllable generation method and system for high-stability amine nanoparticles and the detection of their CO2 gas-solid reaction, so as to solve the problem that the existing amine-based carbon capture aerosol reaction research lacks controllable quantitative generation methods and online detection technology for amine aerosols, which makes it impossible to achieve quantitative and mechanistic analysis of the multiphase reaction between amine particles and CO2.

[0009] The first aspect of this invention provides a method for the controllable generation of highly stable amine nanoparticles and the detection of their CO2 gas-solid reaction, comprising the following steps:

[0010] 1) The amine compound and the sample are placed in an amine aerosol generating device and heated. The gaseous organic impurities are removed by activated carbon decomposition agent to obtain amine aerosol mixed particles.

[0011] 2) The amine aerosol mixed particles obtained in step S1 are fed into a double-layer flow tube reactor to undergo a multiphase reaction with CO2. After the reaction, part of the product is fed into an online amine particle size concentration detection device for detection, and the other part of the product is fed into a CO2 adsorbent to remove residual CO2, thus obtaining the product amine aerosol particles.

[0012] 3) The amine aerosol particles obtained in step S2 are extracted into solvent electrospray, ionized, and then introduced into the HRMS online detection unit for detection by the ion transfer tube.

[0013] In some embodiments of the present invention, in step 1), the amine compound is selected from tetraethylenepentamine, triethanolamine, or N-(3-aminopropyl)diethanolamine.

[0014] In some embodiments of the present invention, in step 1), the sample is squalane or decyltetradecyl alcohol.

[0015] In some embodiments of the present invention, in step 1), the volume ratio of the amine compound to the sample is (1-3):1.

[0016] In some embodiments of the present invention, in step 1), nitrogen gas is introduced during the heating process, and the flow rate of nitrogen gas is 200-300 ml / min.

[0017] In some embodiments of the present invention, in step 1), the heating to a temperature of 112-116°C is performed.

[0018] In some embodiments of the present invention, in step 2), CO2 is introduced during the multiphase reaction process, and the flow rate of CO2 is 0-148.6 ml / min.

[0019] In some embodiments of the present invention, in step 2), nitrogen dilution gas is also introduced during the multiphase reaction process, and the flow rate of nitrogen dilution gas is 900-651.4 ml / min.

[0020] In some embodiments of the present invention, in step 2), the reaction temperature of the multiphase reaction process is 25-70°C; the reaction time is 37s.

[0021] In some embodiments of the present invention, in step 2), the CO2 adsorbent is selected from KOH.

[0022] In some embodiments of the present invention, in step 3), the solvent in the solvent electrospray is a mixture of methanol and acetonitrile or methanol; the volume ratio of methanol to acetonitrile is (1-3):1.

[0023] In some embodiments of the present invention, in step 3), the solvent electrospray is formed by applying a high voltage to the solvent stream, wherein the applied high voltage ranges from 2500 to 3500V.

[0024] A second aspect of the present invention provides a controllable generation system for highly stable amine nanoparticles and its CO2 gas-solid reaction detection system, for implementing the detection method described above, comprising a connected amine aerosol generation device and a double-layer flow tube reaction device for generating product amine aerosol particles; further comprising an EESI-HRMS online detection device for extracting, ionizing and detecting the product amine aerosol particles by high-resolution mass spectrometry; the EESI-HRMS online detection device comprises an extraction-type electrospray ionization unit and an HRMS online detection unit, wherein the ion transmission port of the HRMS online detection unit is located below the solvent transmission port of the extraction-type electrospray ionization unit for receiving ionized gaseous ions.

[0025] In some embodiments of the present invention, the amine aerosol generating device includes a heated glass tube and an activated carbon container connected together, the inlet of the heated glass tube being connected to a nitrogen pipeline, and the outlet of the activated carbon container being connected to the double-layer flow tube reaction device.

[0026] In some embodiments of the present invention, a first flow meter is provided on the nitrogen pipeline.

[0027] In some embodiments of the present invention, the double-layer flow tube reactor includes a connected double-layer flow tube reactor and a CO2 adsorbent container. The inlet of the double-layer flow tube reactor is connected to both a CO2 pipeline and a nitrogen dilution gas pipeline. The outlet is vertically positioned between the solvent transfer port and the ion transfer port. An online amine particulate matter concentration detection device is also provided between the double-layer flow tube reactor and the CO2 adsorbent container. This online amine particulate matter concentration detection device includes an electrostatic classifier, a differential mobility analyzer, and a particle condensation counter connected in sequence. The inlet of the electrostatic classifier is connected to the outlet of the double-layer flow tube reactor.

[0028] In some embodiments of the present invention, a second mass flow meter is provided on the CO2 pipeline, and a third mass flow meter is provided on the nitrogen dilution gas pipeline.

[0029] The present invention has the following beneficial effects:

[0030] 1) Controllable and stable generation of amine aerosols (such as TEPA). A heterogeneous nucleation method for amine aerosol particles is provided, which uses carbon particle heterogeneous nuclei with reactive inertness (such as squalane). By adjusting the temperature of the tube furnace and the carrier gas flow rate, combined with real-time dynamic feedback of amine particle concentration and particle size by scanning electromigration particle size spectrometry, stable and controllable (adjustable concentration and particle size range) generation of amine aerosol particles is achieved, solving the problem of difficult precise control of particulate matter concentration in traditional technologies.

[0031] 2) The innovative coupling of EESI-HRMS online detection technology enables real-time monitoring of reaction product distribution and kinetic process tracking. By quantifying multiphase reaction rates through kinetic parameters, it provides key reaction mechanism data for amine-based carbon capture. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of the overall device structure of Embodiment 1 of the present invention.

[0033] Figure 2 The distribution of N-(3-aminopropyl)diethanolamine particles in homogeneous and heterogeneous nucleation was determined using scanning electromigration particle size spectrometry in Example 1 of this invention. Figure 2a represents the homogeneous nucleation distribution of N-(3-aminopropyl)diethanolamine particles. Figure 2 b represents the distribution of heterogeneous nucleated N-(3-aminopropyl)diethanolamine particles.

[0034] Figure 3 The distribution of homogeneous nucleated TEPA particles determined by scanning electromigration particle size spectrometry in Example 1 of this invention.

[0035] Figure 4 This refers to the distribution of heterogeneous nucleated TEPA particles measured in real time using a scanning electromigration particle size analyzer in Example 1 of the present invention. Figure 4 The heteronucleus in a is decyltetradecyl alcohol. Figure 4 b represents the distribution of controllable TEPA heterogeneous nucleation particles under different conditions, with the heterogeneous nucleus being squalane.

[0036] Figure 5 This is the mass spectrum of the reaction between TEPA particles and CO2 in Example 1 of the present invention. Figure 5 a is the mass spectrum before the reaction. Figure 5 b is the mass spectrum after the reaction.

[0037] Figure 6 This is the decay kinetic curve of TEPA particles in Example 1 of the present invention as CO2 exposure increases.

[0038] Component designation explanation

[0039] 1. Amine aerosol generating device;

[0040] 11. Heating glass tube;

[0041] 12. Activated carbon container;

[0042] 2. Double-layer flow tube reactor;

[0043] 21. Double-layer flow tube reactor;

[0044] 22. Needle valve;

[0045] 23. CO2 adsorbent container;

[0046] 3. EESI-HRMS online detection device;

[0047] 31. Extraction-type electrospray ionization unit;

[0048] 311. Solvent transfer port;

[0049] 32. HRMS online monitoring unit;

[0050] 321. Ion transport port;

[0051] 4. Nitrogen pipeline;

[0052] 41. First mass flow meter;

[0053] 5. CO2 piping;

[0054] 51. Second mass flow meter;

[0055] 6. Nitrogen dilution gas pipeline;

[0056] 61. Third mass flow meter;

[0057] 7. Online detection device for amine particulate matter particle size concentration;

[0058] 71. Electrostatic classifier;

[0059] 72. Differential mobility analyzer;

[0060] 73. Particle condensation counter. Detailed Implementation

[0061] The following details a method and system for the controllable generation of highly stable amine nanoparticles and the detection of their CO2 gas-solid reaction.

[0062] This invention designs a quantitative method for the generation of amine aerosol particles and, based on an aerosol multiphase reaction experimental platform coupled with EESI-HRMS online detection technology, achieves the controllable generation of typical amine particles (TEPA, containing primary and secondary amine functional groups) and applies it to the study of their multiphase reaction with CO2. This method not only solves the problem of quantitative generation of amine aerosol particles, but also, combined with EESI-HRMS online detection technology, enables real-time acquisition of the product distribution of amine particles and CO2 and real-time tracking of the multiphase reaction process. By obtaining the kinetic parameters, the multiphase reaction rate is quantified, providing crucial methodological support for the generation mechanism and evolution of organic amine aerosols in amine-based carbon capture processes. Based on this, this invention was completed.

[0063] It should be understood that the structures, proportions, sizes, etc., illustrated in the accompanying drawings of this specification are merely for illustrative purposes to aid those skilled in the art and are not intended to limit the scope of the invention. Therefore, they have no substantial technical significance. Any modifications to the structure, changes in proportions, or adjustments to size, without affecting the effectiveness and purpose of the invention, should still fall within the scope of the technical content disclosed in this invention. Furthermore, the terms such as "upper," "lower," "left," "right," "middle," and "one" used in this specification are merely for clarity and are not intended to limit the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention.

[0064] [Controllable generation of highly stable amine nanoparticles and detection method for CO2 gas-solid reaction]

[0065] The first aspect of this invention provides a method for the controllable generation of highly stable amine nanoparticles and its application in CO2 gas-solid reaction research, comprising the following steps:

[0066] 1) The amine compound and the sample are placed in an amine aerosol generating device and heated. The gaseous organic impurities are removed by activated carbon decomposition agent to obtain amine aerosol mixed particles.

[0067] 2) The amine aerosol mixed particles obtained in step S1 are fed into a double-layer flow tube reactor to undergo a multiphase reaction with CO2. After the reaction, part of the product is fed into an online amine particle size concentration detection device for detection, and the other part of the product is fed into a CO2 adsorbent to remove residual CO2, thus obtaining the product amine aerosol particles.

[0068] 3) The amine aerosol particles obtained in step S2 are extracted into solvent electrospray, ionized, and then introduced into the HRMS online detection unit for detection by the ion transfer tube.

[0069] This invention provides a controllable method for generating highly stable amine nanoparticles and its application in CO2 gas-solid reactions. Step 1) involves placing an amine compound and a sample into an amine aerosol generating device for heating, and removing gaseous organic impurities using an activated carbon decomposition agent to obtain mixed amine aerosol particles. In a preferred embodiment, squalane and tetraethylenepentamine (TEPA) liquid sample are mixed and placed in a glass tube, then heated in a tube furnace. The introduction of a chemically inert carbon-based heteronucleus (squalane) induces the condensation and nucleation of TEPA in the gas phase. By precisely controlling the tube furnace temperature and carrier gas flow rate, stable and controllable generation of TEPA aerosol particles in terms of particle size distribution and number concentration can be achieved. This method effectively simulates the formation and evolution behavior of amine particles under industrial amine carbon capture conditions, providing a highly reproducible and stable experimental aerosol source for subsequent multiphase reaction kinetics studies.

[0070] In step 1) of this invention, the amine compound is selected from tetraethylenepentamine, triethanolamine or N-(3-aminopropyl)diethanolamine; preferably tetraethylenepentamine (TEPA).

[0071] In step 1) of this invention, the sample is squalane or decyltetradecyl alcohol.

[0072] In step 1) of this invention, the volume ratio of ethyleneamine compound to sample is (1-3):1, which can be (1-2):1 or (2-3):1.

[0073] In step 1) of this invention, nitrogen gas is introduced during the heating process, and the flow rate of nitrogen gas is 200-300 ml / min, which can be selected as 200-250 ml / min or 250-300 ml / min.

[0074] In step 1) of the present invention, the heating temperature is 112-116℃, which can be selected as 112-114℃ or 114-116℃.

[0075] In the method for controlling the generation of amine aerosol particles and the detection of their reaction with CO2 provided by the present invention, in step 2), the amine aerosol mixed particles obtained in step S1 are introduced into a double-layer flow tube reaction device to undergo a multiphase reaction with CO2. After the reaction, part of the product is introduced into an online amine particle size concentration detection device for detection, and the other part of the product is introduced into a CO2 adsorbent to remove residual CO2, thereby obtaining the product amine aerosol particles.

[0076] In step 2) of this invention, CO2 is introduced during the heterogeneous reaction process. The flow rate of CO2 is 0-148.6 ml / min, which can be selected as 0-50 ml / min, 50-100 ml / min or 100-148.6 ml / min.

[0077] In step 2) of this invention, nitrogen dilution gas is also introduced during the multiphase reaction process. The flow rate of the nitrogen dilution gas is 900-651.4 ml / min, which can be selected as 900-800 ml / min, 800-700 ml / min or 700-651.4 ml / min.

[0078] In step 2) of this invention, the reaction temperature of the multiphase reaction process is 25-70℃, which can be selected as 25-50℃, 50-60℃ or 60-70℃.

[0079] In step 2) of this invention, the CO2 adsorbent is selected from KOH.

[0080] In the controllable generation of amine aerosol particles and their gas-solid reaction with CO2 provided by this invention, the amine aerosol particles obtained in step S2 (step 3) are extracted into solvent electrospray ionization (SSI), ionized, and then introduced into the HRMS online detection unit for detection via an ion transfer tube. By constructing a controllable aerosol multiphase reaction platform and coupling it with extraction electrospray ionization high-resolution mass spectrometry (EESI-HRMS) online detection technology, real-time investigation of the multiphase reaction process between amine compound particles (such as TEPA particles) and CO2 can be achieved. Extraction electrospray ionization (EESI), as a soft ionization method, can directly introduce aerosol particles into the solvent electrospray ionization process, effectively avoiding signal interference caused by thermal effects in traditional vaporization detection, thereby achieving online, non-destructive detection of amine particles.

[0081] In one specific embodiment, the reaction rate constant can be directly extracted based on the exponential function fitting of the TEPA signal decay with CO2 exposure, thereby quantifying the multiphase reaction rate of amine particles. To determine the multiphase reaction rate of TEPA with CO2, the decay rate (denoted as k) and effective absorption coefficient (denoted as γ) of TEPA particles were derived from equations E1 and E2 according to the method of Smith et al. (Aerosol Sci. Technol. 2023, 58 (4), 356-373). k was determined by fitting the decay data to an exponential function (1) by monitoring the CO2 exposure, i.e., CO2 concentration × reaction time (37s). Equation (2) was used to calculate γ, which quantifies the reaction rate of TEPA particles colliding with CO2 molecules. In Equation (2), D is the particle center diameter (429.2nm), and ρ0 is the density of TEPA (0.988g / cm³). 3 ), N A is Avogadro's constant, c is the average velocity of CO2 gas molecules (378.8 m / s), and M is the molar mass of TEPA molecules (189.3 g / mol).

[0082]

[0083] In step 3) of the present invention, the solvent in the solvent electrospray is a mixture of methanol and acetonitrile or methanol; the volume ratio of methanol to acetonitrile is (1-3):1, which can be (1-2):1 or (2-3):1.

[0084] In step 3) of this invention, the solvent electrospray is formed by applying a high voltage to the solvent flow. The voltage range of the applied high voltage is 2500-3500V, which can be selected as 2500-3000V or 3000-3500V.

[0085] [Controllable generation of highly stable amine nanoparticles and detection system for CO2 gas-solid reaction]

[0086] like Figure 1As shown, a second aspect of the present invention provides a controllable generation system for highly stable amine nanoparticles and its CO2 gas-solid reaction detection system, used to implement the above-mentioned detection method. The system includes a connected amine aerosol generation device 1 and a double-layer flow tube reaction device 2 for generating product amine aerosol particles; it also includes an EESI-HRMS online detection device 3 for extracting, ionizing, and detecting the product amine aerosol particles using high-resolution mass spectrometry. The EESI-HRMS online detection device 3 includes an extractive electrospray ionization unit 31 and an HRMS online detection unit 32. The ion transmission port 321 of the HRMS online detection unit 32 is located below the solvent transmission port 311 of the extractive electrospray ionization unit 31, for receiving ionized gaseous ions. In one specific embodiment, the extractive electrospray ionization unit 31 includes a metal nozzle for electrospray ionization, typically made of stainless steel or other conductive metal, for achieving efficient electric field focusing. The nozzle is externally connected to a microtube made of polyetheretherketone (PEEK) material for stably introducing liquid solvent or sample solution. During operation, the extraction-type electrospray ionization unit applies a high voltage, creating a strong electric field at the nozzle tip. As liquid flows out from the nozzle tip, the droplets are stretched and atomized under the influence of the electric field, forming charged microdroplets, which then generate gaseous ions through solvent evaporation and coulombic collapse. This electrospray process is a key step in achieving soft ionization in the EESI-HRMS system, effectively converting liquid samples into ionic forms detectable by mass spectrometry while maintaining the integrity of the molecular structure. The nozzle outlet is the solvent transfer port 311.

[0087] Continue reading Figure 1 In the controllable generation and CO2 gas-solid reaction detection system for highly stable amine nanoparticles provided by this invention, the amine aerosol generation device 1 includes a heated glass tube 11 and an activated carbon container 12 connected together. The inlet of the heated glass tube 11 is connected to a nitrogen pipeline 4, and the outlet of the activated carbon container 12 is connected to a double-layer flow tube reaction device 2. In a preferred embodiment, the outlet of the activated carbon container 12 is a horizontally extending glass tube.

[0088] Continue reading Figure 1 In the controllable generation of highly stable amine nanoparticles and the detection system of their CO2 gas-solid reaction provided by the present invention, a first mass flow meter 41 is provided on the nitrogen pipeline 4.

[0089] Continue reading Figure 1In the controllable generation of highly stable amine nanoparticles and the detection system of their CO2 gas-solid reaction provided by this invention, the double-layer flow tube reaction device 2 includes a connected double-layer flow tube reactor 21 and a CO2 adsorbent container 23. The inlet of the double-layer flow tube reactor 21 is connected to the CO2 pipeline 5 and the nitrogen dilution gas pipeline 6, respectively. The outlet of the CO2 adsorbent container 23 is vertically positioned between the solvent transfer port 311 and the ion transfer port 321, and is located below the solvent transfer port 311 and above the ion transfer port 321. This allows the sample to receive spray from the solvent transfer port 311 after release and enter the ion transfer port 321 under the guidance of gravity and airflow, achieving efficient extraction and ion introduction.

[0090] Continue reading Figure 1 In the controllable generation of highly stable amine nanoparticles and the detection system of their CO2 gas-solid reaction provided by the present invention, an online detection device 7 for amine particle size concentration is also provided between the double-layer flow tube reactor 21 and the CO2 adsorbent container 23. The online detection device 7 for amine particle size concentration includes an electrostatic classifier 71 (model 3080, TSI USA), a differential mobility analyzer 72 (Q-DMA-L, Beijing Nanoparticles) and a particle condensation counter 73 (model 3776, TSIUSA) connected in sequence. The front end inlet of the electrostatic classifier 71 is connected to the outlet of the double-layer flow tube reactor 21. In a preferred embodiment, the online amine particulate matter concentration detection device 7 is a scanning electromobility particle size spectrometer (SMPS) for online detection and dynamic feedback of the concentration and particle size distribution of amine aerosol particles. The SMPS includes an electrostatic classifier 71, a differential mobility analyzer 72, and a particle condensation counter 73 connected in sequence. The front end of the electrostatic classifier 71 is connected to an aerosol neutralizer and an impactor in sequence. The inlet of the impactor is connected to the outlet of the double-layer flow tube reactor 21. The product diverted by the needle valve 22 will have its particle concentration and particle size detected online in the online amine particulate matter concentration concentration detection device 7, thereby dynamically feeding back changes in particle concentration and particle size, achieving precise control and stable generation of amine particles.

[0091] Continue reading Figure 1 In the controllable generation of highly stable amine nanoparticles and the detection system of their CO2 gas-solid reaction provided by the present invention, a second mass flow meter 51 is provided on the CO2 pipeline 5, and a third mass flow meter 61 is provided on the nitrogen dilution gas pipeline 6.

[0092] Continue reading Figure 1In the controllable generation of highly stable amine nanoparticles and the detection system of their CO2 gas-solid reaction provided by the present invention, a needle valve 22 is also provided between the double-layer flow tube reaction device and the CO2 adsorbent container to control the flow rate of the reaction products flowing into the CO2 adsorbent, so as to achieve a better CO2 removal effect.

[0093] Usage process:

[0094] like Figure 1 As shown, the sample and amine compound are first placed in a heated glass tube 11 and heated in a tube furnace. The flow rate of nitrogen gas is controlled by a first mass flow meter 41 to form polydisperse amine aerosol mixed particles. The amine aerosol mixed particles are then introduced into an activated carbon container 12 containing activated carbon decomposition agent to remove excess gaseous organic matter, obtaining pure amine aerosol mixed particles.

[0095] Next, the resulting amine aerosol mixture is fed into a double-layer flow tube reactor 21. The flow rate of nitrogen dilution gas is controlled by mass flow meter 61, and the flow rate of CO2 is controlled by mass flow meter 51, allowing the amine aerosol mixture to undergo a multiphase reaction with CO2. After the reaction is complete, the flow rate into the CO2 adsorbent container 23 is controlled by needle valve 22. The CO2 adsorbent in the container reacts with the residual CO2, preventing it from interfering with the subsequent detection results in the ionization zone. The remaining product particles discharged through needle valve 22 are diverted to the online amine particle size concentration detection device 7, used to measure the particle size and concentration distribution of the amine aerosol particles after the reaction.

[0096] Subsequently, the solvent is injected into the electrospray ionization unit 31 (Orbitrap Fusion, Thermo Scientific), and a high voltage is applied to form an electrospray. The reactant aerosol particles are extracted into the electrospray and ionized, and then introduced into a high-resolution mass spectrometer (HRMS) for online detection via the ion transfer port 321 (Orbitrap Fusion, Thermo Scientific).

[0097] To make the technical means, creative features, objectives and effects of this invention easy to understand, the invention will be specifically described below in conjunction with embodiments and accompanying drawings.

[0098] In the following examples, unless otherwise stated, all reactants are commercially available products.

[0099] Unless otherwise specified, the purity of each product in each embodiment of the present invention exceeds 98%.

[0100] Example 1

[0101] The process of using an amine aerosol multiphase reaction platform coupled with an EESI-HRMS online detection system, such as... Figure 1As shown.

[0102] Before the experiment, the carrier gas (nitrogen) was controlled at a flow rate of 200-300 ml / min using the first mass flow meter 41. The TEPA and squalane mixed liquid sample was placed in a heated glass tube 11 and heated. The furnace temperature was set between 112-116℃ to control the concentration and particle size distribution of the generated particles. Since TEPA has a high saturated vapor pressure, it cannot stably generate particles. Attaching it to the surface of non-reactive squalane particles achieves stable particle generation without interfering with the reaction between amine particles and CO2. The generated aerosol particles were treated with activated carbon to remove gaseous organic impurities. The carrier gas (CO2) was controlled at a flow rate of 0-148.6 ml / min using mass flow meter 51 (corresponding to a concentration of 0-135176 ppm in the flow tube). The carrier gas (nitrogen) served as a dilution gas, and its flow rate was controlled at 900-651.4 ml / min using mass flow meter 61 to ensure a total gas flow rate of 1100 ml / min entering the double-layer flow tube reactor 21 (corresponding to a reaction time of approximately 37 seconds). A double-layer flow tube reactor 21 is used to achieve a multiphase reaction between amine particles and CO2, with a total flow rate of 1100 ml / min (corresponding to a reaction time of approximately 37 s). The water bath layer in the middle of the double-layer flow tube reactor 21 allows for precise control of the reaction temperature (50°C). After the reaction, the particles are controlled by needle valve 22 to enter the CO2 adsorbent container 23 (filled with flake KOH) at a flow rate of 150 ml / min to fully remove residual CO2 from the system. Aerosol particles flowing out of the CO2 adsorbent container 23 are introduced into the chamber of the extraction-type electrospray ionization unit 32 via a glass tube. The solvent (methanol: acetonitrile = 1:1) is introduced through the solvent transfer port 311 of the PEEK tube and forms an electrospray under a high electric field (+3000V). The aerosol particles are extracted into the solvent electrospray and ionized to generate molecular ions with almost no fragmentation. These ions are then introduced into the HRMS online detection unit 32 for online detection via the ion transfer port 321. The particles discharged from needle valve 22 are transmitted to amine particulate matter online particle size concentration detection device 7 for detection of amine particulate matter concentration and particle size, so as to dynamically feed back changes in particle concentration and particle size, and realize precise control and stable generation of amine particulate matter.

[0103] like Figure 2 As shown, for N-(3-aminopropyl)diethanolamine (labeled APDEA in the figure), scanning electromigration particle size distribution (SEM) analysis revealed that the pure sample formed a low concentration of particulate matter at a furnace temperature of 115℃ and a carrier gas flow rate of 200 ml / min. However, when mixed with squalane (3:2), a higher concentration of alkanolamine particulate matter (5280 μg / m³) was achieved. 3 ).

[0104] Subsequently, the distribution of TEPA particles from homogeneous and heterogeneous nucleation was determined using scanning electromigration particle size distribution spectrometry. For example... Figure 3 As shown, when the furnace temperature is 113℃ and the carrier gas nitrogen flow rate is 300 ml / min, TEPA cannot form a sufficient concentration of aerosol particles (7.2 μg / m³). 3 This may be related to its high saturated vapor pressure.

[0105] When decyltetradecyl alcohol or squalane samples were mixed into a heated glass tube 11 containing TEPA, particle formation was significantly improved. For example... Figure 4 As shown in Figure a, when the TEPA:decyltetradecyl alcohol ratio is 3:2, a high concentration of TEPA particles (7190 μg / m³) can be generated at a furnace temperature of 116 °C and a carrier gas flow rate of 200 ml / min. 3 ).like Figure 4 As shown in b, when TEPA:squalane = 3:2, the concentration of generated TEPA particles (4660-6330 μg / m³) can be adjusted in real time by changing the carrier gas flow rate (200-300 ml / min) and the furnace temperature (112-116 °C). 3 ) and particle size range (358-400nm).

[0106] like Figure 5 The image shows an online mass spectrum of the reaction between TEPA particles and CO2. Figure 5 TEPA (C8H) can be seen in a. 23 [M+H] of N5, MW 189) + (m / z 190) and [M+Na] + (m / z 212) peak. When CO2 is introduced, Figure 5 As shown in b, the reaction between TEPA and CO2 produces multiple products. Specifically, this includes the products of the TEPA + CO2 reaction, such as [M + CO2 + H]. + (m / z 234), [M + CO2 - H2O + H] + (m / z 216), [M+CO2-H2O+Na] + (m / z 238) and [M+CO2+H2O+H] + (m / z 252); Products of TEPA + 2CO2, such as M + 2CO2 - H2O (m / z 282) and [M + 2CO2 + Na] + (m / z 301); Products of TEPA + 3CO2, such as [M+3CO2-H2O-H] - (m / z 302).

[0107] Furthermore, to quantitatively determine the multiphase reaction rate between TEPA and CO2, the decay rate (denoted as k) and effective absorption coefficient (denoted as γ) of the TEPA particles were derived from equations E1 and E2, following the method of Smith et al. (Aerosol Sci. Technol. 2023, 58 (4), 356-373). k was determined by fitting the decay data to an exponential function (1) by monitoring CO2 exposure, i.e., CO2 concentration × reaction time (37 s). Equation (2) was used to calculate γ, which quantifies the reaction rate of collisions between TEPA particles and CO2 molecules. In Equation (2), D is the central particle size (429.2 nm), and ρ0 is the density of TEPA (0.988 g / cm³). 3 ), N A is Avogadro's constant, c is the average velocity of CO2 gas molecules (378.8 m / s), and M is the molar mass of TEPA molecules (189.3 g / mol).

[0108]

[0109] like Figure 6 The figure shows the decay kinetics of TEPA with increasing CO2 exposure. The fitted reaction rate constant k is 4.93 × 10⁻⁶. -20 The effective absorption coefficient γ was then calculated to be 1.17 × 10⁻⁶. -7 .

[0110] In summary, this invention proposes a method for the tunable generation of amine aerosol particles and applies it to the study of their multiphase reaction kinetics with CO2. By selecting reactive carbon particles (squalane) as a heterogeneous core, stable generation of organic amine particles (TEPA) with controllable particle size and concentration is achieved, providing a stable aerosol source for the multiphase kinetic study of amine aerosols with CO2. Real-time synchronous monitoring of reactant consumption is achieved by coupling high temporal resolution (millisecond-level) online sampling with high-specificity molecular detection (Orbitrap, HRMS). The reaction rate constant is directly obtained by fitting the reactant as a function of CO2 exposure, quantifying the amine aerosol-CO2 multiphase reaction rate and providing a theoretical basis for aerosol emission control in carbon capture processes.

[0111] The above embodiments are preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention.

[0112] The applicant declares that this invention illustrates the method of the online detection system for multiphase oxidation reactions of aerosol particles through the above embodiments, but this invention is not limited to the above embodiments, that is, it does not mean that this invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

[0113] The above embodiments are preferred examples of the present invention and are not intended to limit the scope of protection of the present invention. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the scope of protection of the present invention.

[0114] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

Claims

1. A method for the controllable generation of highly stable amine nanoparticles and the detection of their CO2 gas-solid reaction, characterized in that, Includes the following steps: 1) The amine compound and the sample are placed in an amine aerosol generating device and heated. The gaseous organic impurities are removed by activated carbon decomposition agent to obtain amine aerosol mixed particles. In step 1), the amine compound is selected from tetraethylenepentamine, triethanolamine, or N-(3-aminopropyl)diethanolamine; In step 1), the sample is squalane or decyltetradecyl alcohol; In step 1), the volume ratio of the amine compound to the sample is (1-3):1; In step 1), nitrogen gas is introduced during the heating process, and the flow rate of nitrogen gas is 200-300 ml / min; In step 1), the temperature is heated to 112-116℃; 2) The amine aerosol mixed particles obtained in step S1 are fed into a double-layer flow tube reactor to undergo a multiphase reaction with CO2. After the reaction, part of the product is fed into an online amine particle size concentration detection device for detection, and the other part of the product is fed into a CO2 adsorbent to remove residual CO2, thus obtaining the product amine aerosol particles. 3) The amine aerosol particles obtained in step S2 are extracted into solvent electrospray, ionized, and then introduced into the HRMS online detection unit for detection by the ion transfer tube.

2. The method for controllable generation of highly stable amine nanoparticles and detection of their CO2 gas-solid reaction as described in claim 1, characterized in that, It also includes one or more of the following features: In step 2) of A1), CO2 is introduced during the multiphase reaction process, and the flow rate of CO2 is greater than 0 ml / min and less than or equal to 148.6 ml / min; In step 2) of A2), nitrogen dilution gas is also introduced during the multiphase reaction process, and the flow rate of nitrogen dilution gas is 900-651.4 ml / min; A3) In step 2), the reaction temperature of the multiphase reaction process is 25-70℃; the reaction time is 37s. In step 2) of A4), the CO2 adsorbent is KOH.

3. The method for controllable generation of highly stable amine nanoparticles and detection of their CO2 gas-solid reaction as described in claim 1, characterized in that... It also includes one or more of the following features: In step 3) of A5), the solvent in the solvent electrospray is a mixture of methanol and acetonitrile or methanol; In step 3) of A6), the solvent electrospray is formed by applying a high voltage to the solvent stream.

4. The method for controllable generation of highly stable amine nanoparticles and detection of their CO2 gas-solid reaction as described in claim 3, characterized in that, It also includes one or more of the following features: The volume ratio of methanol to acetonitrile in A51 is (1-3):1; A61) The voltage range for applying high voltage is 2500-3500V.

5. A system for the controllable generation of highly stable amine nanoparticles and the detection of their CO2 gas-solid reaction, used to implement the detection method as described in any one of claims 1-4, characterized in that, The device includes a connected amine aerosol generating device (1) and a double-layer flow tube reaction device (2) for generating product amine aerosol particles; it also includes an EESI-HRMS online detection device (3) for extracting, ionizing and detecting the product amine aerosol particles by high-resolution mass spectrometry; the EESI-HRMS online detection device (3) includes an extraction-type electrospray ionization unit (31) and an HRMS online detection unit (32), the ion transmission port (321) of the HRMS online detection unit (32) is located below the solvent transmission port (311) of the extraction-type electrospray ionization unit (31) for receiving ionized gaseous ions; The double-layer flow tube reactor (2) includes a connected double-layer flow tube reactor (21) and a CO2 adsorbent container (23). An online amine particulate matter particle size concentration detection device (7) is also provided between the double-layer flow tube reactor (21) and the CO2 adsorbent container (23).

6. The controllable generation of highly stable amine nanoparticles and the detection system for their CO2 gas-solid reaction according to claim 5, characterized in that, It also includes one or more of the following features: B1) The amine aerosol generating device (1) includes a heated glass tube (11) and an activated carbon container (12) connected together. The inlet of the heated glass tube (11) is connected to the nitrogen pipeline (4), and the outlet of the activated carbon container (12) is connected to the double-layer flow tube reaction device (2). B2) The inlet of the double-layer flow tube reactor (21) is connected to the CO2 pipeline and the nitrogen dilution gas pipeline respectively, and the outlet of the CO2 adsorbent container (23) is located vertically between the solvent transfer port (311) and the ion transfer port (321).

7. The controllable generation of highly stable amine nanoparticles and the detection system for its CO2 gas-solid reaction as described in claim 6, characterized in that, In feature B1), a first mass flow meter (41) is provided on the nitrogen pipeline.

8. The controllable generation of highly stable amine nanoparticles and the detection system for their CO2 gas-solid reaction according to claim 6, characterized in that, In feature B2), the online detection device (7) for amine particulate matter particle size concentration includes an electrostatic classifier (71), a differential mobility analyzer (72), and a particle condensation counter (73) connected in sequence. The front-end inlet of the electrostatic classifier (71) is connected to the outlet of the double-layer flow tube reactor (21).

9. The controllable generation of highly stable amine nanoparticles and the detection system for their CO2 gas-solid reaction according to claim 8, characterized in that, The CO2 pipeline (5) is equipped with a second mass flow meter (51), and the nitrogen dilution gas pipeline (6) is equipped with a third mass flow meter (61).

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