An enrichment and analysis device for detecting carbonaceous components in atmospheric particulate matter, a detection device and a detection method

Abstract

The application provides an enrichment and analysis device for detecting carbon components of atmospheric particulate matters, comprising: a tube body, an inner part of which is provided with a sleeve, and the tube body is communicated with a desorption tube and an air outlet tube respectively; the sleeve has a sample inlet and a sample outlet on two sides respectively; a filter membrane and a heating component are arranged at the sample outlet of the sleeve in the sample feeding direction of the particulate matters, wherein the heating component can heat the filter membrane; the desorption tube is communicated with the tube body downstream or upstream of the filter membrane in the sample feeding direction of the particulate matters, and is preferably downstream; the air outlet tube is communicated with the tube body downstream of the filter membrane in the sample feeding direction of the particulate matters. The electromagnetic direct heating mode is adopted, and the cold spots, heat preservation shells and filter membranes in the current structural device which are easy to take out and other components are optimized correspondingly, so that the analysis efficiency is maximally ensured, the transmission loss of substances is reduced, and the sensitivity and accuracy of OCEC measurement are improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of environmental monitoring, and relates to an enrichment and analysis device for detecting carbon components in atmospheric particulate matters, a detection equipment and a detection method, in particular to an enrichment and analysis device for detecting carbon components based on electromagnetic heating, a detection equipment and a detection method. BACKGROUND

[0002] Atmospheric aerosol carbon components mainly include organic carbon (OC) and elemental carbon (EC), which are important components of atmospheric fine particles and have a very important influence on the atmospheric environment and human health. In the research of atmospheric aerosol carbon components, accurate determination of the concentrations of OC and EC is of great significance for studying atmospheric chemical reactions and source analysis of pollutants.

[0003] At present, the monitoring of atmospheric particulate carbon components is mainly based on thermal decomposition-photochemical calibration analysis method. The principle is based on the thermodynamic characteristics of OC and EC. The collected organic carbon substance OC and elemental carbon substance EC are respectively subjected to programmed temperature under oxygen-free and oxygen-containing conditions in steps, and then the resolved substances are introduced into a catalytic oxidation furnace for oxidation into carbon dioxide, which is measured by using an NDIR detector. Or the carbon dioxide is introduced into a reduction furnace for reduction into methane, and the methane signal is measured by using an FID. In order to correct the content of OPC (pyrolytic carbon) generated by the thermal decomposition of OC in the oxygen-free stage, a 633nm laser is used to irradiate the filter film throughout the process, and the split point of OC and EC is determined according to the change of the transmitted light or reflected light signal, so as to correct the OPC content.

[0004] Based on the principle of thermal optical method to monitor atmospheric OCEC, ensure its rapid, accurate temperature rise and optical stability is the key factor of accurate cutting and measurement. At present, the filter membrane high temperature thermal analysis in the monitoring system of carbonaceous components in atmospheric particulate matter in domestic manufacturers basically adopts heating wire winding pipe outer wall or self-made external heating module to heat the pipe (such as CN202110932037.8, CN201420653203.6, etc.), the traditional resistance type heating method has low heating efficiency, and the high heating temperature leads to large thermal hysteresis, which is not easy to accurately control temperature, and the resistance wire is easy to burn out due to high temperature aging, that is, the resistance type heating method is not suitable for higher temperature heating; In addition, the resistance heating is based on two-stage heat conduction to heat the filter membrane, that is, the heat generated by the heating wire / rod is transferred to the filter membrane through the quartz outer tube, which is an indirect heating method. The filter membrane heating is slow, which is easy to cause uneven heating of the filter membrane surface, and cannot guarantee the rapid programmed temperature rise demand of the captured OCEC, which reduces the desorption efficiency and measurement accuracy of OCEC. In addition, at present, major manufacturers do not emphasize the cold spot problem between the filter membrane and the oxidation furnace when preparing the instrument, but in actual application, at the last high temperature stage (850℃) of analysis, the pipeline between the filter membrane and the oxidation furnace simply relies on heat transfer, which often fails to reach 850℃, which will cause the measured substances desorbed from the filter membrane to adhere to the inner wall of the quartz tube before entering the oxidation furnace, resulting in transmission loss and incomplete and inaccurate measurement.

[0005] In terms of ensuring the stability of the optical path and the gas path, there is no unified regulation for the connection and fixation of the furnace and the heat preservation shell, but in actual application, slight instability of the furnace can easily lead to instability of the optical path, thereby affecting the cutting and measurement of OC and EC. In addition, at present, major manufacturers basically use long tweezers or long needles with hooks to hook out the filter membrane when replacing the filter membrane, which will damage the surface of the filter membrane and cannot guarantee the integrity of the substance information enriched in the filter membrane. SUMMARY

[0006] In view of the deficiencies in the prior art, the present application optimizes the enrichment thermal desorption and monitoring of carbonaceous components of atmospheric particulate matter, and designs a detection device and method for carbonaceous components of atmospheric particulate matter based on electromagnetic heating. The sampled filter membrane is heated and cooled by electromagnetic direct heating and fan refrigeration, combined with a designed non-uniform heat preservation device, which meets the rapid heating demand of the filter membrane and the high heat preservation performance of the remaining constant high temperature components, and also ensures the rapid cooling of the filter membrane during OC-EC desorption switching, improving the efficient and accurate desorption of organic carbon substance OC and elemental carbon substance EC. In addition, the gas path transmission component between the pipe body and the oxidation furnace is designed with a heat tracing control device consistent with the filter membrane desorption heating process, which maximizes the loss of material transmission caused by cold spots. For the requirement of non-destructive removal of the filter membrane, a quartz sleeve with a built-in quartz filter membrane-metal tungsten sheet is arranged in the quartz main pipe, which can be directly operated on the quartz sleeve to meet the portable removal and replacement of the filter membrane.

[0007] In terms of measurement means diversification, a single separation and measurement method is not conducive to the comparison of results between laboratories, so the present measurement system provides two measurement methods, CO2-NDIR and CH4-FID, and two optical correction methods, reflection correction and transmission correction. In practical applications, one or both of the two measurement and correction methods can be selected, and the use of two measurement and correction methods can complement and improve each other to ensure the integrity and comparability of the monitoring information.

[0008] The technical scheme of the present application is as follows:

[0009] 1. An enrichment and desorption device for detecting carbonaceous components in atmospheric particulate matter, comprising:

[0010] a pipe body having a sleeve arranged therein, and the pipe body being in communication with a desorption pipe and an air outlet pipe respectively;

[0011] a sleeve, the two sides of the sleeve being respectively an inlet and an outlet; in the sampling direction of the particulate matter, a filter membrane and a heating component are arranged at the outlet of the sleeve, wherein the heating component can heat the filter membrane;

[0012] a desorption pipe, the desorption pipe being in communication with the pipe body downstream or upstream of the filter membrane in the sampling direction of the particulate matter, preferably downstream;

[0013] an air outlet pipe, the air outlet pipe being in communication with the pipe body downstream of the filter membrane in the sampling direction of the particulate matter.

[0014] 2. The device of item 1,

[0015] a heating component is arranged outside the desorption pipe.

[0016] 3. The device of item 2,

[0017] The device further comprises a synchronous heating device capable of synchronously heating the heating component arranged inside the sleeve and the heating component outside the desorption tube;

[0018] Preferably, the synchronous heating device comprises an electromagnetic heating control board, an induction coil and a heating element, the electromagnetic heating control board is connected with the induction coil, and the induction coil is arranged outside the tube body and outside the desorption tube to meet the common heating requirement of the heating component wound at the desorption tube and the heating component placed downstream of the filter membrane.

[0019] 4. The device according to item 3,

[0020] The heating component is a magnetic conductive film, and further preferably the magnetic conductive film is a metal tungsten sheet, a metal molybdenum sheet, a ferrosilicon sheet or a ferro-nickel sheet.

[0021] 5. The device according to item 1,

[0022] The tube body further comprises a support structure arranged downstream of the sleeve in the sampling direction of the particulate matter to fix the position of the filter membrane and the heating component downstream of the filter membrane.

[0023] 6. The device according to item 1,

[0024] The device further comprises an inner lining arranged inside the sleeve between the sampling port and the filter membrane to block the movement of the filter membrane inside the tube body.

[0025] 7. The device according to item 1,

[0026] The filter membrane is a quartz fiber filter membrane.

[0027] 8. The device according to item 1,

[0028] The device further comprises a first temperature sensor for detecting the temperature of the filter membrane.

[0029] Preferably, the first temperature sensor is the first patch temperature sensor, which is located on the outside of the tube body close to the filter membrane and away from the side of the tube body with the desorption tube.

[0030] 9. The device according to item 1,

[0031] One side of the desorption tube is welded to the side surface of the tube body, and the other side extends radially outward along the tube body;

[0032] The gas outlet tube extends outward from the other side surface of the tube body opposite to the side surface with the welded desorption tube.

[0033] 10. The device of item 1,

[0034] The bottom of the sample outlet of the sleeve is a hollowed middle annular structure to realize the transmission of the gas path and the position fixing of the filter membrane and the heating component in the sleeve.

[0035] 11 The device of item 1,

[0036] The heating component in the sleeve is an annular and hollow middle structure.

[0037] 12. A detection device for detecting carbonaceous components in atmospheric particulate matter,

[0038] The enrichment and resolution device of any one of items 1-11.

[0039] 13. The device of item 12,

[0040] The desorption tube is connected to the oxidation furnace on the side opposite to the side in communication with the tube body, and the oxidation furnace is externally wound with a resistance wire, wherein the resistance wire can heat the oxidation furnace.

[0041] 14. The device of item 13,

[0042] The device further comprises an NDIR detector connected to the oxidation furnace for detecting the gas sample treated by the oxidation furnace.

[0043] 15. The device of item 13,

[0044] The device further comprises a reduction furnace connected to the side opposite to the side in communication with the oxidation furnace.

[0045] 16. The device of item 15,

[0046] The device further comprises an FID detector connected to the reduction furnace for detecting the gas sample treated by the reduction furnace.

[0047] 17. The device of item 13,

[0048] The device further comprises a reduction furnace connected to the oxidation furnace through a tee valve.

[0049] 18. The device of item 17,

[0050] The device further comprises an NDIR detector connected to the oxidation furnace for detecting the gas sample treated by the oxidation furnace, and an FID detector connected to the reduction furnace for detecting the gas sample treated by the reduction furnace.

[0051] 19. The apparatus of item 13,

[0052] The apparatus further comprises a second temperature sensor for detecting the temperature of the oxidation furnace;

[0053] Preferably, the second temperature sensor is the second patch temperature sensor, which is located outside the oxidation furnace.

[0054] 20. The apparatus of item 15 or 17,

[0055] The apparatus further comprises a third temperature sensor for detecting the temperature of the reduction furnace;

[0056] Preferably, the third temperature sensor is the third patch temperature sensor, which is located outside the reduction furnace.

[0057] 21. The apparatus of item 12,

[0058] The gas outlet pipe is connected with a flow controller on the side opposite to the side in communication with the pipe body, and the flow controller is used for precisely controlling the sampling flow of the apparatus.

[0059] 22. The apparatus of item 12,

[0060] The side of the pipe body opposite to the sample inlet is provided with a first detector (detector B), and the side of the pipe body outside and adjacent to the sample inlet is provided with a light source, a light splitting piece and a second detector (detector A) for optical detection.

[0061] 23. The apparatus of item 15 or 17,

[0062] The apparatus further comprises a heat preservation device, which is arranged outside the filter membrane, the heating component, the support structure, the desorption pipe, the oxidation furnace and the reduction furnace.

[0063] 24. A method for detecting carbonaceous components in atmospheric particulate matter by using the device of any one of items 1-11 and the apparatus of any one of items 12-23.

[0064] 25. The method of item 24, comprising

[0065] the enrichment step, the purging step, the OC analysis step, the EC analysis step and the calibration step; wherein,

[0066] the enrichment step: passing the sample to be detected into the enrichment and resolution device so that the carbonaceous components are enriched in the enrichment and resolution device;

[0067] the purging step: purging the apparatus and its transmission route with carrier gas to remove excess gas;

[0068] OC analysis step: under anaerobic condition, organic carbon matter OC adsorbed in carbonaceous component in enrichment and resolution device is desorbed and enters into oxidation furnace with carrier gas; organic carbon matter entering into oxidation furnace is oxidized into CO2; oxidized CO2 enters into NDIR detector for measurement;

[0069] EC analysis step: under aerobic condition, element carbon matter EC adsorbed in carbonaceous component in enrichment and resolution device is desorbed and enters into oxidation furnace; element carbon matter entering into oxidation furnace is oxidized into CO2; oxidized CO2 enters into NDIR detector for measurement;

[0070] Calibration process: helium / methane standard gas in quantitative ring is oxidized into CO2 by subsequent oxidation furnace, and oxidized CO2 enters into NDIR detector for quantitative detection.

[0071] 26. The method according to item 24, comprising

[0072] enrichment step, purge step, OC analysis step, EC analysis step and calibration step; wherein,

[0073] Enrichment step: sample to be detected is introduced into enrichment and resolution device, so that carbonaceous component is enriched in the enrichment and resolution device;

[0074] Purge step: carrier gas is purged to the equipment and its transmission route to remove excess gas;

[0075] OC analysis step: under anaerobic condition, organic carbon matter OC adsorbed in carbonaceous component in enrichment and resolution device is desorbed and enters into oxidation furnace with carrier gas; organic carbon matter entering into oxidation furnace is oxidized into CO2; oxidized CO2 enters into reduction furnace and is reduced into CH4; reduced CH4 enters into FID detector for measurement;

[0076] EC analysis step: under aerobic condition, element carbon matter EC adsorbed in carbonaceous component in enrichment and resolution device is desorbed and enters into oxidation furnace; element carbon matter entering into oxidation furnace is oxidized into CO2; oxidized CO2 enters into reduction furnace and is reduced into CH4; reduced CH4 enters into FID detector for measurement;

[0077] Calibration process: helium / methane standard gas in quantitative ring is respectively converted into CO2 and CH4 by subsequent oxidation furnace and reduction furnace, and reduced CH4 enters into FID detector for quantitative detection.

[0078] 27. The method according to item 24, comprising

[0079] The enrichment step, the purging step, the enrichment step, the purging step, the OC analysis step, the EC analysis step and the calibration step; wherein,

[0080] The enrichment step: the sample to be detected is introduced into the enrichment and analysis device, so that the carbonaceous components are enriched in the enrichment and analysis device;

[0081] The purging step: the equipment and its transmission route are purged with carrier gas to remove excess gas;

[0082] The OC analysis step: under an oxygen-free state, the organic carbon material OC in the carbonaceous components adsorbed in the enrichment and analysis device is desorbed and enters the oxidation furnace with the carrier gas; the organic carbon material entering the oxidation furnace is oxidized into CO2; part of the oxidized CO2 enters the NDIR detector for direct measurement; the other part enters the reduction furnace and is reduced into CH4, and the reduced CH4 enters the FID detector for measurement;

[0083] The EC analysis step: under an oxygen-containing state, the elemental carbon material EC in the carbonaceous components adsorbed in the enrichment and analysis device is desorbed and enters the oxidation furnace; the elemental carbon material entering the oxidation furnace is oxidized into CO2; part of the oxidized CO2 enters the NDIR detector for direct measurement; the other part enters the reduction furnace and is reduced into CH4, and the reduced CH4 enters the FID detector for measurement;

[0084] The calibration process: the helium / methane standard gas in the quantitative ring is oxidized into CO2 by the subsequent oxidation furnace, and part of the oxidized CO2 enters the NDIR detector for direct measurement; the other part enters the reduction furnace and is reduced into CH4, and the reduced CH4 enters the FID detector for quantitative detection.

[0085] Compared with the prior art, the application has the following beneficial effects:

[0086] (1) For the current research on accurate measurement of carbonaceous components in atmospheric particulate matter, an enrichment device, enrichment and analysis equipment and detection method for carbonaceous component detection based on electromagnetic heating are developed. A novel low-energy electromagnetic direct heating method is used to realize rapid analysis of the measured substance, and the wall cold spots, heat preservation shells and filter membranes in the current structure device are optimized accordingly, which maximizes the reduction of material transmission loss and improves the efficiency and accuracy of OCEC measurement.

[0087] (2) The application provides a filter membrane heating mode based on electromagnetic direct heating, that is, a quartz fiber filter membrane and a magnetic conductive membrane piece structure are integrated and nested into the pipeline of a quartz sleeve. The enrichment device directly heats the quartz filter membrane by using efficient electromagnetic heating, avoids the uneven heating phenomenon caused by slow heating in the previous resistance type secondary heat conduction heating mode, and realizes direct heating and temperature rise of the surface area of the quartz filter membrane by using the integrated structure design mode of the surface-to-surface contact of the quartz filter membrane and the heating element, so as to ensure uniform heating of the surface of the filter membrane and high resolution efficiency in the pyrolysis stage.

[0088] (3) The device adopts a desorption tube at the side end of the quartz tube body to perform subsequent oxidation treatment on the thermal desorption sample, forms an integrated collection and resolution and oxidation component, and if the sample needs to be further reduced and monitored, a reduction component is directly welded at the rear end of the oxidation component, that is, an integrated collection and resolution, oxidation and reduction device is formed. The whole device has compact structure, small size, and maximally reduces the dead volume in the gas path transmission.

[0089] (4) The gas path transmission components between the filter membrane and the detector of the device are heated to a certain predetermined high temperature, and are controlled and adjusted by PID, and the temperature accuracy is 0.2℃. The whole section heating and heat tracing setting avoid the wall loss and water vapor condensation of the measured substances, and ensure the authenticity and accuracy of the measurement. +

[0090] (5) In order to ensure the rapid cooling of the filter membrane in the OCEC analysis stage, the application designs a non-uniform heat preservation component. The component performs thin heat preservation at the position of the filter membrane, and thick heat preservation at the remaining parts needing constant high temperature. Combined with electromagnetic heating and fan refrigeration, the design ensures the rapid heating in the filter membrane resolution stage and the efficient heat preservation of the remaining high-temperature constant temperature components, and also ensures the rapid cooling of the filter membrane in the OCEC conversion stage, so as to meet the temperature change requirements of different high and low temperatures in the OCEC measurement. In order to ensure the stability of the device in the measurement stage, viscous substances are designed in the quartz components and the heat preservation module. The fixing mode ensures the stability of the whole device, and avoids the abnormal light path transmission caused by unstable structure. BRIEF DESCRIPTION OF DRAWINGS

[0091] Figure 1 a is a schematic view of a quartz sleeve structure in the enrichment device;

[0092] Figure 1 b is a schematic view of the connection between the sleeve and the tube body in the enrichment device;

[0093] Figure 2 is a schematic view of a detection device for carbon component detection;

[0094] Figure 3 is a schematic view of a detection device for carbon component detection;​

[0095] Figure 4 Schematic diagram of detection device for carbon component detection

[0096] Figure 5 Schematic diagram of non-uniform heating device structure

[0097] Explanation of reference signs:

[0098] 1. quartz tube body; 2. quartz sleeve; 3. quartz lining; 4. quartz support structure; 5. quartz filter membrane; 6. heating component; 7. induction coil; 8. oxidation furnace; 9. resistance wire; 10. desorption tube; 11. gas outlet tube; 12. optical tube; 13. flow control; 14. electromagnetic heating control panel; 15. light source; 16. light splitting piece; 17. detector A; 18. detector B; 19. NDIR detector; 20. reduction furnace; 21. FID detector; 22. fan; 23. heat preservation device; 24. heat preservation coating; 25. first temperature sensor; 26. second temperature sensor; 27. third temperature sensor; 29. joint; 30. first electric three-way valve; 31. cutting head; 32. dissolver; 33. gas supply and pressure control system; 34. computer interactive control system; 35. second electric three-way valve. DETAILED DESCRIPTION

[0099] At present, the filter membrane high temperature pyrolysis of the atmospheric particulate matter carbon element monitoring system of domestic major manufacturers basically adopts heating wire winding outer wall or self-made external heating module to heat the tube. For example, patent documents CN202110932037.8, CN201420653203.6, etc. This heating method is based on the low-efficiency resistance heating two-stage heat conduction, that is, the heat generated by the heating wire / rod is transferred to the filter membrane through the quartz outer tube. This indirect heating method of the filter membrane has slow heating and large high-temperature hysteresis, which easily leads to uneven heating of the filter membrane surface, cannot guarantee the rapid programmed temperature rise requirement of the captured OCEC, and reduces the desorption efficiency and measurement accuracy of the OCEC. In addition, in order to avoid the phenomenon of incomplete separation of carbon components caused by slow heating, patent document 201910248081.X uses two collection devices to collect separately, which increases the cost of the equipment.

[0100] In addition, the current carbon element monitoring system generally designs the collection / analysis component and the oxidation component as an integrated device, that is, a detached side pipe is opened at the end of the main pipe side for placing the oxidation reagent. Although the integrated structure design causes part of the heat transfer at the intermediate quartz transmission pipe due to the constant high temperature at the oxidation furnace and the heat transfer of the surface program heating of the filter membrane, in the last stage of the analysis heating, that is, the filter membrane surface needs to be heated to 850°C, the oxidation furnace part also maintains a constant temperature of 850°C. If the gas transmission component between the two has no heat tracing device, and simply relies on the high temperature heat conduction of the oxidation furnace and the filter membrane surface, it generally cannot reach 850°C, which easily leads to the condensation wall loss of the measured substances from the 850°C filter membrane surface before entering the oxidation component due to the existence of a cold spot in the transmission pipeline, reducing the accuracy of the measurement.

[0101] In addition, since the filter membrane and the oxidation and reduction components must be kept at a specific high temperature, manufacturers generally design a well-insulated outer shell for the furnace for efficient insulation, which leads to the need for a large flow blower or a series of complex external refrigeration equipment to rapidly cool the filter membrane during the analysis cooling phase in order to achieve the initial filter membrane temperature for EC oxidation analysis. Although the filter membrane can finally be cooled to the required initial low temperature, the refrigeration method is generally more cumbersome and the cost is not low.

[0102] The current filter membrane position designed by manufacturers is integrated with the collection / analysis device, that is, the filter membrane is placed in the quartz main pipe with tweezers, and when the filter membrane needs to be replaced, the filter membrane is hooked out with tweezers. This filter membrane replacement method easily causes damage to the filter membrane surface when the filter membrane is removed, and cannot guarantee the integrity of the material information when further analyzing the attached substances on the old filter membrane surface.

[0103] For example, Figure 1 and 2As shown, this application provides an enrichment device for detecting carbonaceous components, comprising: a tube body 1, wherein a sleeve 2 is disposed inside the tube body 1, and the tube body 1 is connected to a desorption tube 10 and an outlet tube 11 respectively; the sleeve 2, with an inlet and an outlet on both sides respectively; in the direction of particulate matter inlet, a filter membrane 5 and a heating element 6 are disposed at the outlet of the sleeve 2, wherein the heating element 6 is capable of heating the filter membrane; the desorption tube 10, in the direction of particulate matter inlet, the downstream or upstream end of the filter membrane 5 is connected to the tube body, preferably the downstream end; and the outlet tube 11, in the direction of particulate matter inlet, the downstream end of the filter membrane 5 is connected to the tube body. This application adopts an integrated structure of filter membrane 5 and heating element 6, nested within sleeve 2, forming an enrichment and desorption component. It directly heats the quartz filter membrane using electromagnetic heating, avoiding the uneven heating caused by the slow heating of previous low-efficiency resistance-type two-stage heat conduction heating methods. This non-contact heating method allows for direct, face-to-face heating of the quartz filter membrane, ensuring uniform heating and high efficiency in the thermal desorption stage. Simultaneously, a sleeve structure for easy membrane removal is designed. The filter membrane and heating element are placed within the sleeve, and the quartz sleeve is placed inside the tube. This design allows for easy replacement of the filter membrane simply by removing the sleeve, ensuring the integrity of the material on the filter membrane surface.

[0104] In one embodiment of this application, the tube body 1 is a quartz tube body 1.

[0105] In one embodiment of this application, the sleeve 2 is a quartz sleeve 2.

[0106] In one embodiment of this application, the filter membrane 5 is a quartz filter membrane 5.

[0107] In one embodiment of this application, the heating element 6 is a tungsten sheet 6.

[0108] like Figure 2 As shown, a heating element 6 is still provided on the outside of the desorption tube 10. To minimize the loss of the analyte during gas transmission, this application provides heating elements, i.e., a heat tracing device, in the gas transmission section of the tube body and desorption tube. A magnetic diaphragm is used to wrap the intermediate transmission pipeline, with the diaphragm placed outside the desorption tube. The heating elements at the desorption tube and the filter membrane are synchronously controlled by an electromagnetic heating control board. This ensures that the temperature of this transmission section is synchronized with the temperature rise at the filter membrane, guaranteeing that the analyte desorbed from the filter membrane remains at the same temperature as during filter membrane desorption before entering the oxidation furnace. There are no cold spots throughout the process, preventing loss of the analyte during transmission and increasing the measurement accuracy of the instrument.

[0109] like Figure 2As shown, in some embodiments of the present application, the device further comprises a synchronous heating device capable of synchronously heating the heating component 6 arranged in the sleeve and the heating component 6 arranged outside the desorption tube; preferably, the synchronous heating device comprises an electromagnetic heating control panel 14 and an induction coil 7, the electromagnetic heating control panel 14 is connected with the induction coil 7, and the induction coil 7 is arranged outside the tube body 1 and outside the desorption tube 10 to meet the common heating requirement of the heating component wound at the desorption tube and the heating component placed at the downstream of the filter membrane. The present application adopts a relatively new and efficient heating mode, i.e. electromagnetic filter membrane direct contact heating mode, integrates the magnetically conductive element with the filter membrane, places it in the excitation coil with alternating current, and cuts the alternating magnetic lines by using the magnetically conductive element, so as to generate eddy current inside the magnetically conductive element, and the heat energy generated by the eddy current directly heats the filter membrane, which not only ensures the rapid heating requirement in the desorption stage, but also ensures the uniform heating of the filter membrane surface and the efficient thermal desorption of the enriched substance. The synchronous heating device can further comprise a temperature control component, which comprises a temperature control module or a Siemens PLC control system, and is connected with the electromagnetic heating control panel to control the power output of the electromagnetic heating control panel through negative feedback regulation of temperature, so as to control the temperature. The electromagnetic heating can only realize the temperature rise, and the temperature control component realizes the control of the temperature by controlling the output of the heating power through the external temperature control instrument and the like.

[0110] In some embodiments of the present application, the heating component 6 is a magnetically conductive film piece, and further preferably the magnetically conductive film piece is a metal tungsten piece, a metal molybdenum piece, an iron-silicon piece or an iron-nickel piece.

[0111] In some embodiments of the present application, a fan is arranged outside the tube body near the filter membrane 5 to cool the filter membrane.

[0112] As shown in Figure 1 and Figure 2 , the tube body 1 further comprises a support structure 4, which is arranged downstream of the sleeve 2 in the particle sample introduction direction to fix the positions of the filter membrane 5 and the heating component 6.

[0113] In one embodiment of the present application, the support structure 4 is a quartz support structure 4.

[0114] In some embodiments of the present application, the support structure 4 is two blocking pieces arranged on the tube body, which are respectively located on the opposite sides of the sample outlet of the tube body 1.

[0115] As shown in Figure 1 and Figure 2As shown, the device also includes a liner 3, which is disposed inside the sleeve 2 and located between the sample inlet and the filter membrane 5 to prevent the filter membrane 5 from moving freely inside the sleeve 2.

[0116] In one embodiment of this application, the liner 3 is a quartz liner 3.

[0117] In some embodiments of this application, the filter membrane is a quartz fiber filter membrane.

[0118] like Figure 2 As shown, the device further includes a first temperature sensor 25, which is used to detect the temperature of the filter membrane; preferably, the first temperature sensor 25 is a first patch temperature sensor, which is located on the outside of the tube body near the filter membrane and opposite to the side of the tube body with the desorption tube.

[0119] like Figure 2 As shown, one side of the desorption tube 10 is welded to the side surface of the tube body 1, and the other side extends radially outward along the tube body 1. The desorption tube 10 is connected to the tube body 1 downstream or upstream of the filter membrane 5 in the sample introduction direction of the particulate matter, preferably downstream.

[0120] like Figure 2 As shown, the outlet pipe 11 extends outward from the opposite surface of the pipe body 1, which is opposite to the surface of the side where the desorption pipe 10 is welded. The outlet pipe 11 communicates with the pipe body downstream of the filter membrane 5 in the sample introduction direction of the particulate matter.

[0121] like Figure 2 As shown, when the desorption tube 10 is connected to the tube body 1 downstream of the filter membrane 5 in the sample feeding direction of the particulate matter, the desorption tube 10 and the outlet tube 11 are on the same vertical plane and are connected vertically.

[0122] In some embodiments of this application, the bottom of the sample outlet of the sleeve 2 is a hollowed-out annular structure to facilitate gas transmission and fix the positions of the filter membrane 5 and the heating component 6 inside the sleeve 2. From the projection of the left view, the bottom of the sample outlet of the sleeve has two baffles, which are located on opposite sides of the sample outlet.

[0123] In some embodiments of this application, the heating element 6 inside the sleeve 2 is annular with a hollowed-out center.

[0124] This application provides a detection device for detecting carbonaceous components in atmospheric particulate matter, including the aforementioned enrichment and analysis apparatus.

[0125] like Figure 2 , Figure 3 , Figure 4As shown, the desorption tube 10 is connected with an oxidation furnace 8 on the other side opposite to the side in communication with the tube body 1, and the oxidation furnace 8 is externally wound with a resistance wire 9, wherein the resistance wire 9 can heat the oxidation furnace 8.

[0126] As shown in Figure 2 and Figure 4 , the device further comprises an NDIR detector 19 connected with the oxidation furnace 8 for detecting the gas sample treated by the oxidation furnace 8.

[0127] As shown in Figure 3 and Figure 4 , the device further comprises a reduction furnace 20 on the side opposite to the side in communication with the oxidation furnace 8.

[0128] As shown in Figure 3 and Figure 4 , the device further comprises an FID detector 21 connected with the reduction furnace 20 for detecting the gas sample treated by the reduction furnace 20.

[0129] As shown in Figure 4 , the device further comprises a reduction furnace 20 connected with the oxidation furnace 8 through a three-way valve. The device further comprises an NDIR detector 19 connected with the oxidation furnace 8 for detecting the gas sample treated by the oxidation furnace 8, and an FID detector 21 connected with the reduction furnace 20 for detecting the gas sample treated by the reduction furnace 20.

[0130] As shown in Figure 2 , Figure 3 , Figure 4 , the device further comprises a second temperature sensor 26 for detecting the temperature of the oxidation furnace 8; preferably, the second temperature sensor 26 is the second patch temperature sensor, which is located outside the oxidation furnace.

[0131] As shown in Figure 3 , Figure 4 , the device further comprises a third temperature sensor 27 for detecting the temperature of the reduction furnace 20; preferably, the third temperature sensor 27 is the third patch temperature sensor, which is located outside the reduction furnace.

[0132] As shown in Figure 2 , the gas outlet tube 11 is connected with a flow controller on the other side opposite to the side in communication with the tube body 1, and the flow controller is used to precisely control the sampling flow of the device.

[0133] As shown in Figure 2As shown, the tube body 1 is provided with a first detector (detector B) on the side opposite to the sample inlet, and a light source, a light splitting sheet, and a second detector (detector A) are provided on the side outside the tube body and adjacent to the sample inlet for optical detection.

[0134] As shown in the drawings, Figure 5 As shown, the device further comprises a heat preservation device 23 arranged outside the filter membrane, the heating component, the support structure, the desorption tube, the oxidation furnace and the reduction furnace. The heat preservation device 23 contains a heat preservation coating 24 inside, the thickness of the heat preservation part at the filter membrane is thinner, and the thickness of the rest of the heat preservation part is thicker. The present application designs a non-uniform heat preservation device, that is, based on the advantages of rapid heating of electromagnetic heating, a relatively thin heat preservation coating is designed at the filter membrane, and a thick heat preservation coating is designed at the rest of the part that needs to maintain a constant high temperature. The design of this special heat preservation device enables us to meet the cooling requirements of the filter membrane in the analysis stage by using a fan for refrigeration, ensuring the rapid heating and cooling of the filter membrane and not affecting the constant high temperature of the rest of the components. The device structure is simple and the power consumption is low.

[0135] In the present application, stability is the premise of precision. At present, the connection mode of the oxidation furnace 8 and the reduction furnace 20 with the heat preservation device 23 basically relies on natural fixation. In order to ensure the stability of the furnace, high-temperature adhesive is used to connect between the furnace and the heat preservation device, which ensures the stability of the furnace in the measurement stage.

[0136] As shown in the drawings, Figure 1 As shown in the drawings, in one embodiment of the present application, the quartz tube body 1 has a size of 20 mm in diameter, 100 mm in length and 1.5 mm in wall thickness, and the quartz sleeve 2 has a size of 16 mm in diameter, 70 mm in length and 1.5 mm in wall thickness. A smooth and flat quartz support structure 4 with a length of 5 mm is welded at each end of the quartz tube body 1, and the distance between the quartz support structure 4 and the sample inlet is 70 mm, which is used to fix the installation position of the quartz sleeve 2. A 10 mm hole is opened in the middle of the sample outlet downstream of the quartz sleeve 2 for gas transmission, and 3 mm quartz platforms are left on both sides for placing filter membranes 5 and other elements. The quartz filter membrane 5 and the tungsten sheet 6 are placed in the annular structure of the quartz sleeve 2 in turn. In order to avoid the movement of the filter membrane position in the gas transmission, a thin-walled quartz lining 3 is placed in front of the quartz filter membrane 5. The thin-walled quartz lining 3 upstream and the annular structure of the quartz sleeve 2 downstream together fix the position of the quartz filter membrane, ensuring its stability in the sampling and analysis stages.

[0137] As shown in the drawings, Figure 2As shown, the collection, analysis and oxidation are integrated, i.e. a device for collecting, analyzing and oxidizing atmospheric particulate phase OCEC is formed. The collection, analysis and oxidation are designed as an integrated structure, and a heat preservation device 23 is designed in the whole road section to maximize the simplification of the gas path and avoid the loss of the measured substance in the transmission process. The gas path flow of the device is in the shape of "T". The sampling quartz tube body 1 and the gas outlet pipe 11 are in the shape of "positive 7", and the sampling quartz tube body 1 and the desorption pipe 10 are in the shape of "inverted 7". The light path transmission structure of the sampling quartz tube body 1 and the optical tube 12 is in the shape of "one". The diameter of the quartz tube body 1 is 20 mm, the length is 100 mm, and the wall thickness is 1.5 mm. The diameter of the gas outlet pipe 11 is 15 mm, the length is 60 mm, and the wall thickness is 1.5 mm. The diameter of the optical tube 12 is 20 mm, the length is 100 mm, and the wall thickness is 1.5 mm. The diameter of the desorption pipe 10 is 15 mm, the length is 50 mm, and the wall thickness is 1.5 mm. A oxidation furnace 8 with a diameter of 20 mm, a length of 60 mm and a wall thickness of 1.5 mm is connected behind the desorption pipe 10. The oxidation furnace 8 is internally provided with manganese dioxide, which is always kept at a constant high temperature of 850°C. The function of the oxidation furnace 8 is to oxidize the measured substance analyzed from the filter membrane 5 into carbon dioxide. An NDIR detector is connected behind the oxidation furnace 8 to measure the carbon dioxide content generated by the oxidation furnace 8. The heating of the filter membrane 5 and the desorption pipe 10 between the filter membrane and the oxidation furnace 8 during the analysis period is realized by electromagnetic heating. Specifically, the electromagnetic heating control panel 14 controls the electromagnetic induction coil 7 to generate alternating current, and the metal tungsten sheet 6 is a magnetically conductive element. When the alternating current passes through the electromagnetic induction coil 7, a magnetic field is generated. The metal tungsten sheet 6 placed in the magnetic field cuts the alternating magnetic force lines, thereby generating eddy current in the metal tungsten sheet 6. The eddy current causes the atoms in the metal tungsten sheet 6 to move at high speed in a random manner, and the atoms collide and rub against each other to generate heat. The heat generated by the eddy current of the metal tungsten sheet 6 is directly transmitted to the quartz filter membrane 5 and the desorption pipe 10, thereby realizing the synchronous heating of the quartz filter membrane 5 and the desorption pipe 10 during the analysis stage. During the EC measurement in the analysis stage, the filter membrane 5 is cooled by controlling the metal tungsten sheet 6 not to be heated by the electromagnetic heating control panel 14, i.e. the quartz filter membrane 5 and the desorption pipe 10 have no heat transmission, and the fan 22 is controlled to work continuously to ensure that the temperature of the quartz filter membrane 5 can be reduced from 850°C to 400°C within 30 s, and the subsequent EC stage of the substance analysis is performed. Since the oxidation furnace 6 is always at a constant high temperature, a heating wire or an electromagnetic heating device can be used to heat it to achieve high temperature of the oxidation furnace.

[0138] As shown in the above Figure 3 , on the basis of Figure 2 , the device Figure 2The collection, analysis and oxidation structure in the reduction furnace are combined, that is, an integrated device for collection, analysis, oxidation and reduction is formed, that is, a quartz tube with a diameter of 15 mm and a length of 50 mm is welded after the oxidation furnace, a reduction reagent is arranged in the quartz tube, and a reduction furnace 20 is formed. The carbon dioxide from the oxidation furnace 8 is further reduced to methane, and a FID detector 21 is used for measurement. Since the carbon dioxide material is not easy to adhere to the wall and be lost, special heat tracing is not required between the oxidation furnace and the reduction furnace. The reduction furnace 20 maintains a constant temperature during use, and has sufficient time to reach the temperature, so that a heating wire or an electromagnetic heating can be used for heating. The device can reduce the carbon dioxide oxidized to methane, and the concentration is measured by using the FID detector.

[0139] As shown in Figure 4 The laser calibration system includes a reflection laser calibration system and a transmission laser calibration system. A laser emitter 15 is arranged at the sample inlet. The laser emitted by the laser emitter 15 enters a transmission laser receiver 1 after passing through a quartz fiber filter film 5. At the same time, another part of the laser is reflected by the quartz fiber filter film 5, enters a reflection laser receiver 17 after passing through a light splitting sheet 16. The laser calibration system provides a basis for the cutting point of the OCEC by detecting the change of the reflected light and the transmission light intensity signal in the analysis stage.

[0140] In the present application, the cutting point of the OCEC can refer to the commonly used carbon component program temperature rising protocol cutting method recommended by the US EPA (US EPA).

[0141] The gas path structure is "T" shape, the sampling quartz tube body 1 and the outlet pipe 11 are "positive 7" shape, the sampling quartz tube body 1 and the desorption pipe 10 are "inverted 7" shape. The light path transmission structure of the sampling quartz tube body 1 and the optical tube 12 is "one" shape. The diameter of the sampling quartz tube body 1 is 20mm, the length is 100mm, the wall thickness is 1.5mm, the size of the outlet pipe 11 is diameter 15mm, length 60mm, wall thickness 1.5mm, the diameter of the optical tube 12 is 20mm, the length is 100mm, the wall thickness is 1.5mm, the diameter of the desorption pipe 10 is 15mm, the length is 50mm, the wall thickness is 1.5mm, and then a diameter of 20mm, a length of 60mm, and a wall thickness of 1.5mm of the oxidation furnace 8 is connected, the oxidation furnace 8 is built-in manganese dioxide, which is always kept at a constant high temperature of 850℃, and its function is to oxidize the measured substance analyzed by the filter membrane into carbon dioxide. The first electric three-way valve 28 is connected behind the oxidation furnace 8, by controlling the first electric three-way valve 28, the flow direction of the oxidized carbon dioxide can be selectively controlled according to the monitoring requirements, which can enter the NDIR detector 21 to directly measure the carbon dioxide content generated by the oxidation furnace 8. It can also be introduced into the reduction furnace 20 for further reduction, and the FID detector 22 is used for quantitative measurement of the substance. The temperature range and the implementation method are as follows: the temperature change range of the quartz filter membrane 5 is 100-950℃, the temperature of the oxidation furnace 8 is constant at 850℃ high temperature, and the temperature of the reduction furnace 20 is constant at 420℃. The desorption pipe 10 between the quartz filter membrane 5 and the oxidation furnace 8 is heated synchronously with the quartz filter membrane 5, and both of them are realized by electromagnetic heating and fan refrigeration to realize rapid temperature rise and fall; the quartz transmission pipe between the oxidation furnace 8 and the reduction furnace 20 does not need special heating, which is arranged in the heat preservation device 23, and the temperature in the heat preservation device 23 can avoid the loss of carbon dioxide cold spot; the oxidation furnace 8 and the reduction furnace 20 always keep constant high temperature during the operation of the instrument, so the temperature change frequency is low, therefore, the heating of the oxidation furnace 8 can use resistance wire 7 to wrap outside the wall for heating, or use electromagnetic heating to keep constant temperature. The advantages of this heating structure design are: from the filter membrane to the detector, they are all heated to a certain predetermined high temperature, and the temperature is adjusted by PID, the temperature accuracy is 0.2℃, the whole heating and heating setting avoids the wall loss of the measured substance, water vapor condensation and other phenomena, and ensures the accuracy of measurement. + 0.2℃, full road heating and heating setting avoids the wall loss of the measured substance, water vapor condensation and other phenomena, and ensures the accuracy of measurement.

[0142] For example, Figure 5As shown, the role of the heat preservation device 23 is to preserve the quartz filter membrane, desorption tube, oxidation furnace and reduction furnace which need to be raised to a higher temperature and maintained for a certain period of time, and to reduce heat dissipation. The present application adopts an electromagnetic heating temperature rising mode for the quartz filter membrane, and the oxidation furnace and the reduction furnace always maintain a certain high temperature during actual operation, without the need for rapid temperature rising and falling changes. Based on this, a non-uniform heat preservation device 23 is designed. No heat preservation coating is needed at the quartz filter membrane, and only electromagnetic heating and temperature control devices can meet the high temperature reaching and maintaining of the quartz filter membrane, and the fan 22 can ensure that the quartz filter membrane is reduced from 850℃ to 300℃ in 30s during the cooling stage. The heat preservation coating 24 of the remaining components is 5mm, which can ensure the constant high temperature maintenance of the oxidation furnace / reduction furnace.

[0143] The present application takes the high efficiency and accurate measurement of OCEC in atmospheric particulate matter as the starting point, and develops an OCEC measurement device and method based on electromagnetic direct heating. The high-efficiency electromagnetic direct heating mode ensures the rapid temperature rising requirement in the analysis stage, and ensures the uniform heating and precise thermal desorption of particulate matter collected at the filter membrane. In addition, the cold spots, heat preservation shells and filter membranes in the current structural device are optimized accordingly, which maximizes the reduction of material transmission loss and ensures the complete measurement and accurate monitoring of the collected OCEC.

[0144] The present application provides a method for detecting carbonaceous components in atmospheric particulate matter by using the above-mentioned device.

[0145] In some embodiments of the present application, the method comprises an enrichment step, a purging step, an OC analysis step, an EC analysis step and a calibration step; wherein the enrichment step: the sample to be detected is introduced into the enrichment and analysis device, so that the carbonaceous components are enriched in the enrichment and analysis device; the purging step: the device and its transmission route are purged with carrier gas to remove excess gas; the OC analysis step: in the absence of oxygen, the organic carbon material OC in the carbonaceous components adsorbed in the enrichment and analysis device is desorbed and enters the oxidation furnace with the carrier gas; the organic carbon material entering the oxidation furnace is oxidized to CO2; the oxidized CO2 enters the NDIR detector for measurement; the EC analysis step: in the presence of oxygen, the elemental carbon material EC in the carbonaceous components adsorbed in the enrichment and analysis device is desorbed and enters the oxidation furnace; the elemental carbon material entering the oxidation furnace is oxidized to CO2; the oxidized CO2 enters the NDIR detector for measurement; the calibration process: the helium / methane standard gas in the quantitative ring is oxidized to CO2 by the subsequent oxidation furnace, and the oxidized CO2 enters the NDIR detector for quantitative detection.

[0146] In some embodiments of the present application, the method comprises an enrichment step, a purge step, an OC analysis step, an EC analysis step, and a calibration step; wherein the enrichment step: the sample to be detected is introduced into the enrichment and analysis device, so that the carbonaceous components are enriched in the enrichment and analysis device; the purge step: the equipment and its transmission route are purged with carrier gas to remove excess gas; the OC analysis step: under an oxygen-free state, the organic carbon substance OC in the carbonaceous components adsorbed in the enrichment and analysis device is desorbed and enters the oxidation furnace with the carrier gas; the organic carbon substance entering the oxidation furnace is oxidized into CO2; the oxidized CO2 enters the reduction furnace and is reduced into CH4; the reduced CH4 enters the FID detector for measurement; the EC analysis step: under an oxygen-containing state, the elemental carbon substance EC in the carbonaceous components adsorbed in the enrichment and analysis device is desorbed and enters the oxidation furnace; the elemental carbon substance entering the oxidation furnace is oxidized into CO2; the oxidized CO2 enters the reduction furnace and is reduced into CH4; the reduced CH4 enters the FID detector for measurement; the calibration process: the helium / methane standard gas in the quantitative ring is introduced, which is converted into CO2 and CH4 by the subsequent oxidation furnace and reduction furnace, respectively; the reduced CH4 enters the FID detector for quantitative detection.

[0147] In some embodiments of the present application, the method comprises an enrichment step, a purge step, an enrichment step, a purge step, an OC analysis step, an EC analysis step, and a calibration step; wherein,

[0148] The enrichment step: the sample to be detected is introduced into the enrichment and analysis device, so that the carbonaceous components are enriched in the enrichment and analysis device;

[0149] The purge step: the equipment and its transmission route are purged with carrier gas to remove excess gas;

[0150] The OC analysis step: under an oxygen-free state, the organic carbon substance OC in the carbonaceous components adsorbed in the enrichment and analysis device is desorbed and enters the oxidation furnace with the carrier gas; the organic carbon substance entering the oxidation furnace is oxidized into CO2; the oxidized CO2 enters the reduction furnace and is reduced into CH4; the reduced CH4 enters the FID detector for measurement;

[0151] The EC analysis step: under an oxygen-containing state, the elemental carbon substance EC in the carbonaceous components adsorbed in the enrichment and analysis device is desorbed and enters the oxidation furnace; the elemental carbon substance entering the oxidation furnace is oxidized into CO2; the oxidized CO2 enters the reduction furnace and is reduced into CH4; the reduced CH4 enters the FID detector for measurement;

[0152] Calibration step: Helium / methane standard gas is introduced into the quantitative ring, which is converted into CO2 by the subsequent oxidation furnace. Part of the oxidized CO2 enters the NDIR detector for measurement; the other part enters the reduction furnace to be reduced into CH4, and the reduced CH4 enters the FID detector for measurement;

[0153] In some embodiments of the present application, the method comprises an enrichment step, a purge step, an enrichment step, a purge step, an OC analysis step, an EC analysis step, and a calibration step; specifically as follows:

[0154] Enrichment step: the computer interactive control system 34 controls the fan 22 to work, and the quartz filter membrane 5 is in a 30°C collection state. Through the suction action of the flow control system 13, the atmospheric sample passes through the cutting head 31, the erodent 32, the first electric three-way valve 30, the connector 29, the quartz filter membrane 5, the tungsten sheet 6, and the second electric three-way valve 35 in turn and is discharged through the flow control system 13, so as to trap the atmospheric particulate matter at the quartz fiber filter membrane 5 in the quartz sleeve device. The sampling time is generally 40 min, which can also be adjusted according to the atmospheric air quality. The desorption tube 10 is not heated in this stage, the heating device 9 of the oxidation furnace 8 is heated and maintained at 500°C, and is monitored in real time by the second temperature sensor 26. The reduction furnace 20 is heated to 420°C, and is monitored in real time by the third temperature sensor 27. The NDIR detector 21 and the FID detector 22 are in standby stage;

[0155] Purge step: after the enrichment is completed, the quartz filter membrane 5 is still kept at a low temperature of 30°C. At this time, helium gas enters the quartz sleeve 2 after passing through the gas supply and pressure control system 33 and the second electric three-way valve 30, and is blown out through the third electric three-way valve 35 and the flow control system 13, so as to blow out the impurity gas remaining in the tube and keep the system in an oxygen-free environment. In this stage, the oxidation furnace 8 is controlled to start heating and maintain at 850°C, and is monitored in real time by the second temperature sensor 26. The temperature of the reduction furnace 20 is still kept at 420°C, and is monitored in real time by the third temperature sensor 27. The NDIR detector 21 and the FID detector 22 are in standby stage;

[0156] OC analysis step: after the purge is completed, the computer interactive control system 34 controls the electromagnetic heating module to start working, that is, the quartz filter membrane 5 starts the program temperature rising, the OC enriched in the quartz filter membrane 5 is gradually pyrolyzed in the oxygen-free environment, one way of helium gas passes through the gas supply and pressure control system 33, the third electric three-way valve 35, enters the quartz sleeve 3, and the other way of helium gas passes through the gas supply and pressure control system 33, the second electric three-way valve 30, enters the quartz sleeve 2, the two ways of helium gas are blown from the upper and lower of the quartz filter membrane 5, the substances resolved from the quartz filter membrane 5 are taken into the oxidation furnace 8 through the desorption tube 10 and oxidized into CO2, at this time, the first electric three-way valve 28 can be controlled to turn, that is, the oxidized CO2 can be taken into the NDIR detector 21 for quantitative detection, or the first electric three-way valve 28 can be controlled to communicate with the reduction furnace 20, the CO2 is reduced into CH4 and then enters the FID detector 22 for measurement and detection. In the OC resolution stage, part of the OC is carbonized into EC at high temperature. At this time, the laser emitting end 15 always emits a light source to irradiate to the surface of the quartz filter membrane 5, and the reflected light receiver 17 and the transmitted light receiver 18 monitor the light intensity change reflected from the quartz filter membrane 5 and transmitted in real time;

[0157] EC analysis step: after the OC measurement is completed, the computer interactive control system 34 controls the metal tungsten sheet 6 at the quartz filter membrane and the desorption tube to stop temperature rising, and controls the fan 22 to start, that is, the temperature at the quartz filter membrane is reduced to the starting temperature of the EC analysis. At this time, one way of He / O2 mixed gas passes through the gas supply and pressure control system 33, the second electric three-way valve 30, enters the quartz sleeve 3, and the other way of He / O2 mixed gas passes through the gas supply and pressure control system 33, the third electric three-way valve 35, enters the quartz sleeve 3; the computer interactive control system 34 controls the fan 22 to stop working, and controls the metal tungsten sheet 6 at the quartz filter membrane and the desorption tube to work, the quartz filter membrane continues the program temperature rising, the EC is oxidized into OC and escapes; the two ways of He / O2 mixed gas entering the quartz sleeve take the measured substances resolved from the quartz filter membrane into the desorption tube 10 and the oxidation furnace 8 at high temperature and are converted into CO2; at this time, the first electric three-way valve 28 can be controlled to turn, that is, the oxidized CO2 can be taken into the NDIR detector 21 for quantitative detection, or the first electric three-way valve 28 can be controlled to communicate with the reduction furnace 20, the CO2 is reduced into CH4 and then enters the FID detector 22 for measurement. At this time, the laser emitting end 15 always emits a light source to irradiate to the surface of the quartz filter membrane 5, and the reflected light receiver 17 and the transmitted light receiver 18 monitor the light intensity change reflected from the quartz filter membrane 5 and transmitted in real time, and judge the amount of OC carbonized into EC according to the change of the light source;

[0158] Cooling standby step: after the OCEC analysis measurement is completed, the computer interactive control system 34 controls the metal tungsten sheet 6 at the quartz filter membrane and the desorption pipe to stop heating, the fan 22 is opened and the filter membrane is cooled; the temperature of the oxidation furnace 8 is kept at 500 DEG C, the temperature of the reduction furnace 20 is kept at 420 DEG C, the instrument enters the standby process, and waits for the next sampling analysis;

[0159] So far, a complete atmospheric particulate OCEC carbon component online measurement cycle program is completed. The time sequence control of the whole system and components is realized by the computer interactive control system 34, and the five modes can be automatically cycled.

[0160] The present application is based on the current high efficiency analysis and measurement precision and integrity of atmospheric particulate OCEC carbon component as the starting point, and develops a kind of atmospheric particulate carbon component analysis and monitoring device and system based on high efficiency electromagnetic heating. The electromagnetic heating based on magnetic conductive element greatly increases the heating speed and efficiency of the sampling filter membrane, the face-to-face contact heating ensures the uniform heating of the filter membrane surface, improves the analysis efficiency and measurement accuracy of atmospheric OCEC, and further ensures that the collected substances enter the subsequent measurement device without loss. A heat tracing device is designed in the whole section after analysis, which is synchronized with the collection and analysis, greatly reducing the wall surface cold spot loss of organic matter after analysis. While ensuring the high temperature of the filter membrane and the oxidation and reduction components, a non-uniform heat preservation device is designed to ensure the rapid cooling requirement of the filter membrane. In order to ensure the integrity of the filter membrane replacement, a quartz sleeve nested in the quartz main pipe is designed, and the quartz filter membrane and the magnetic conductive element are placed in the quartz sleeve. The design structure only needs to take out the quartz sleeve when replacing the filter membrane, without using tweezers to blindly take out the filter membrane, avoiding the damage of the filter membrane surface caused by the use of tweezers to hook out the filter membrane during the replacement of the filter membrane at present. The taking out mode preserves the integrity and secondary analysis of the filter membrane surface material information.

[0161] In the present application, the filter membrane heating method is new, the heating efficiency is high, the electromagnetic heating device has a long high temperature service life, and it is a heating method suitable for filter membranes working at high temperature for a long time. The electromagnetic heating based on magnetic conductive element is used to heat the filter membrane in face-to-face mode, which ensures the heating rate and the uniformity of the filter membrane heating, improves the analysis efficiency and measurement accuracy of atmospheric particulate chemical components, and further specifically designs a non-uniform heat preservation device to meet the rapid cooling requirement of the filter membrane during the OC to EC analysis conversion. The combination of electromagnetic rapid heating and low energy consumption small volume fan refrigeration can meet the rapid cooling requirement of the filter membrane during the OC to EC analysis conversion, and also can ensure the rapid heating requirement of the filter membrane during the analysis and heating period.

[0162] In the present application, the device is designed with integrated structure, the gas path is simplified, the structure is compact, various detectors can be integrated, and the portability is strong. In addition, the device is combined with a quartz fiber filter membrane and a tungsten sheet to form a set of enrichment and analysis integrated device module which can realize non-destructive replacement of the filter membrane. A desorption side pipe is designed on the side end of the main pipe, the oxidation reagent is placed in the side pipe, and a heating device is arranged between the two, thereby forming an enrichment, analysis and oxidation integrated device. Furthermore, if the oxidized substance needs to be reduced and measured by FID, a reduction furnace is arranged on the side end of the oxidation component, and the transmission pipeline of carbon dioxide between the two does not need to be heated, thereby forming an enrichment, analysis, oxidation and reduction integrated device. The entire device meets the performance requirements, and the gas path is simplified as much as possible according to the measurement needs, the device structure is small and compact, and the layout is compact.

[0163] In the present application, various optional light cutting and substance measurement methods are provided to realize accurate segmentation and measurement of atmospheric OCEC. Not only two freely selectable measurement methods of CO2-NDIR and / or CH4-FID are provided, but also light transmission and / or light reflection OCEC cutting methods are provided to maximize the accurate cutting and measurement of OCEC in atmospheric particulate matter.

[0164] Embodiment 1

[0165] As Figure 4As shown, the laser correction system includes a reflective laser correction system and a transmission laser correction system, a laser emitter 15 is arranged at the sample inlet, the emitted laser passes through the quartz fiber filter film 5 and enters the transmission laser receiver 1; At the same time, another part of the laser is reflected by the quartz fiber filter film 5, passes through the light splitting sheet 16 and enters the reflective laser receiver 17. The collection, analysis and oxidation structure is combined with the reduction furnace, that is, an integrated collection, analysis, oxidation and reduction device is formed, the gas path structure is "T" shape, the sampling quartz tube body 1 and the gas outlet pipe 11 are "positive 7" shape, the sampling quartz tube body 1 and the desorption pipe 10 are "inverted 7" shape. The light path transmission structure of the sampling quartz tube body 1 and the optical tube 12 is "one" shape. The diameter of the sampling quartz tube body 1 is 20mm, the length is 100mm, and the wall thickness is 1.5mm. The size of the gas outlet pipe 11 is diameter 15mm, length 60mm, and wall thickness 1.5mm. The diameter of the optical tube 12 is 20mm, the length is 100mm, and the wall thickness is 1.5mm. The diameter of the desorption pipe 10 is 15mm, the length is 50mm, and the wall thickness is 1.5mm. Then a oxidation furnace 8 with a diameter of 20mm, a length of 60mm and a wall thickness of 1.5mm is connected, the oxidation furnace 8 is internally provided with manganese dioxide, which is always kept at a constant high temperature of 850℃, and its function is to oxidize the measured substance analyzed by the filter film into carbon dioxide. The oxidation furnace 8 is connected with a first electric three-way valve 28, by controlling the first electric three-way valve 28, the flow direction of the oxidized carbon dioxide can be selectively controlled according to the monitoring requirement, which can enter the NDIR detector 21 to directly measure the carbon dioxide content generated by the oxidation furnace 8. It can also be introduced into the reduction furnace 20 for further reduction, and the FID detector 22 is used for quantitative measurement of the substance. The temperature change range of the quartz filter film 5 is 100-950℃, the temperature of the oxidation furnace 8 is constant at 850℃, and the temperature of the reduction furnace 20 is constant at 420℃. The desorption pipe 10 between the quartz filter film 5 and the oxidation furnace 8 is heated synchronously with the quartz filter film 5, and both use electromagnetic heating and fan cooling to realize rapid temperature rise and fall; The quartz transmission pipe between the oxidation furnace 8 and the reduction furnace 20 does not need special heating, it is arranged in the heat preservation device 23, and the temperature in the heat preservation device 23 can avoid the loss of carbon dioxide; The oxidation furnace 8 and the reduction furnace 20 always maintain a constant high temperature during the operation of the instrument, so the temperature change frequency is low, the heating of the oxidation furnace 8 can be realized by winding the resistance wire 7 outside the wall for temperature rise, or using electromagnetic heating to maintain constant temperature. From the filter film to the detector, they are all heated to a certain predetermined high temperature, and the temperature is adjusted by PID, the temperature accuracy is + 0.2℃, the whole heating and heating setting avoids the wall loss of the measured substance, water vapor condensation and other phenomena, and ensures the accuracy of measurement.

[0166] The heating rate and high temperature control of atmospheric particulate carbon components are key factors for accurate analysis and measurement. At present, the traditional resistance filter membrane heating method has low efficiency and slow heating. The high heating temperature causes large thermal hysteresis of the resistance heating method, which is not easy to control the temperature accurately, cannot guarantee the uniformity of the filter membrane surface high temperature in a short time, and the resistance wire is easy to burn out due to high temperature aging, and the service life is short, which is not suitable for application in the system device which keeps at high temperature for a long time. Based on this, the device of the application is different from the current heating method, adopts efficient and reliable electromagnetic heating method, can realize the temperature of the sampling filter membrane surface from 30 DEG C to 1000 DEG C in 10s, the temperature control precision is +0.2 DEG C, greatly improves the heating rate and analysis efficiency; and combined with low energy consumption fan refrigeration, non-uniform heat preservation device and temperature control device, the rapid change of high and low temperature of the filter membrane surface can be met. The current market particulate carbon component heating and analysis method is innovated, and the whole road heat tracing of gas transmission is optimized, which can improve the sensitivity and accuracy of particulate carbon component measurement. The whole device system has compact structure, low energy consumption and low cost, and has great application prospect in high temperature analysis and quantitative precision of particulate carbon component.

Claims

1. An integrated enrichment and resolution device for the detection of carbonaceous components in atmospheric particulate matter of organic carbon (OC) and elemental carbon (EC), characterized by, The device comprises: a tube body provided with a sleeve inside and communicated with a desorption tube and an outlet tube respectively, the tube body is a quartz tube body, the quartz tube body has a diameter of 20 mm, a length of 100 mm and a wall thickness of 1.5 mm; the sleeve has a sample inlet and a sample outlet at two sides respectively, a filter membrane and a heating component are arranged at the sample outlet of the sleeve in the sample inlet direction of the particulate matter, the heating component can heat the filter membrane, the sleeve is a quartz sleeve, the quartz sleeve has a diameter of 16 mm, a length of 70 mm and a wall thickness of 1.5 mm; the desorption tube is communicated with the tube body downstream or upstream of the filter membrane in the sample inlet direction of the particulate matter, the desorption tube has a diameter of 15 mm, a length of 50 mm and a wall thickness of 1.5 mm; the outlet tube is communicated with the tube body downstream of the filter membrane in the sample inlet direction of the particulate matter, the outlet tube has a diameter of 15 mm, a length of 60 mm and a wall thickness of 1.5 mm; the device further comprises a synchronous heating device which can synchronously heat the heating component arranged in the sleeve and the heating component outside the desorption tube; the synchronous heating device comprises an electromagnetic heating control board, an induction coil and a heating element, the electromagnetic heating control board is connected with the induction coil, and the induction coil is arranged outside the tube body and the desorption tube to realize the common heating requirement of the heating component wound around the desorption tube and the heating component placed downstream of the filter membrane; the heating component is a magnetic conductive film piece, which is a metal tungsten piece, a metal molybdenum piece, an iron-silicon piece or an iron-nickel piece; the tube body further comprises a support structure arranged downstream of the sleeve in the sample inlet direction of the particulate matter to fix the position of the filter membrane and the heating component downstream of the filter membrane, a quartz support structure with a length of 5 mm is welded at each end of the quartz tube body, and the distance between the quartz support structure and the sample inlet is 70 mm; one side of the desorption tube is welded to the side surface of the tube body, and the other side extends radially outward along the tube body; the outlet tube extends outward from the other side surface of the tube body opposite to the side surface where the desorption tube is welded; The synchronous heating device can be heated to 1000℃ within 10s, and the temperature control precision of the synchronous heating device is + 0.2℃.

2. The device according to claim 1, further comprising an inner lining arranged inside the sleeve between the sample inlet and the filter membrane to block the movement of the filter membrane in the tube body.

3. The device according to claim 1, wherein the filter membrane is a quartz fiber filter membrane.

4. The device according to claim 1, further comprising a first temperature sensor for detecting the temperature of the filter membrane.

5. The device according to claim 1, wherein the bottom of the sample outlet of the sleeve is an upper and lower annular structure with a hollow middle part to realize the transmission of the gas path and the position fixing of the filter membrane and the heating component in the sleeve.

6. The device according to claim 1, wherein the heating component in the sleeve is an annular structure with a hollow middle part.

7. The device according to claim 4, wherein ​ ​ ​ ​ ​ The first temperature sensor is a first patch temperature sensor, which is located outside the tube body close to the filter membrane and away from the side of the desorption tube.

8. The device of claim 1, wherein, The downstream of the filter membrane is in communication with the tube body.

9. A device for detecting carbonaceous components in atmospheric particulate matter, wherein, The device for detecting carbonaceous components in atmospheric particulate matter according to any one of claims 1-8.

10. The device of claim 9, wherein, The desorption tube is connected to an oxidation furnace on the side opposite to the side in communication with the tube body, and the oxidation furnace is externally wound with a resistance wire, wherein the resistance wire can heat the oxidation furnace.

11. The device of claim 10, wherein, The device further comprises an NDIR detector connected to the oxidation furnace for detecting the gas sample treated by the oxidation furnace.

12. The device of claim 10, wherein, The device further comprises a reduction furnace connected to the side opposite to the side in communication with the oxidation furnace.

13. The device of claim 12, wherein, The device further comprises an FID detector connected to the reduction furnace for detecting the gas sample treated by the reduction furnace.

14. The device of claim 10, wherein, The device further comprises a reduction furnace connected to the oxidation furnace through a tee valve.

15. The device of claim 14, wherein, The device further comprises an NDIR detector connected to the oxidation furnace for detecting the gas sample treated by the oxidation furnace and an FID detector connected to the reduction furnace for detecting the gas sample treated by the reduction furnace.

16. The device of claim 10, wherein, The device further comprises a second temperature sensor for detecting the temperature of the oxidation furnace.

17. The device of claim 12 or 14, wherein, The device further comprises a third temperature sensor for detecting the temperature of the reduction furnace.

18. The device of claim 9, wherein, The outlet tube is connected to a flow controller on the side opposite to the side in communication with the tube body, and the flow controller is used to accurately control the sampling flow of the device.

19. The device of claim 9, wherein, The side of the tube body opposite to the sampling inlet is provided with a first detector, and the side of the tube body outside and adjacent to the sampling inlet is provided with a light source, a light splitting sheet, and a second detector for optical detection.

20. The device of claim 12 or 14, wherein, The device further comprises a heat preservation device arranged outside the filter membrane, the heating component, the support structure, the desorption tube, the oxidation furnace, and the reduction furnace.

21. The device of claim 20, wherein, The second temperature sensor is a second patch temperature sensor, which is located outside the oxidation furnace.

22. The apparatus of claim 17, wherein, The third temperature sensor is a third patch temperature sensor, which is located outside the reduction furnace.

23. A method for detecting carbonaceous components in atmospheric particulate matter using the device of any one of claims 1-8 or the apparatus of any one of claims 9-22.

24. The method of claim 23, wherein, Comprising The enrichment step, the purging step, the OC analysis step, the EC analysis step, and the calibration step; wherein, The enrichment step: introducing the sample to be detected into the enrichment and analysis device, so that the carbonaceous components are enriched in the enrichment and analysis device; The purging step: purging the apparatus and its transmission route with carrier gas to remove excess gas; The OC analysis step: in the absence of oxygen, the organic carbon material OC in the carbonaceous components adsorbed in the enrichment and analysis device is desorbed and enters the oxidation furnace with the carrier gas; the organic carbon material in the oxidation furnace is oxidized to CO2; the oxidized CO2 enters the NDIR detector for measurement; The EC analysis step: in the presence of oxygen, the elemental carbon material EC in the carbonaceous components adsorbed in the enrichment and analysis device is desorbed and enters the oxidation furnace; the elemental carbon material in the oxidation furnace is oxidized to CO2; the oxidized CO2 enters the NDIR detector for measurement; The calibration process: helium / methane standard gas is introduced into the quantitative ring, which is oxidized to CO2 by the subsequent oxidation furnace, and the oxidized CO2 enters the NDIR detector for quantitative detection.

25. The method of claim 23, wherein, Comprising The enrichment step, the purging step, the OC analysis step, the EC analysis step, and the calibration step; wherein, The enrichment step: introducing the sample to be detected into the enrichment and analysis device, so that the carbonaceous components are enriched in the enrichment and analysis device; The purging step: purging the apparatus and its transmission route with carrier gas to remove excess gas; The OC analysis step: in the absence of oxygen, the organic carbon material OC in the carbonaceous components adsorbed in the enrichment and analysis device is desorbed and enters the oxidation furnace with the carrier gas; the organic carbon material in the oxidation furnace is oxidized to CO2; the oxidized CO2 enters the reduction furnace and is reduced to CH4; the reduced CH4 enters the FID detector for measurement; The EC analysis step: in the presence of oxygen, the elemental carbon material EC in the carbonaceous components adsorbed in the enrichment and analysis device is desorbed and enters the oxidation furnace; the elemental carbon material in the oxidation furnace is oxidized to CO2; the oxidized CO2 enters the reduction furnace and is reduced to CH4; the reduced CH4 enters the FID detector for measurement; The calibration process: helium / methane standard gas is introduced into the quantitative ring, which is converted to CO2 and CH4 by the subsequent oxidation furnace and reduction furnace, respectively; the reduced CH4 enters the FID detector for quantitative detection.

26. The method of claim 23, wherein, Comprising The enrichment step, the purging step, the enrichment step, the purging step, the OC analysis step, the EC analysis step, and the calibration step; wherein, The enrichment step: introducing the sample to be detected into the enrichment and analysis device, so that the carbonaceous components are enriched in the enrichment and analysis device; Purge step: Purge the equipment and its transmission line with carrier gas to remove excess gas; OC analysis step: Under the condition of no oxygen, the organic carbon material OC adsorbed in the carbonaceous component in the enrichment and resolution device is desorbed and enters the oxidation furnace with the carrier gas; the organic carbon material entering the oxidation furnace is oxidized into CO2; the oxidized CO2 is partly directly measured by the NDIR detector; the other part enters the reduction furnace and is reduced into CH4, and the reduced CH4 enters the FID detector for measurement; EC analysis step: Under the condition of oxygen, the elemental carbon material EC adsorbed in the carbonaceous component in the enrichment and resolution device is desorbed and enters the oxidation furnace; the elemental carbon material entering the oxidation furnace is oxidized into CO2; the oxidized CO2 is partly directly measured by the NDIR detector; the other part enters the reduction furnace and is reduced into CH4, and the reduced CH4 enters the FID detector for measurement; Calibration process: The helium / methane standard gas in the quantitative ring is oxidized into CO2 by the subsequent oxidation furnace, and the oxidized CO2 is partly directly measured by the NDIR detector; the other part enters the reduction furnace and is reduced into CH4, and the reduced CH4 enters the FID detector for quantitative detection.

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