CN115979782A - Enrichment analysis device, detection equipment and detection method for measuring chemical components and concentration of atmospheric particulate matters - Google Patents

Enrichment analysis device, detection equipment and detection method for measuring chemical components and concentration of atmospheric particulate matters Download PDF

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CN115979782A
CN115979782A CN202211683200.2A CN202211683200A CN115979782A CN 115979782 A CN115979782 A CN 115979782A CN 202211683200 A CN202211683200 A CN 202211683200A CN 115979782 A CN115979782 A CN 115979782A
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tube
temperature
enrichment
filter membrane
analysis
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杜玥萱
曾立民
胡素娟
敖小强
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Beijing SDL Technology Co Ltd
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Beijing SDL Technology Co Ltd
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Abstract

The application provides an enrichment analytical equipment for atmospheric particulates chemical composition and concentration measurement thereof includes: a tube body, a desorption tube; the device comprises a pipe body, wherein a sample inlet and a gas outlet are respectively arranged at two sides of the pipe body; in the sampling direction of the particles, a filter membrane, a magnetic conduction membrane and a support structure are sequentially arranged in the tube body; a desorption tube having one side welded to a side surface of the tube body and the other side extending radially outward along the tube body; in the sampling direction of particulate matter, bearing structure the analysis pipe sets up on the different positions of body. The electromagnetic heating mode can realize the surface-to-surface contact temperature rise of the heating element and the quartz filter membrane, and ensures the high-efficiency analysis efficiency in the thermal analysis stage. The whole device is compact in structure and small in size, only one analysis branch pipe is adopted at the side end of the quartz main pipe to perform subsequent processing analysis on a thermal analysis sample, and the dead volume is small.

Description

Enrichment analysis device, detection equipment and detection method for measuring chemical components and concentration of atmospheric particulate matters
Technical Field
The application belongs to the technical field of environmental monitoring, and relates to an enrichment analysis device, detection equipment and a detection method for measuring chemical components and concentration of atmospheric particulates.
Background
In recent years, pollution of atmospheric fine particulate matters (PM 2.5) is still the focus of air improvement in China. The fine particles not only can influence atmospheric visibility to generate direct climate effect by absorbing or scattering sunlight, but also can generate indirect climate effect on formation of cloud condensation nuclei, precipitation and the like, and can influence human health. The chemical composition of the atmospheric particulates is complex and mainly comprises carbonaceous components, organic substances, water-soluble ions, trace element components and the like. Atmospheric carbon components (mainly OC, EC) as important constituents of atmospheric PM2.5 account for 10-70% of PM2.5 mass concentration, which has important influence on atmospheric visibility. The organic matter is used as the substance type of the atmospheric particulate matter molecule level, and the measurement result has important significance for the refined control of the particulate matter.
At present, pretreatment methods for OCEC and organic matters in atmospheric particulates are approximately similar, and most of the pretreatment methods are based on a substance filter membrane collection-thermal decomposition method for enrichment. The off-line acquisition-laboratory decomposition analysis process is complex, the time resolution is low, and the atmospheric composition change cannot be reflected in real time. The on-line measurement method mainly has the advantages of high time resolution, automation, labor and time cost saving, real-time reflection of atmospheric components and the like. The measurement devices for particulate matter vary greatly for a particular monitoring device. The online enrichment device for the granular organic matters is generally made of stainless steel, but the organic matters are too viscous and are easily attached to the inner wall, so that incomplete measurement is caused, and therefore special internal passivation treatment is generally needed, and the operation undoubtedly increases the cost of equipment to a great extent and prolongs the equipment integration time. OCEC gathers analytic equipment on line and generally adopts the quartz material, and this material inner wall active point position is low, generally need not to passivate when using, but generally adopts the heater strip of winding at the quartz capsule outer wall, heating coil or heating rod module to carry out the high temperature analysis to the filter membrane of built-in at the quartz capsule when the high temperature is analytic, and this resistance-type heating and filter membrane intensification mode based on second grade heat-conduction are slower, thereby easily lead to the inhomogeneous accurate analysis and the monitoring that can't guarantee OCEC of filter membrane surface heating.
The existing device mainly has the following problems: for example, the modularization is low, the commonality is low, and is with high costs, and each big producer respectively has one set of enrichment analytical equipment to the atmospheric particulates collection analysis at present, especially still need passivation to the enrichment module of organic matter, has increased the cost. The thermal analysis stage intensifies slowly, and analysis inefficiency adopts heater strip winding outer of tubes wall or self-made heating module geminate transistors to heat to the pyrolysis analysis of filter membrane at present, and this heating method is based on traditional resistance-type heating and second grade heat-conduction heaies up the filter membrane, and the heat that the heater strip produced passes through outer of tubes wall and takes it to the filter membrane again promptly, and this heating method is inefficient, and it is slow to generate heat, and the loss is big, and can't guarantee the even heating to the filter membrane surface. When the filter membrane is used in an atmospheric particle chemical component monitoring system, particularly sulfate and other substances which can be thermally resolved only at 600 ℃ and the OCEC carbon component substances are resolved by heating the filter membrane to 850 ℃, the heating mode is low in heating efficiency, the resistance heating mode is large in thermal lag due to overhigh heating temperature, accurate temperature control is difficult, insufficient resolution and incomplete measurement can be caused, the resistance wire is easy to burn off due to high-temperature aging, and the service life is short.
Disclosure of Invention
This application is optimized in the aspect of the analytic equipment of particulate matter collection, has designed the analytic integrated device of particulate matter enrichment of a quartz material. The collection part based on quartz materials does not need to carry out passivation pretreatment on the interior of the collection part, reduces the preparation time and the instrument cost in the early stage, and in addition, the electromagnetic direct heating mode is adopted to carry out rapid heating on the filter membrane after sampling, thereby ensuring the effective analysis of particle substances. The whole device has the advantages of higher module integration level, lower cost, compact structure and higher applicability, can be used as an enrichment analysis module for an atmospheric particulate organic matter monitoring system, and can also be used as an acquisition analysis furnace for atmospheric OCEC monitoring equipment. In addition, the device can be applied to an atmospheric particle chemical component measurement network as a public acquisition module, namely, an acquisition device is used for enriching, analyzing and subsequently analyzing atmospheric particle chemical substances, and monitoring and analyzing the atmospheric particle chemical characteristics under the same acquisition condition are important ways for knowing atmospheric particles, understanding the formation and aging mechanism of pollutants and tracing the sources of the pollutants.
The technical scheme of the application is as follows:
1. an enrichment and desorption device for measuring chemical components and concentration of atmospheric particulates comprises:
a tube body, a desorption tube;
the device comprises a pipe body, wherein a sample inlet and a gas outlet are respectively arranged at two sides of the pipe body;
in the sampling direction of the particles, a filter membrane, a magnetic conduction membrane and a support structure are sequentially arranged in the tube body;
a desorption tube having one side welded to a side surface of the tube body and the other side extending radially outward along the tube body;
in the sampling direction of particulate matter, the supporting structure the analysis tube is arranged at different positions of the tube body.
2. The enrichment resolving device according to item 1,
the enrichment analysis device further comprises an electromagnetic heating control panel which is connected with the induction coil, and the induction coil is arranged on the outer side of the tube body and wound on the outer portion of the tube body corresponding to the magnetic conduction membrane and the filter membrane.
3. The enrichment resolving device according to item 1,
the support structure is arranged at the downstream of the desorption tube in the sampling direction of the particles;
preferably, the ratio of the distance between the support structure and the resolving tube to the total length of the tube body is (0.3-0.7): 3;
further preferably, the ratio of the distance between the analysis tube and the sample inlet to the total length of the tube body is (0.5-1.3): 3.
4. The enrichment resolving device according to item 1,
the support structure is arranged at the upstream of the desorption tube in the sampling direction of the particles;
preferably, the ratio of the distance between the support structure and the resolving tube to the total length of the tube body is (0.3-0.7): 3;
further preferably, the ratio of the distance between the analysis tube and the sample inlet to the total length of the tube body is (1-1.7): 3.
5. The enrichment resolving device according to item 1,
the enrichment analysis device further comprises a lining, wherein the lining is arranged inside the tube body and located between the sample inlet and the filter membrane.
6. The enrichment resolving device according to item 1,
the enrichment analysis device further comprises a patch temperature sensor, wherein the patch temperature sensor is positioned outside the tube body and close to the filter membrane, and is back to one side of the tube body with the analysis tube.
7. The enrichment resolving device according to item 1,
two sides of the pipe body are sealed by using first O rings, preferably, the first O rings are made of fluororubber or polytetrafluoroethylene;
the analysis tube is sealed by a second O-ring, preferably made of polyimide.
8. The enrichment resolving device according to item 1,
the filter membrane is a quartz filter membrane.
9. The enrichment resolving device according to item 1,
the magnetic conductive membrane is a metal tungsten sheet, a metal molybdenum sheet, an iron silicon sheet or an iron nickel sheet.
10. A detection device for measuring the chemical components and concentration of atmospheric particulates comprises the enrichment analysis device and a shunt component, wherein the enrichment analysis device is provided with any one of items 1 to 9.
11. The detection apparatus of item 10, further comprising:
means for detecting organic compounds in the C8-C40 volatility range in the atmospheric particulates and/or means for detecting carbonaceous components in the particulates and/or means for detecting ionic components in the particulates;
preferably, the first and second liquid crystal display panels are,
the device for detecting the organic matters in the C8-C40 volatility range in the atmospheric particulates comprises an organic matter focusing component and a GCMS detector;
the device for detecting the carbonaceous components in the atmospheric particulates comprises an OCEC oxidation furnace, an OCEC reduction furnace and an FID detector;
the device for detecting the ion components in the atmospheric particulates comprises a capillary sample inlet pipe and a mass spectrometer;
the flow dividing component is connected with a resolving pipe on the enrichment resolving device;
the shunt part is respectively connected with the organic matter focusing part, the OCEC oxidation furnace and the capillary sampling tube;
the organic matter focusing component is connected with the GCMS detector;
the OCEC oxidation furnace is connected with the OCEC reduction furnace, and the OCEC reduction furnace is connected with the FID detector.
The capillary sampling pipe is connected with the mass spectrometer.
12. The detection device according to the above item 10,
the organic matter focusing component comprises a high-temperature and low-temperature component;
the high-low temperature component comprises a high-temperature module, a low-temperature module and a high-low temperature switching module.
13. The detection apparatus according to item 12, wherein,
the high-temperature module comprises an adsorption tube and a resistance wire wound outside the adsorption tube, and a Tenax adsorbent is filled inside the adsorption tube;
preferably, a layer of insulating sleeve is further arranged between the adsorption tube and the resistance wire, and the insulating sleeve is wrapped on the periphery of the adsorption tube;
further preferably, the high-temperature module further comprises a protection unit, and the protection unit is wrapped on the periphery of the resistance wire;
more preferably, the high temperature module further includes a temperature sensor, the temperature sensor is disposed outside the adsorption pipe body and located between the insulation sleeve and the adsorption pipe.
14. The detection apparatus according to item 12, wherein,
the low-temperature module comprises a refrigerating piece and a metal block, the metal block is composed of two symmetrical sub-metal blocks which are provided with semicircular grooves at the center and can be opened and closed, and the adsorption tube can be attached to the groove formed by the two symmetrical sub-metal blocks;
preferably, the first and second electrodes are formed of a metal,
the cold end of the refrigeration sheet is tightly attached to the metal block.
15. The detection apparatus according to item 12, wherein,
the high-low temperature switching module comprises a pneumatic driving device, and the pneumatic driving device controls the low-temperature metal block to open and close so as to realize the switching of the adsorption tube between a high-temperature mode and a low-temperature mode;
preferably, the first and second electrodes are formed of a metal,
when the pneumatic driving device is filled with carrier gas, the two symmetrical sub metal blocks move relatively, so that an interval exists between the two symmetrical sub metal blocks and the adsorption tube, the heating module is controlled to work, and the heating module is in a high-temperature mode;
when the pneumatic device is not communicated with carrier gas, the two symmetrical sub-metal blocks move oppositely, so that the two symmetrical sub-metal blocks are attached to the adsorption tube, the heating module is controlled to stop working, and the pneumatic device is in a low-temperature mode.
16. An enrichment analysis device according to any one of items 1 to 9 or a detection device according to any one of items 10 to 15, which is used for an online measurement and analysis method for chemical components and concentrations of atmospheric particulates.
17. The method of item 16, comprising
Sampling, purging, analyzing and shunting, and measuring; wherein the content of the first and second substances,
a sampling step: introducing a sample to be detected into an enrichment and desorption device to enrich particulate matters in the enrichment and desorption device;
a purging step: carrying out carrier gas purging on the enrichment analysis device and a transmission line thereof or the detection equipment and a transmission line thereof to remove redundant gas;
analyzing and shunting steps: the particle matter adsorbed in the enrichment desorption device is subjected to high-temperature thermal desorption and is divided into one, two or three air flows, wherein the divided air flow enters an organic matter focusing component for secondary capture and/or enters an OCEC oxidizing furnace, and/or the divided air flow enters a capillary sampling pipe;
a measurement step: thermally analyzing the granular organic matters secondarily enriched in the organic matter focusing component again after shunting, and separating and measuring the granular organic matters in a GCMS detector; and/or the sample entering the OCEC oxidizing furnace after being divided is oxidized into CO 2 Then CO 2 Enters an OCEC reducing furnace to be reduced into CH 4 After, CH 4 Entering an FID detector for quantitative detection; and/or the particles after the shunting enter a mass spectrometer through a capillary sampling tube to directly detect the substance characteristic ion signals.
Compared with the prior art, the beneficial effect of this application is:
(1) This application is through the sampling enrichment characteristics of studying atmospheric particulates chemical composition, develops an atmospheric particulates enrichment analytical equipment with universality, and the device is with low costs, and the integrated level is high, and the commonality is strong. The atmospheric particulate chemical substance collection and enrichment device can be applied to an online monitoring system, the atmospheric particulate is collected and enriched, the requirements of subsequent different temperature rise programs for rapid analysis are met, the trapping and efficient analysis of atmospheric particulate chemical substance components are achieved, and basic data are provided for the analysis of atmospheric particulate sources. In addition, the device can also be applied to an off-line collection system, and can directly carry out laboratory analysis on collected samples without carrying out separate film preservation and additional thermal analysis operation.
(2) The enrichment and desorption device takes the quartz tube as a main frame, passivation pretreatment on the inner wall is not needed, and time and equipment cost are saved. The device integrates a sandwich structure of a quartz fiber filter membrane-metal tungsten sheet-quartz supporting structure, is nested into a quartz pipeline, and adopts a built-in quartz lining tube to ensure the stability of the quartz membrane under long-time large-flow sampling. The electromagnetic heating mode can realize the surface-to-surface contact temperature rise of the heating element and the quartz filter membrane, and ensures the high-efficiency analysis efficiency in the thermal analysis stage. The whole device is compact in structure and small in size, only one analysis branch pipe is adopted at the side end of the quartz main pipe to perform subsequent processing analysis on a thermal analysis sample, and the dead volume is small.
(3) This device adopts electromagnetic heating device to carry out the direct heating to the quartz filter membrane, has avoided the low efficiency in the past to generate heat slow, the great traditional resistance-type heating of thermal hysteresis nature and the inhomogeneous phenomenon of filter membrane surface heating that leads to based on the heat-conduction intensification mode of second grade, and this electromagnetic heating mode can realize the one-to-one contact intensification of heating element and quartz filter membrane, has guaranteed the high-efficient analytic efficiency in thermal analysis stage. The whole device is compact in structure and small in size, only one analysis branch pipe is adopted at the side end of the quartz main pipe to perform subsequent processing analysis on a thermal analysis sample, and the dead volume is small. And the whole process of the resolving branch pipe is subjected to high-temperature heat tracing, so that the transmission loss of the resolved substance due to a cold spot is avoided.
(4) The device has high integration level and strong applicability, not only can be used as a trapping device in an atmospheric particulate organic matter monitoring system, but also can be used for applying an analytical furnace in OCEC (optical compensated ec) measuring equipment, and can also be used as a pretreatment community in an atmospheric particulate chemical component online monitoring system.
Drawings
FIG. 1 is a schematic view of an enrichment and desorption device for atmospheric particulates;
FIG. 2 is a schematic diagram of an enrichment and desorption device for atmospheric particulates;
FIG. 3 is a schematic diagram of a device for detecting particulate matter in an atmospheric particulate phase;
FIG. 4 is a schematic diagram of a device for detecting particulate matter in an atmospheric particulate phase;
FIG. 5 is a schematic view of an organic focusing element.
Reference numerals are as follows: 1.O ring; 2. a quartz liner; 3. a desorption tube; 4. the device comprises a high-temperature resistant graphite sealing O ring, 5 parts of a quartz filter membrane, 6 parts of a metal tungsten sheet, 7 parts of a supporting structure, 8 parts of an induction coil, 9 parts of a temperature sensor, 10 parts of an electromagnetic heating control panel and 11 parts of a quartz glass tube body; 12. enrichment analysis device, 13 cutting head, 14 corrosion device, 15 first electric three-way valve, 16 second electric three-way valve, 17 mass flow controller, 18 air pump, 19 micro shunt part, 20 organic focusing part, 21 GCMS detector, 22 OCEC oxidation furnace, 23 OCEC reduction furnace, 24 FID detector, 25 air supply and gas circuit pressure control system, 26 computer interactive control system, 27-micro shunt part, 28-capillary sample feeding pipe, 29-mass spectrometer, 100 aluminum protective shell, 102: heat preservation cotton, 103: copper block, 104: refrigeration piece, 105: resistance wire, 106: adsorption tube, 107: glass fiber wool, 108: thick-walled quartz tube, 109: connection screw, 110: low temperature sensor, 111: finger platform cylinder, 112: stainless steel joining column, 113: support rod, 114: heat insulating pad, 115: protection unit, 116: adsorbent, 117: temperature sensor, 118: stainless steel screws.
Detailed Description
At present, the on-line monitoring instrument for the atmospheric particulate organic matter at home and abroad basically carries out enrichment by taking the stainless steel material of the built-in filter membrane as a frame. Since particulate organics tend to adhere to the stainless steel inner wall, the apparatus requires a passivating pretreatment prior to use, an operation which undoubtedly reduces time efficiency and increases costs. In addition, at present, various domestic large manufacturers basically adopt a quartz tube with a built-in filter membrane for enriching and analyzing carbon elements of atmospheric particulates, although inner wall passivation is not needed, heating analysis of the filter membrane basically adopts resistance type heating modes such as heating wires or heating rods wound on the outer wall of the quartz tube for thermal analysis, and the heating mode has low efficiency, slow heating and large loss, is easy to age at high temperature and is not suitable for high-temperature heating; and the temperature of the filter membrane is raised based on the secondary heat conduction, namely, the heat generated by the heating wires or the heating rods is transferred to the filter membrane through the quartz tube, and the indirect heating mode of the filter membrane is slower in temperature rise, so that the temperature of the surface of the filter membrane is easily uneven, and the measurement accuracy and the segmentation accuracy of the OCEC are greatly reduced.
Based on this, this application uses present collection analytic high efficiency, the saving demand to atmospheric particulates as the starting point, develops one kind and can realize the analytic device of atmospheric particulates enrichment, and the device both can avoid present operation that needs the passivation in advance to granule organic matter enrichment module, and the electromagnetism direct heating mode of adoption has guaranteed the rapid heating up demand of analytic stage in addition, guarantees to gather the thermally uniform heating and the high-efficient thermal analysis of the particulate matter of filter membrane surface department. The device has compact structure and high integration level, can be applied to an OCEC carbon element analysis system in the atmosphere and can also be applied to a monitoring system of particle organic matters as a collecting and analyzing device, namely the collecting and analyzing device can realize enrichment and analysis of multicomponent elements of atmospheric particulates.
In the present application, the atmospheric particulates refer to particulates with an aerodynamic equivalent diameter of 2.5 microns or less in ambient air, also called fine particulates, and the composition of the substances is complex, including organic substances, carbon elements, water-soluble ions, and the like.
As shown in fig. 1, an enrichment analysis device for measuring the chemical components and concentration of atmospheric particulates comprises: a tube body 11, a desorption tube 3; the two sides of the tube body 11 are respectively provided with a sample inlet and an air outlet; in the sampling direction of the particles, a filter membrane 5, a magnetic conductive membrane 6 and a support structure 7 are sequentially arranged in the tube body 11; one side of the analysis tube 3 is welded on the side surface of the tube body 11, and the other side of the analysis tube extends outwards along the radial direction of the tube body 11; in the sampling direction of the particulate matter, the support structure 7 and the desorption tube 3 are arranged at different positions of the tube body 11. The enrichment analysis device further comprises an electromagnetic heating control panel 10 which is connected with the induction coil 8, and the induction coil 8 is arranged on the outer side of the tube body 11 and wound outside the tube corresponding to the magnetic conductive membrane 6 and the filter membrane 5. The filter membrane 5, the magnetic conduction membrane 6 and the supporting structure 7 form a sandwich structure, the filter membrane can be directly heated by the electromagnetic element, the induction coil and the controller, the heating mode is fast in temperature rise, the temperature rise rate in a thermal desorption stage can be ensured, and the OCEC cutting efficiency and the desorption efficiency of high-carbon substances C35-C40 are improved. The heating device can solve the defects that the heat generated by a heating wire or a heating rod resistance type heating element with lower efficiency is brought to a filter membrane through the outer wall of a main pipe at present, and the heating device adopts a secondary conduction low-efficiency heating mode, the temperature rise of the resistance type heating mode is slower, the thermal hysteresis is larger, the filter membrane is easy to heat unevenly, the thermal resolution of the particle substances, particularly OCEC and high-carbon organic matters, which are enriched can be insufficient, and the detection limit of the instrument is reduced. The electromagnetic heating mode can realize the surface-to-surface contact temperature rise of the heating element and the quartz filter membrane, and ensures the high-efficiency analysis efficiency in the thermal analysis stage. The whole device is compact in structure and small in size, only one analysis branch pipe is adopted at the side end of the quartz main pipe to perform subsequent processing analysis on a thermal analysis sample, and the dead volume is small.
This application adopts a comparatively neotype heating methods, filter membrane direct contact heating element's electromagnetism intensification mode promptly, be about to magnetic conductive element and filter membrane and carry out the integrated design, place it in the excitation coil that is in the alternating current change, and utilize magnetic conductive element to cut the alternating magnetic line of force, thereby at the inside vortex that produces of magnetic conductive element, the heat energy that the vortex produced carries out the direct heating to the filter membrane, both guaranteed the rapid heating up demand in analytic stage, also ensure the high-efficient thermal analysis of filter membrane surface even heating and enrichment material. The heating device also comprises a temperature control component, wherein the temperature control component comprises a temperature control module or a Siemens PLC control system, the temperature control component is connected with the electromagnetic heating control board, and the power output of the electromagnetic heating control board is controlled through negative feedback regulation of temperature so as to realize control of the temperature. The electromagnetic heating can only realize temperature rise, and the temperature control component realizes the output of temperature rise power through control components such as an external temperature controller and the like, thereby realizing the regulation of the temperature. The heating mode can realize that the surface temperature of the filter membrane reaches the temperature range of 30-1000 ℃, and the temperature control precision is+0.2℃
In the present application, the induction coil 8 functions to provide a magnetic field so that the heating element permeable membrane 6 cuts the alternating magnetic lines of force, thereby generating eddy currents in the interior thereof to generate heat.
In the present application, the support structure 7 is used to support the filter membrane 5 and the magnetically permeable membrane 6, and to fix the support filter membrane 5 and the magnetically permeable membrane 6 inside the tube 11.
In the present application, the desorption tube 3 is used for carrying the thermally precipitated substances to a subsequent analysis element or detector for further measurement through a carrier gas, and in order to reduce the cold spot loss of the desorbed substances, particularly high boiling point substances, in the transmission pipeline, the desorption quartz branch tube 3 is provided with a heat tracing system, so that the desorption quartz branch tube 3 and the subsequent components are sealed by an Agilent high temperature O ring 4.
In this application, bearing structure 7 can be for the support holder for bear magnetic conduction diaphragm and filter membrane, and bearing structure also can be for setting up in two separation blades of body opposite side, and two separation blades are axisymmetric.
In the present application, the tube body 11 and the analyzing tube 3 are both a quartz glass tube body and a quartz glass analyzing tube.
In the present application, the filter membrane 5 is a quartz filter membrane.
In the present application, the magnetic conductive diaphragm 6 is a metal tungsten sheet, a metal molybdenum sheet, an iron silicon sheet or an iron nickel sheet.
As shown in fig. 1, the two sides of the pipe body are sealed by using first O-rings 1, and the first O-rings are preferably made of fluororubber or polytetrafluoroethylene. The two sides of the tube body are sealed by the first O-rings 1, and the first O-rings can resist 150 ℃, have low cost and are easy to obtain on the market.
As shown in fig. 1, the analytical tube is sealed with a second O-ring 4, and the second O-ring 4 is preferably made of polyimide. The second O-ring resists 350 ℃, and can ensure stable sealing and no release of redundant substances under the high-temperature heat tracing of the desorption tube.
As shown in fig. 1, the enrichment and desorption device further comprises a lining 2, the lining 2 is arranged inside the tube body and located between the sample inlet and the filter membrane 5, the lining 2 is a quartz lining, and the stability of the quartz filter membrane 5 under long-time large-flow sampling is ensured by adopting the built-in quartz lining 2.
In one embodiment of the present application, the tube 11 is a quartz tube 11.
In one embodiment of the present application, the filter membrane 5 is a quartz filter membrane 5.
In one embodiment of the present application, the magnetically permeable membrane 6 is a tungsten metal sheet 6.
In one embodiment of the present application, the support structure 7 is a quartz support structure 7.
In some embodiments of the present application, the supporting structure 7 is two blocking pieces disposed on the tube body, and the two blocking pieces are respectively located on two opposite sides of the sample outlet of the tube body 11.
In one embodiment of the present application, the liner 2 is a quartz liner 2.
In some embodiments of the present application, the filter membrane is a quartz fiber filter membrane.
As shown in fig. 1, the enrichment and desorption device further comprises a patch temperature sensor, wherein the patch temperature sensor is located at the outer side of the tube body, is close to the filter membrane, and is opposite to the side of the tube body with the desorption tube. The patch temperature sensor is used for monitoring the actual temperature of the filter membrane in real time, is connected with the electromagnetic heating control panel and an external temperature control device, and controls the power output of the electromagnetic heating control panel through negative feedback regulation of the temperature so as to realize control and regulation of the temperature.
As shown in fig. 1, the support structure 7 is arranged downstream of the resolving tube 3 in the sample introduction direction; preferably, when the support structure 7 is arranged downstream of the resolving pipe 3, the ratio of the distance between the support structure 7 and the resolving pipe 3 to the total length of the pipe body 11 is (0.3-0.7): 3; further preferably, when the supporting structure 7 is arranged at the downstream of the analysis tube 3, the ratio of the distance between the analysis tube 3 and the sample inlet to the total length of the tube body is (0.5-1.3): 3;
for example, when a support structure is disposed downstream of the resolving tube, the ratio of the distance between the support structure and the resolving tube to the total length of the tube body may be in the range of 0.3;
when the support structure 7 is disposed downstream of the desorption tube 3, the ratio of the distance between the desorption tube 3 and the sample inlet to the total length of the tube body can be. Thus, the sampling and analyzing gas path can be guaranteed to be simplified to the utmost extent.
As shown in fig. 2, the support structure 7 is arranged upstream of the resolution tube 3 in the direction of the particle introduction; preferably, when the support structure 7 is arranged upstream of the resolving tube 3, the ratio of the distance between the support structure 7 and the resolving tube 3 to the total length of the tube body is (0.3-0.7): 3; further preferably, when the supporting structure 7 is arranged at the upstream of the analysis tube 3, the ratio of the distance between the analysis tube and the sample inlet to the total length of the tube body is (1-1.7): 3;
for example, when the support structure 7 is disposed upstream of the resolving tube 3, the ratio of the distance between the support structure 7 and the resolving tube 3 to the total length of the tube body may be 0.3;
when the support structure 7 is disposed upstream of the resolving tube 3, the ratio of the distance between the resolving tube 3 and the injection port to the total length of the tube body may be 1.0.
In one embodiment of the present application, the quartz glass tube body 11 can be designed according to actual requirements, for example, in one embodiment, the quartz glass tube body 11 has the dimensions of 20mm in diameter, 100mm in length and 1.5mm in wall thickness.
As shown in fig. 1, in a specific embodiment, the size of the quartz glass tube 11 is 3cm long, the inner diameter is 8mm, and the wall thickness is 4mm, a quartz support structure 7 is welded at 1cm of the upstream injection port of the quartz glass tube 11, at this time, the quartz support structure 7 is two blocking pieces welded at 1cm of the upstream injection port of the quartz glass tube 11 and arranged at opposite sides of the tube, and the two blocking pieces are axisymmetric and used for supporting and protecting a sampling quartz filter membrane 5 and the like; a metal tungsten sheet 6 and a quartz filter membrane 5 which correspond to a 1/2 inch quartz glass tube body 11 in size are placed above a quartz supporting structure 7, the quartz filter membrane 5 is a particle collecting element, the metal tungsten sheet 6 is used as an electromagnetic heating element, and the requirement of heating from 30 ℃ to 1000 ℃ for rapid temperature rise can be realized through an external induction coil 8 and an electromagnetic heating control panel 10, wherein the induction coil is arranged outside the tube body and is wound outside the magnetic conductive membrane and the filter membrane corresponding to the outside of the tube; in order to avoid the position of the quartz filter membrane 5 from changing in the flowing process of the airflow, a quartz lining 2 tube with the outer diameter of 7.6mm and the length of 0.7cm is arranged at the position above the quartz filter membrane 5, so that the stability of the device is improved. Because the electromagnetic heating mode adopted by the device only plays a role in the magnetic metal tungsten sheet 6, the temperature of both ends of the quartz glass tube body 11 cannot exceed 150 ℃ even at the high-temperature analysis stage at 1000 ℃, so that the whole device can be connected with the front-end air inlet pipeline and the rear-end flow control system only by using a 150 ℃ resistant polytetrafluoroethylene connector and a common O ring when the whole device is connected with the air inlet pipeline and the rear-end flow control system. The analysis quartz tube 3 with the outer diameter of 6.3mm and the wall thickness of 3mm is arranged at the position 5mm at the upper end of the quartz filter membrane 5 and is used for carrying substances absorbed by pyrolysis to a subsequent analysis element or detector through carrier gas for further measurement, in order to reduce the cold point loss of the analyzed substances, particularly high-boiling-point substances, in a transmission pipeline, the analysis quartz tube 3 is provided with a heat tracing system, and therefore the analysis quartz tube 3 and the subsequent components are sealed by an Agilent high-temperature resistant O ring.
In some embodiments, the enrichment and desorption device for atmospheric particulates uses the quartz filter membrane 5 as the collection component, and adopts a Tisuquart whole quartz filter membrane of PALL or a quartz filter membrane of waterman, where the quartz filter membrane 5 has a retention rate of particulate matter of 0.3um of 99.9%. The realization of low temperature depends on a vortex fan which is arranged at the outer side of the quartz glass tube body 11 corresponding to the quartz filter membrane through a fixed bracket; the realization of the high temperature of the quartz filter membrane 5 depends on the metal tungsten sheet 6 as a magnetic conduction element, the induction coil and the electromagnetic heating control panel 14 to carry out electromagnetic heating, the metal tungsten sheet 6 is tightly attached to the quartz filter membrane 5, and the heating requirements of different stages can be directly carried out on the filter membrane. The heating mode depends on electromagnetic direct heating, the temperature rise is fast, the heating is even, and the resolution efficiency is high.
This enrichment analytical equipment of atmospheric particulates has developed an enrichment and analysis integrated device that has universality, popularization nature according to atmospheric particulates collection characteristics. The device is in order to adopt the quartz material, only needs simple wall cleaning (alcohol or distilled water supersound, high temperature dry by the fire hold can), need not carry out surface passivation and handle, has reduced the preliminary stage preparation time and the cost of instrument to a certain extent. In addition, the device adopts a centralized filter membrane heating mode, so that the temperature of two ends of the quartz main pipe provided with the filter membrane does not exceed 150 ℃, a basic sealing ring type can be used for gas circuit connection, the device can be connected with different analysis elements, and the universality and universality of the device are improved by the simple connection mode.
The application provides a check out test set that is arranged in atmospheric particulates chemical composition and concentration measurement thereof, includes above-mentioned enrichment analytical equipment and reposition of redundant personnel part.
In the application, the shunting part is a metal part with a micro cross pore (small dead volume) formed inside after surface deactivation, substances analyzed in the atmospheric particulate enrichment and analysis device can be shunted through internal gas path connection and a gas path trend control system, the number of specific shunts can be controlled according to actual needs, and in some specific implementation modes, for example, the shunting part can be divided into one strand, two strands or three strands. The shunt part is a micro shunt part 19 or a micro shunt part 27.
As shown in fig. 3, the micro flow dividing part 19 may divide the material desorbed from the atmospheric particulate enrichment and desorption device into one or two flows.
As shown in fig. 4, the micro flow dividing part 27 may divide the material desorbed from the atmospheric particulate enrichment and desorption device into one, two or three streams. As shown in fig. 3, the detection apparatus further comprises means for detecting organic substances in the volatile range of the particulate matter C8-C40 and/or means for detecting carbon elements in the particulate matter and/or means for detecting ionic components in the particulate matter.
As shown in FIG. 3, the device for detecting the organic matters in the particles in the volatility range of C8-C40 in the atmospheric particulates comprises an organic matter focusing component and a GCMS detector.
As shown in fig. 3, the apparatus for detecting carbon in atmospheric particulates includes an OCEC oxidation furnace, an OCEC reduction furnace, and a FID detector.
As shown in fig. 4, the apparatus for detecting ionic components in atmospheric particulates comprises a capillary sample inlet 28 and a mass spectrometer 29.
As shown in fig. 4, the flow dividing member is connected to the analyzing tube 3 of the enrichment analyzing apparatus; the shunt part is respectively connected with the organic matter focusing part 20, the OCEC oxidation furnace 22 and the capillary sampling tube 28; the organic matter focusing component 20 is connected with the GCMS detector 21; the OCEC oxidation furnace 22 is connected with the OCEC reduction furnace 23, and the OCEC reduction furnace 23 is connected with the FID detector 24; the capillary sample inlet 28 is connected to the mass spectrometer 29.
In some embodiments of the present application, an apparatus for detecting chemical constituents in atmospheric particulates includes a device for detecting C8-C40 range of volatility organic matter in the particulates, and the device for detecting C8-C40 range of volatility particulate organic matter includes an organic matter focusing component, a GCMS detector. At this time, the detection device can be used for detecting the organic matter components of the particles in the volatility range of C8-C40 in the atmospheric particulates. The material that is decomposed from heat in the atmospheric particulate enrichment and desorption device can be divided into one stream. The method comprises the steps of enriching particulate matters in the atmosphere on the surface of a filter membrane at 30 ℃, raising the temperature of the filter membrane to 320 ℃ by controlling the output power of electromagnetic heating, gasifying and resolving organic matters enriched on the surface of the filter membrane at the temperature, carrying out secondary enrichment in a subsequent focusing component, and carrying the resolved organic matters into a GCMS detector by controlling the temperature of a focusing trap for component measurement.
In some embodiments of the present application, an apparatus for detecting chemical components in atmospheric particulates includes a device for detecting carbon elements in particulates, and the device for detecting carbon elements in particulates includes an OCEC oxidation furnace, an OCEC reduction furnace, and an FID detector, the OCEC oxidation furnace is connected to the OCEC reduction furnace, and the OCEC reduction furnace is connected to the FID detector. At this time, the detection apparatus can be used to detect the carbon element component in the particulate matter. The material thermally resolved from the atmospheric particulate enrichment and resolution device can be divided into one stream. The particulate matter components in the atmosphere are enriched on the surface of the filter membrane at 30 ℃, the power is output by controlling the electromagnetic heating,respectively carrying out high-temperature desorption of different temperature rise steps on the filter membrane in aerobic and anaerobic environments, carrying the substances thermally desorbed from the surface of the filter membrane into a subsequent oxidation furnace by using carrier gas, and oxidizing the substances to be detected into CO 2 CO after oxidation 2 Enters a reduction furnace to be reduced into CH 4 Finally measuring the generated CH by FID detector 4 The concentration of the particulate carbon component is calculated.
In some embodiments of the present application, a detection apparatus for detecting a chemical component in atmospheric particulates includes a means for detecting an ionic component in the particulates, and the means for detecting an ionic component in the particulates includes a capillary sample inlet and a mass spectrometer. At this time, the detection apparatus is used to detect the ionic component in the particulate matter. The material that is decomposed from heat in the atmospheric particulate enrichment and desorption device can be divided into one stream. The method comprises the steps of enriching particulate matters in the atmosphere on the surface of a filter membrane at 30 ℃, gradually raising the temperature of the filter membrane to 600 ℃ by controlling the output power of electromagnetic heating, gasifying and desorbing water-soluble substances, chlorides and other substances enriched on the surface of the filter membrane at the temperature, feeding the substances into a subsequent capillary sample feeding tube along with carrier gas, wherein capillary sample feeding is mainly used for reducing the flow entering a mass spectrometer, maintaining the vacuum degree of the mass spectrometer in a normal use state, then feeding the substances to be detected into the mass spectrometer for measurement, and performing qualitative and quantitative analysis through the characteristic ion peak intensity of a mass spectrum monitoring signal.
In some embodiments of the present application, a detection apparatus for chemical constituents in atmospheric particulates includes a means for detecting particulate organics in the C8-C40 volatility range and a means for detecting carbon elements in the particulates. The device for detecting the organic matters in the particles in the volatility range of C8-C40 comprises an organic matter focusing component and a GCMS detector; the device for detecting carbon element in the particulate matter comprises an OCEC oxidation furnace, an OCEC reduction furnace and a FID detector. The OCEC oxidation furnace is connected with the OCEC reduction furnace, and the OCEC reduction furnace is connected with the FID detector. The material that makes the thermal desorption of the particulate matter that adsorbs in the enrichment analytical equipment come out divides into two strands, and this check out test set can detect granule organic matter and carbon element component in the particulate matter in C8-C40 volatility scope simultaneously this moment. The method comprises the steps of enriching particulate matters in the atmosphere on the surface of a filter membrane at 30 ℃, raising the temperature of the filter membrane according to a program by controlling the output power of electromagnetic heating, raising the temperature to 320 ℃ and keeping the temperature for 10min, gasifying organic substances enriched on the surface of the filter membrane at the temperature, feeding the gasified organic substances into a subsequent flow distribution system along with carrier gas, feeding part of the gasified organic substances into a focusing component in an organic matter measuring system for secondary enrichment, and feeding organic matters subjected to thermal decomposition into a GCMS detector by controlling the temperature of a focusing trap for component measurement. The other part enters a capillary sample inlet pipe and then enters a mass spectrometer for partial measurement of the particle ion component. And then, the filter membrane is gradually increased to the high temperature of 600 ℃ from 320 ℃, water-soluble substances, chlorides and other substances enriched on the surface of the filter membrane are all gasified and desorbed at the temperature, enter a subsequent capillary sampling tube along with carrier gas, and then the substance to be detected enters a mass spectrometer for measurement, and is qualitatively and quantitatively analyzed through the characteristic ion peak intensity of a mass spectrum monitoring signal.
In some embodiments of the present application, a detection apparatus for chemical composition of atmospheric particulates includes means for detecting particulate organic matter in the C8-C40 volatility range and means for detecting ionic composition of the particulate matter. The device for detecting the organic matters in the particles in the volatility range of C8-C40 comprises an organic matter focusing component and a GCMS detector; the device for detecting the ion components in the particles comprises a capillary sample inlet pipe and a mass spectrometer. The material separated by thermal decomposition of the particulate matter adsorbed in the enrichment and desorption device is divided into two parts, and at the moment, the detection equipment can simultaneously detect the particle organic matter and the ion component in the particulate matter in the volatility range of C8-C40. The method comprises the steps of enriching particulate matters in the atmosphere on the surface of a filter membrane at 30 ℃, raising the temperature of the filter membrane according to a program by controlling the output power of electromagnetic heating, raising the temperature to 320 ℃ and keeping the temperature for 10min, gasifying organic substances enriched on the surface of the filter membrane at the temperature, feeding the gasified organic substances into a subsequent flow distribution system along with carrier gas, feeding part of the gasified organic substances into a focusing component in an organic matter measuring system for secondary enrichment, and feeding organic matters subjected to thermal decomposition into a GCMS detector by controlling the temperature of a focusing trap for component measurement. The other part enters a capillary sample inlet pipe and then enters a mass spectrometer for partial measurement of the particle ion component. And then, the filter membrane is gradually increased to the high temperature of 600 ℃ from 320 ℃, water-soluble substances, chlorides and other substances enriched on the surface of the filter membrane are all gasified and desorbed at the temperature, enter a subsequent capillary sampling tube along with carrier gas, and then the substance to be detected enters a mass spectrometer for measurement, and is qualitatively and quantitatively analyzed through the characteristic ion peak intensity of a mass spectrum monitoring signal.
In some embodiments of the present application, a detection apparatus for chemical composition of atmospheric particulates includes a means for detecting carbon elements in the particulates and a means for detecting ionic composition in the particulates. The device for detecting the carbon element in the particulate matter comprises an OCEC oxidizing furnace, an OCEC reducing furnace and an FID detector. The OCEC oxidation furnace is connected with the OCEC reduction furnace, and the OCEC reduction furnace is connected with the FID detector; the device for detecting the ion components in the particles comprises a capillary sample inlet pipe and a mass spectrometer. At this time, the material that the thermal desorption of the particulate matter adsorbed in the enrichment desorption device was made is split into two strands, and this check out test set can detect carbon element in the particulate matter and the ionic component in the particulate matter simultaneously. Enriching particulate matter components in the atmosphere on the surface of a filter membrane at 30 ℃, gradually increasing the temperature of the filter membrane to 615 ℃ by controlling the output power of electromagnetic heating in an anaerobic state according to a NIOSH program, keeping the temperature for 10min, gasifying organic carbon OC1, OC2 and OC3, water-soluble substances, chlorides and the like enriched on the surface of the filter membrane at the temperature, feeding the gasified organic carbon OC1, OC2 and OC3, the water-soluble substances, the chlorides and the like into a subsequent flow distribution system along with anaerobic carrier gas, feeding a part of the gasified organic carbon OC1, OC2 and OC3 into a capillary sample feeding pipe, and then feeding the gasified organic carbon into a mass spectrometer for qualitative and quantitative measurement and analysis of particulate matter ion components; the other part enters an oxidation furnace in the carbon component monitoring system, and part of organic carbon substances are oxidized into CO 2 CO after oxidation 2 Enters a reduction furnace to be reduced into CH 4 And finally measured by a FID detector. Then, the temperature of the filter membrane is gradually increased from 615 ℃ to 870 ℃, organic matters on the surface of the filter membrane are all desorbed, and the filter membrane enters a carbon element measuring system to carry out OC4 material information measurement; then making an aerobic ringGradually raising the temperature of the filter membrane in the environment, carrying the EC substance thermally resolved from the surface of the filter membrane into a subsequent oxidation furnace by using carrier gas, and oxidizing the substance to be detected into CO 2 CO after oxidation 2 Enters a reduction furnace to be reduced into CH 4 Finally measuring the generated CH by FID detector 4 The concentration of the particulate elemental carbon component is calculated.
In some embodiments of the present application, as shown in fig. 4, a detection apparatus for chemical constituents in atmospheric particulates includes means for detecting particulate organic matter in the C8-C40 volatility range, means for detecting carbon elements in the particulates, and means for detecting ionic constituents in the particulates. The device for detecting the organic matters in the particles in the volatility range of C8-C40 comprises an organic matter focusing component 20 and a GCMS detector 21, wherein the shunting component 19 shunts 3 strands; the device for detecting carbon element in the particulate matter comprises an OCEC oxidation furnace 22, an OCEC reduction furnace 23 and an FID detector 24. The OCEC oxidation furnace 22 is connected with the OCEC reduction furnace 23, and the OCEC reduction furnace 23 is connected with the FID detector 24; the means for detecting the ionic component of the particulate matter includes a capillary sample inlet 28 and a mass spectrometer 29. At the moment, the detection equipment can simultaneously detect granular organic matters, carbon elements and ion components in the granules in the volatility range of C8-C40.
As shown in fig. 5, the organic focusing part includes high and low temperature members; the high-low temperature component comprises a high-temperature module, a low-temperature module and a high-low temperature switching module.
As shown in fig. 5, the high temperature module includes an adsorption tube 106 and a resistance wire 105 wound outside the adsorption tube, and the inside of the adsorption tube 106 is filled with Tenax series adsorbent; and a layer of insulating sleeve is further arranged between the adsorption tube and the resistance wire, and the insulating sleeve is wrapped on the periphery of the adsorption tube 106. The high-temperature module further comprises a protection unit 115, and the protection unit 115 is wrapped on the periphery of the resistance wire 105; the high temperature module further includes a temperature sensor 117, and the temperature sensor 117 is disposed outside the adsorption pipe 106.
As shown in FIG. 5, the material of the tube body of the adsorption tube is 316 stainless steel or Germany Schott-Duran high-precision quartz glass, and the gas flow rate can be controlled within 0.05-2L/min by using the tube body of the adsorption tube.
As shown in fig. 5, a thick-walled quartz tube 108 is disposed at a position of the strong adsorbent near the gas outlet, and the thick-walled quartz tube 108 is used for protecting the adsorbent to avoid the loss of the adsorbent due to long-time sampling.
As shown in fig. 5, the adsorption tube further includes a heating unit 105, the heating unit 105 is a resistance wire wound outside the adsorption tube body, and the resistance wire is wound on the outer wall of the adsorption tube body; preferably, the resistance wire is a nickel-chromium resistance wire, and the resistance wire can heat the adsorption tube body to 50-350 ℃ for providing high temperature for thermal desorption.
As shown in fig. 5, the adsorption tube further includes a protection unit 115, and the protection unit is wrapped around the heating unit; preferably, the protection unit is made of glass fiber cotton. The protection unit 115 is used as a protection sleeve and wraps the periphery of the resistance wire 105, so that the phenomenon that the resistance wire 105 is abraded due to the impact clamping action of the resistance wire 105 and a refrigeration metal block can be avoided, and the protection sleeve is used for protecting the heating unit 105.
As shown in fig. 5, the adsorption tube 106 further includes a temperature sensor 117, the temperature sensor 117 is disposed outside the adsorption tube body and is used for displaying the temperature of the adsorbent, the temperature sensor 117 is tightly attached to the outer wall of the adsorption tube and can relatively and truly display the real-time temperature of the adsorbent to reduce insufficient organic matter enrichment and analysis caused by temperature discrimination, and an external PID control system is used to control the temperature of the adsorbent to be ± 0.1 ℃ to ensure the temperature accuracy of the adsorbent.
As shown in fig. 5, the low temperature module includes a refrigerating sheet and a metal block; the metal block comprises two sub-metal blocks which are provided with semicircular grooves at the center and are of symmetrical structures, and the adsorption tube can be attached to the groove formed by the two sub-metal blocks. Wherein the high temperature module further comprises a protection unit 115; the low-temperature module further comprises a refrigeration plastic screw, a temperature sensor and a heat dissipation unit.
The low-temperature modules in the high-low temperature component comprise two low-temperature modules and a high-low temperature switching module, the two low-temperature modules are symmetrically arranged oppositely, and are fixedly connected with the finger platform cylinder 111 through stainless steel connecting columns 112 to provide constant enrichment low temperature for the adsorption tubes; the pneumatic driving device is connected with the two low-temperature modules and can drive the two low-temperature modules to move oppositely or oppositely along the longitudinal direction, when the two low-temperature modules move oppositely and are in contact with each other, the adsorption tube can be tightly clamped, and when the two low-temperature modules move oppositely and are separated from each other, the adsorption tube can be released.
The low-temperature module comprises a refrigerating sheet 104, a metal block 103, a plastic screw, a temperature sensor and a heat dissipation unit; the refrigeration piece is a three-stage semiconductor refrigeration element which can reduce the temperature of the adsorption tube to-40 ℃ and can continuously provide low temperature. The metal block selects the metal block 103 with low specific heat capacity as a heat conducting medium, for example, the metal block 103 is a copper block, the metal block is composed of two symmetrical sub-metal blocks which are provided with semicircular grooves at the center and can be opened and closed, the adsorption tube can be attached to the groove formed by the two sub-metal blocks, and the two sub-metal blocks are symmetrically and oppositely arranged to form the low-temperature module.
The cold end of the refrigeration sheet 104 is tightly attached to the metal block 103, the metal block 103 is tightly arranged with the cold end of the refrigeration sheet through a heat conduction silicone layer, and the hot end of the refrigeration sheet 104 can be connected with a copper pipe radiator and a cooling fan through another heat conduction silicone layer; the copper pipe radiator is used for radiating the refrigerating fins, and outputs heat to the radiating fan by utilizing the excellent heat conductivity of the copper pipe and the condensation and conversion of liquid in the copper pipe. One side of the copper pipe radiator is connected with the hot end of the refrigerating fin 104 through a heat-conducting silicone layer; the other side is connected with the heat radiation fan through a button screw. A thin-wall aluminum protective shell is placed on the outer layer of the metal block 103, heat insulation cotton is tightly arranged between the metal block 103 and the aluminum protective shell, and the metal block is connected with the aluminum protective shell through plastic screws.
In one embodiment of the present application, as shown in fig. 5, the low temperature module is composed of two sub-low temperature modules which are symmetrical to each other, and the sub-modules are controlled by the pneumatic driving device to perform a separating or closing operation, so as to realize a rapid switching function of high and low temperatures of the adsorption tube. The sub-temperature module uses the copper block 103 with lower specific heat capacity as a heat conducting medium, the size of the copper block 103 is 130mm 30mm, a semicircular groove corresponding to the outer diameter of the adsorption pipe is formed in the center of the copper block 103, the adsorption pipe 6 is placed in the circular groove, and the adsorption pipe can be wrapped in a seamless mode when the sub-temperature module is closed, so that temperature transmission is achieved. In order to reduce the temperature loss of the copper block 3, an aluminum protective housing 100 is added outside the copper block 3, the size of the aluminum protective housing 100 is 140 × 33mm, the aluminum protective housing 100 and the copper block 103 are connected by using a teflon screw 9 of M4 × 12, and a gap between the aluminum protective housing 100 and the copper block is filled with heat insulation cotton so as to reduce the transmission loss of the temperature and the air of the sub-temperature module. Meanwhile, a support rod 113 is used to fix and connect the adsorption tube 106, and the lower end of the support rod is connected to the worktable through an insulating pad 114, so as to reduce the temperature transmission loss. The temperature sensor 110 of the low-temperature module is placed at the side opening of the copper block 103, that is, the copper block 103 and the side of the aluminum protective shell 100 are opened, the size of the opening is adapted to the outer diameter (4 mm) of the low-temperature sensor 110, the low-temperature sensor 110 is placed inside the aluminum block 103, so as to display the real temperature of the aluminum block 103 in real time, and the temperature of the low-temperature module is generally controlled to be kept unchanged at-40 ℃.
The high-temperature module, namely a heating unit of the adsorption tube is mainly heated by direct-current voltage of a resistance wire 105, the resistance wire is uniformly and tightly wound on the outer wall of the adsorption tube body, in order to avoid the phenomena that the resistance wire is short-circuited due to mechanical impact and the like caused by clamping the adsorption tube by a low-temperature module during low-temperature transmission, the outer wall of the adsorption tube body wound with the resistance wire is coated with a layer of insulating protective sleeve made of glass fiber cotton, so that the short-circuit of the resistance wire can be prevented, the low-temperature transmission cannot be interfered, and the heating temperature can be increased to 320 ℃ from minus 40 ℃ within 4 s; the resistance wire is heated only when the adsorption tube needs high temperature, and is not heated in other time.
The low temperature module, namely refrigeration, realizes the low temperature of 40 ℃ below zero through the three-level semiconductor refrigeration element 104, and the temperature control module can be integrally at the constant low temperature of 40 ℃ below zero by using the three-level refrigeration piece due to the small size of the temperature module. The cold junction of refrigeration piece 104 is installed on the copper billet 3 of the relative opposite side of semicircle groove end, and both closely link up through heat conduction silicone grease, and this refrigeration piece 104's hot junction can be connected with the copper pipe radiator through another heat conduction silicone grease layer, guarantees the high-efficient work of refrigeration piece. The refrigerating sheet is always in a refrigerating working state after being started, and the temperature sensor 110 displays the low-temperature in real time, namely, the sub-temperature module is always kept at the constant temperature of minus 40 ℃ so as to carry out rapid low-temperature transfer on the adsorption pipe at any time.
The high-low temperature switching module comprises a pneumatic driving device, and the pneumatic driving device controls the opening or closing of the low-temperature sub-metal block by controlling the introduction or non-introduction of carrier gas, so that the switching of the adsorption tube between a high-temperature mode and a low-temperature mode is finally realized;
when carrier gas is introduced into the pneumatic driving device, the two symmetrical sub metal blocks move relatively and are separated along the longitudinal direction, at the moment, the two symmetrical sub metal blocks are opened, so that an interval is formed between the two symmetrical sub metal blocks and the adsorption tube, the heating module is controlled to work, and the adsorption tube is in a high-temperature mode; when no carrier gas is introduced into the pneumatic device, the two symmetrical sub-metal blocks move oppositely along the longitudinal direction, at the moment, the two symmetrical sub-metal blocks are closed, so that the two symmetrical sub-metal blocks clamp the adsorption tube, the heating module is controlled to stop working, and the adsorption tube is in a low-temperature mode.
The switching between the high-temperature mode and the low-temperature mode is mainly realized by controlling a pneumatic driving device to enable the adsorption tube to be in a high-temperature state and a low-temperature state, and the switching method comprises the following specific steps:
as shown in fig. 5, the pneumatic device includes a micro finger platform cylinder, a two-position five-way valve, a PU pneumatic high-pressure pipe and a high-pressure gas source, the micro finger platform cylinder is connected with the bottoms of the two sub-metal blocks through a stainless steel connecting column, an air inlet and an air outlet of the micro finger platform cylinder are respectively connected with a working port of the two-position five-way valve, an air inlet of the two-position five-way valve is connected with the high-pressure gas source, two air outlets of the two-position five-way valve are connected with a silencer, the micro finger platform cylinder can drive the two semi-metal blocks to move in opposite directions or opposite directions along the longitudinal direction through the drive of the two-position five-way valve and the high-pressure gas source, and further control the whole temperature module to open or close, so as to realize the requirement that the adsorption pipe is switched from low temperature to high temperature;
thereby realize the switching of adsorption tube high microthermal through the axial switching motion of the miniature finger platform cylinder 111 of pneumatic drive device control, specifically mainly be: when the adsorption tube 106 needs to work in a high-temperature state, the pneumatic device controls the micro finger platform cylinder 111 to axially open to drive the two sub-metal blocks to separate, so that the adsorption tube 106 is released, namely, at the moment, a gap is formed between the adsorption tube 106 and the two metal blocks, the adsorption tube 106 is not attached to the two metal blocks, a resistance wire wound on the outer wall of the adsorption tube 106 is controlled to work, the adsorption tube is heated to the required high temperature, and the adsorption tube 106 is in a high-temperature mode; when the adsorption tube 106 needs to work under the low temperature state, the control resistance wire stops heating, and the pneumatic device controls the miniature finger platform cylinder 111 to be axially closed, so that the two sub-metal blocks are driven to be closed and the adsorption tube is clamped, the low temperature of the two sub-metal blocks is transferred to the adsorption tube, the low temperature conversion is realized, and the adsorption tube 106 is in the low temperature mode.
The application provides an online measurement and analysis method for measuring the chemical components and the concentration of the atmospheric particulate matters by using the enrichment analysis device or the detection equipment.
In some embodiments of the present application, the online measurement analysis method includes: sampling, purging, analyzing and shunting, and measuring; wherein, the sampling step: introducing a sample to be detected into an enrichment and desorption device to enrich particulate matters in the enrichment and desorption device; a purging step: carrying out carrier gas purging on the enrichment analysis device and the transmission line thereof or the detection equipment and the transmission line thereof to remove redundant gas; analyzing and shunting steps: the particles adsorbed in the enrichment desorption device are desorbed at high temperature and are divided into two or three air flows, wherein the shunted air flows enter an organic matter focusing component for secondary capture and/or enter an OCEC oxidizing furnace, and/or enter a capillary sampling pipePerforming the following steps; a measurement step: the gas flow after the flow splitting enters an organic matter focusing component for secondary enrichment and analysis, and a GCMS detector is used for separating and measuring particle phase organic matters; and/or the gas flow after being divided enters an OCEC oxidizing furnace to be oxidized into CO 2 Then CO 2 Enters an OCEC reducing furnace to be reduced into CH 4 After, CH 4 Entering an FID detector for quantitative detection; and/or the split gas flow enters a mass spectrometer for ion detection.
In one embodiment, taking the example of simultaneously detecting the organic matter in the volatility range of C8-C40 in the atmospheric particulates and the carbonaceous component information of the particulates as the example, the method specifically comprises the following steps:
a sampling step: the computer interaction control system 26 controls the enrichment and analysis device 12 to be in a 30 ℃ collection state, and through the suction effect of the air pump 18, the atmospheric sample is discharged through the air pump 18 after sequentially passing through the cutting head 13, the erosion device 14, the first electric three-way valve 15, the enrichment and analysis device 12, the second electric three-way valve 16 and the mass flow controller 17, so that particulate matters in the atmosphere are retained at the quartz fiber filter membrane in the enrichment and analysis device 12, and the sampling time can be adjusted according to the atmospheric air quality. In the stage, the organic matter monitoring system (the organic matter focusing module 20 and the GCMS detector 21) and the OCEC monitoring system (the OCEC oxidizing furnace 22, the OCEC reducing furnace 23 and the FID detector 24) are in a standby stage;
a purging step: after sampling is finished, the enrichment and desorption device 12 is kept in a low-temperature state of 30 ℃, and in this mode, after oxygen-free carrier gas passes through the gas supply and pressure control system 25 and the first electric three-way valve 15, carrier gas purging is performed on the quartz fiber filter membrane and subsequent pipeline parts in the enrichment and desorption device 12 to remove residual oxygen and other redundant interference gases adsorbed in the quartz fiber filter membrane. In the stage, the organic matter monitoring system (the organic matter focusing module 20 and the GCMS detector 21) and the OCEC monitoring system (the OCEC oxidizing furnace 22, the OCEC reducing furnace 23 and the FID detector 24) are in a standby stage;
analyzing and shunting steps: after purging is completed, the computer interaction control system 26 controls the enrichment and analysis device 12 to be in a temperature rising state, and the temperature of the filter membrane is rapidly raised to 31 DEGKeeping the temperature at 0 ℃ for 8min (namely meeting the first stage of the OCEC NIOSH2 heating protocol), after oxygen-free carrier gas passes through the gas supply and pressure control system 25 and the first electric three-way valve 15, the organic matter to be detected which is enriched in the enrichment and analysis device 12 and released at the high temperature of the quartz filter membrane passes through the analysis quartz branch pipe 3 and the micro flow dividing part 19, and then the gas flow is uniformly divided into 1:1 equal proportion of two gases, one is brought into an organic matter focusing module 20 in a low-temperature enrichment state to carry out secondary capture on organic matters, and the other is oxidized into CO through an OCEC oxidation furnace 22 2 And reduced to CH in OCEC reducing furnace 23 4 And then into the FID detector 24 for measurement. In the stage, when the temperature of the filter membrane is increased to 310 ℃, the substance components in the particulate organic matter, which are enriched at the filter membrane, are completely resolved, and OC, which is measured by OCEC according to the NIOSH2 heating mode, is OC1;
after the substances analyzed in the first stage are shunted, the granular organic substances are secondarily enriched by the organic substance focusing part 20 at low temperature so as to improve the subsequent chromatographic peak, after the organic substances are completely enriched in the organic substance focusing part 20, the computer interaction control system 26 controls the organic substance focusing part 20 to rapidly heat up, the adsorbed organic substances are rapidly released, and the substances to be detected are brought into the GCMS detector 21 through carrier gas for separation and monitoring; and the OCEC system continues to rapidly heat the filter membrane according to a NIOSH2 heating mode until the final stage. At this stage, the micro flow dividing part 19 is controlled to be in the non-flow dividing mode, that is, the analyzed OC/EC substances are all carried to the OCEC oxidation furnace 22 through the micro flow dividing part 19 and are oxidized into CO 2 And reduced to CH in OCEC reducing furnace 23 4 And then into the FID detector 24 for measurement.
Cooling standby mode: after the measurement is completed, the computer interaction control system 26 controls the enrichment analysis device 12 to be in a low-temperature state to be enriched, controls the organic matter monitoring system and the OCEC monitoring system to be in a standby state, and waits for the next particulate matter collection process.
In one embodiment, taking the simultaneous detection of organic matter, carbonaceous component and ionic component information in the volatility range of C8-C40 in the atmospheric particulates as an example, the method specifically comprises the following steps:
a sampling step: the computer interaction control system 26 controls the enrichment and analysis device 12 to be in a 30 ℃ collection state, and through the pumping action of the air pump 18, the atmospheric sample is discharged through the air pump 18 after sequentially passing through the cutting head 13, the corrosion device 14, the first electric three-way valve 15, the enrichment and analysis device 12, the second electric three-way valve 16 and the mass flow controller 17, so that particulate matters in the atmosphere are retained at the quartz fiber filter membrane in the enrichment and analysis device 12, and the sampling time can be adjusted according to the atmospheric air quality. In the stage, an organic matter monitoring system (an organic matter focusing module 20 and a GCMS detector 21), an OCEC monitoring system (an OCEC oxidizing furnace 22, an OCEC reducing furnace 23 and a FID detector 24) and an ion component monitoring system (a capillary sampling tube 28 and a mass spectrometer 29) are in a standby stage;
a purging step: after sampling is finished, the enrichment and desorption device 12 is kept in a low-temperature state of 30 ℃, and in this mode, carrier gas sweeps the quartz fiber filter membrane and subsequent pipeline parts in the enrichment and desorption device 12 after passing through the gas supply and pressure control system 25 and the first electric three-way valve 15, so as to remove residual oxygen and other redundant interference gases adsorbed in the quartz fiber filter membrane. In the stage, an organic matter monitoring system (an organic matter focusing module 20 and a GCMS detector 21), an OCEC monitoring system (an OCEC oxidizing furnace 22, an OCEC reducing furnace 23 and a FID detector 24) and an ion component monitoring system (a capillary sampling tube 28 and a mass spectrometer 29) are in a standby stage;
analyzing and shunting steps: after the purging is completed, the computer interaction control system 26 controls the enrichment and desorption integrated device 12 to be in a temperature rising state, the temperature at the filter membrane is rapidly raised to 310 ℃ and kept for 8min (namely, the first stage of the OCEC NIOSH2 temperature rising protocol is met), at the temperature, organic substances, partial ionic components and OC1 of carbonaceous components enriched on the surface of the filter membrane are all gasified and enter a subsequent flow distribution system along with oxygen-free carrier gas, the oxygen-free carrier gas passes through the gas supply and pressure control system 25 and the first electric three-way valve 15, the to-be-tested substances released at the high temperature of the quartz filter membrane enriched in the enrichment and desorption device 12 pass through the desorption quartz branch pipe 3 and the micro flow distribution part 27,the gas flow is uniformly divided into 1:1:1 equal proportion of three parts of gas, one part is brought into the organic matter focusing module 20 in a low-temperature enrichment state to carry out secondary capture on organic matters, and the other part is oxidized into CO through an OCEC oxidation furnace 22 2 And reduced to CH in OCEC reducing furnace 23 4 Then the sample enters an FID detector 24 for measurement, the last sample enters a subsequent capillary sampling tube 28 along with the carrier gas and is transmitted to a mass spectrometer 29 for qualitative and quantitative analysis and measurement of partial characteristic ion peaks, and at this time, the analysis of the particle organic matters is finished;
after the substances resolved in the first stage are shunted, the granular organic substances are secondarily enriched by the organic substance focusing part 20 at low temperature to improve the subsequent chromatographic peak, after the organic substances are completely enriched in the organic substance focusing part 20, the computer interaction control system 26 controls the organic substance focusing part 20 to rapidly heat up, the adsorbed organic substances are rapidly released, and the substances to be detected are brought into the GCMS detector 21 by carrier gas to be separated and monitored, at this time, the measurement of the granular organic substances is finished; then, the temperature of the surface of the filter membrane is controlled to gradually rise from 310 ℃ to 610 ℃ and is kept for 8min, at the temperature, the ionic component on the surface of the filter membrane and OC2 and OC3 of the carbonaceous component are gasified, and after the ionic component and the OC3 enter the resolving quartz branch pipe 3 and the micro-diversion part 27 along with the oxygen-free carrier gas, the gas flow is uniformly divided into 1:1 equal proportion of two portions of gas, one portion being oxidized to CO in OCEC oxidation oven 22 2 And reduced to CH in an OCEC reduction furnace 23 4 Then the mixture enters a FID detector 24 to measure substances of OC2 and OC3 carbon components, and the other mixture enters a capillary sample inlet tube 28 in an ion component measuring system along with oxygen-free carrier gas and is transmitted to a mass spectrometer 29 to carry out qualitative and quantitative analysis and measurement on ion components, and at the moment, the measurement on the particle ion components is finished;
and (3) carbon component detection: finally, according to the temperature rise requirement of the measurement program of the carbon components of the atmospheric particulates, the surface temperature of the filter membrane is controlled to gradually rise from 610 ℃ to 870 ℃, and at the moment, the OC4 substances of the carbon components on the surface of the filter membrane are gasified and enter the resolving quartz branch pipe 3 and the micro flow dividing part 27 along with oxygen-free carrier gas, and then, the gas flow is not dividedThe stream is oxidized to CO in an OCEC oxidizer 22 2 And reduced to CH in OCEC reducing furnace 23 4 Then the particles enter a FID detector 24 to measure OC4 substances, so that the quantitative monitoring of organic carbon components of the particles is completed; then controlling electromagnetic heating to stop working, controlling fan output, reducing the surface temperature of the filter membrane from 870 ℃ to 550 ℃, introducing helium-oxygen carrier gas, controlling the surface temperature of the filter membrane to gradually rise from 550 ℃ to 626 ℃, from 625 ℃ to 700 ℃, from 700 ℃ to 775 ℃, from 775 ℃ to 850 ℃, from 850 ℃ to 900 ℃, and sequentially introducing the desorbed elemental carbon substances into the desorption quartz branch pipe 3 and the micro-diversion part 27, and allowing the airflow to enter the OCEC oxidation furnace 22 without diversion to be oxidized into CO 2 And reduced to CH in OCEC reducing furnace 23 4 Then the particles enter an FID detector 24 to measure the elemental carbon substances, so that the quantitative detection of the carbon components of the particles is completed;
cooling standby mode: after the measurement is completed, the computer interaction control system 26 controls the enrichment analysis device 12 to be in a low-temperature state to be enriched, and controls the organic matter monitoring system, the OCEC monitoring system and the ion component monitoring system to be in a standby state to wait for the next particulate matter collection process.
Examples
Example 1
As shown in fig. 1, in the enrichment analysis device for measuring the chemical components and concentration of atmospheric particulates, a quartz glass tube 11 is made of quartz glass with a length of 30mm, an inner diameter of 8mm and a wall thickness of 2mm, a quartz support structure 7 is welded at a 10mm upstream sample inlet of the quartz glass tube 11, the quartz support structure 7 is two baffle plates welded at the 10mm upstream sample inlet of the quartz glass tube 11 and arranged at opposite sides of the tube, and the two baffle plates are axisymmetric and used for supporting and protecting a sampling quartz filter membrane 5 and the like; a metal tungsten sheet 6 and a quartz filter membrane 5 which correspond to a 1/2 inch quartz glass tube body 11 in size are placed above a quartz supporting structure 7, the quartz filter membrane 5 is a particle collecting element, the metal tungsten sheet 6 is used as an electromagnetic heating element, the requirement of heating from 30 ℃ to 1000 ℃ for rapid temperature rise can be realized through an external induction coil 8 and an electromagnetic heating control panel 10, wherein the induction coil is arranged outside the tube body so as to realize winding outside a magnetic conductive membrane and the filter membrane; a quartz lining 2 tube with the outer diameter of 7.6mm and the length of 7mm is arranged in the quartz glass tube body 11 and is arranged above the quartz filter membrane 5. And when the whole integrated device is connected with the front-end air inlet pipeline and the rear-end flow control system through the air circuit, a conventional polytetrafluoroethylene connector and an O ring are selected for connection. The quartz tube 3 is provided with a heat tracing system in order to reduce the cold point loss of the analyzed substances, particularly high boiling point substances, in a transmission pipeline, so that the analyzed quartz tube 3 and the subsequent components are sealed by an Agilent high temperature resistant O ring. The quartz filter membrane 5 is used as a collecting component, a Tisuquart all-quartz filter membrane of PALL or a quartz filter membrane of waterman is selected, and the rejection rate of the quartz filter membrane 5 to the particulate matters of 0.3um is 99.9 percent. The realization of the low temperature relies on a vortex fan mounted on the outside of the quartz glass tube body 11 corresponding to the quartz filter membrane by means of a fixed support.
Example 2
The detection equipment for measuring the chemical components and the concentration of the atmospheric particulate matters comprises a device for detecting organic matters of particles in a C8-C40 volatility range, a device for detecting carbon elements in the particulate matters and a device for detecting ionic components in the particulate matters. The device for detecting the organic matters in the particles in the volatility range of C8-C40 comprises an organic matter focusing component and a GCMS detector; the device for detecting carbon elements in the particles comprises an OCEC oxidizing furnace, an OCEC reducing furnace and an FID detector, wherein the OCEC oxidizing furnace is connected with the OCEC reducing furnace, and the OCEC reducing furnace is connected with the FID detector; the device for detecting the ion components in the particulate matter comprises a capillary sample inlet pipe and a mass spectrometer. At the moment, the detection equipment can simultaneously detect the information characteristics of organic matters, carbon components and ion components in the volatility range of C8-C40 in the atmospheric particulates.
The enrichment heat analysis of the atmospheric particulate filter membrane is a common component measurement pretreatment mode, and the rapid and accurate arrival of the surface temperature of the filter membrane is a key factor for ensuring the full material analysis of particulate matters. The device is based on one-to-one contact combination of the filter membrane and the heating element and is embedded into the quartz tube, a high-efficiency low-energy electromagnetic heating mode is adopted, and the temperature control device is combined, so that the surface temperature of the sampling filter membrane is increased to 1000 ℃ from 30 ℃ in 10s, the temperature control precision is +/-0.2 ℃, the requirements of different high-temperature analysis ranges of chemical components of particles are met, and the whole device is compact in structure, low in energy consumption, low in cost, high in integration level and high in universality. The enrichment and analysis integrated device is integrated with different detectors, so that the synchronous analysis and measurement of single components or multiple substances of carbon components, organic components and ion components of atmospheric particulates can be realized. According to the diversity of the synchronous measurement of the multi-component substances of the atmospheric particulates and the traceability demand of chemical components in the current market, the device and the measurement system have a better application and development scene.

Claims (17)

1. An enrichment and desorption device for measuring chemical components and concentration of atmospheric particulates is characterized by comprising: a tube body, a desorption tube;
the device comprises a pipe body, wherein a sample inlet and a gas outlet are respectively arranged at two sides of the pipe body;
in the sampling direction of the particles, a filter membrane, a magnetic conductive membrane and a support structure are sequentially arranged inside the tube body;
a desorption tube having one side welded to a side surface of the tube body and the other side extending radially outward along the tube body;
in the sampling direction of particulate matter, bearing structure the analysis pipe sets up on the different positions of body.
2. The enrichment resolving device according to claim 1, wherein,
the enrichment analysis device further comprises an electromagnetic heating control panel which is connected with the induction coil, and the induction coil is arranged on the outer side of the tube body and wound on the outer portion of the tube body corresponding to the magnetic conduction membrane and the filter membrane.
3. The enrichment resolving device according to claim 1, wherein,
the support structure is arranged at the downstream of the desorption tube in the sampling direction of the particles;
preferably, the ratio of the distance between the support structure and the resolution tube to the total length of the tube body is (0.3-0.7): 3;
further preferably, the ratio of the distance between the analysis tube and the sample inlet to the total length of the tube body is (0.5-1.3): 3.
4. The enrichment resolving device according to claim 1, wherein,
the support structure is arranged at the upstream of the desorption tube in the sampling direction of the particles;
preferably, the ratio of the distance between the support structure and the resolution tube to the total length of the tube body is (0.3-0.7): 3;
further preferably, the ratio of the distance between the analysis tube and the sample inlet to the total length of the tube body is (1-1.7): 3.
5. The enrichment resolving device according to claim 1, wherein,
the enrichment analysis device further comprises a lining, wherein the lining is arranged inside the tube body and located between the sample inlet and the filter membrane.
6. The enrichment resolution device according to claim 1,
the enrichment analysis device further comprises a patch temperature sensor, wherein the patch temperature sensor is positioned outside the tube body and close to the filter membrane, and is back to one side of the tube body with the analysis tube.
7. The enrichment resolution device according to claim 1,
two sides of the pipe body are sealed by using first O rings, preferably, the first O rings are made of fluororubber or polytetrafluoroethylene;
the analysis tube is sealed by a second O-ring, preferably made of polyimide.
8. The enrichment resolving device according to claim 1, wherein,
the filter membrane is a quartz filter membrane.
9. The enrichment resolving device according to claim 1, wherein,
the magnetic conductive membrane is a metal tungsten sheet, a metal molybdenum sheet, an iron silicon sheet or an iron nickel sheet.
10. A detection device for measuring the chemical components and concentration of atmospheric particulates, which is characterized by comprising the enrichment resolution device and a flow dividing component of any one of claims 1 to 9.
11. The detection apparatus according to claim 10, further comprising:
means for detecting organic compounds in the C8-C40 volatility range in the atmospheric particulates and/or means for detecting carbonaceous components in the particulates and/or means for detecting ionic components in the particulates;
preferably, the first and second electrodes are formed of a metal,
the device for detecting the organic matters in the C8-C40 volatility range in the atmospheric particulates comprises an organic matter focusing component and a GCMS detector;
the device for detecting the carbonaceous components in the atmospheric particulates comprises an OCEC oxidation furnace, an OCEC reduction furnace and an FID detector;
the device for detecting the ion components in the atmospheric particulates comprises a capillary sample inlet pipe and a mass spectrometer;
the flow dividing component is connected with a resolving pipe on the enrichment resolving device;
the shunt part is respectively connected with the organic matter focusing part, the OCEC oxidation furnace and the capillary sampling tube;
the organic matter focusing component is connected with the GCMS detector;
the OCEC oxidation furnace is connected with the OCEC reduction furnace, and the OCEC reduction furnace is connected with the FID detector.
The capillary sampling pipe is connected with the mass spectrometer.
12. The detection apparatus according to claim 10,
the organic matter focusing component comprises a high-temperature and low-temperature component;
the high-low temperature component comprises a high-temperature module, a low-temperature module and a high-low temperature switching module.
13. The detection apparatus according to claim 12,
the high-temperature module comprises an adsorption tube and a resistance wire wound outside the adsorption tube, and a Tenax adsorbent is filled inside the adsorption tube;
preferably, a layer of insulating sleeve is further arranged between the adsorption tube and the resistance wire, and the insulating sleeve is wrapped on the periphery of the adsorption tube;
further preferably, the high-temperature module further comprises a protection unit, and the protection unit wraps the periphery of the resistance wire;
more preferably, the high temperature module further includes a temperature sensor, the temperature sensor is disposed outside the adsorption pipe body and located between the insulation sleeve and the adsorption pipe.
14. The detection apparatus of claim 12,
the low-temperature module comprises a refrigerating piece and a metal block, the metal block is composed of two symmetrical sub-metal blocks which are provided with semicircular grooves at the center and can be opened and closed, and the adsorption tube can be attached to the groove formed by the two symmetrical sub-metal blocks;
preferably, the first and second electrodes are formed of a metal,
the cold end of the refrigeration sheet is tightly attached to the metal block.
15. The detection apparatus of claim 12,
the high-low temperature switching module comprises a pneumatic driving device, and the pneumatic driving device controls the low-temperature metal block to be separated and closed so as to realize the switching of the adsorption tube between a high-temperature mode and a low-temperature mode;
preferably, the first and second liquid crystal display panels are,
when the pneumatic driving device is filled with carrier gas, the two symmetrical sub metal blocks move relatively, so that an interval exists between the two symmetrical sub metal blocks and the adsorption tube, the heating module is controlled to work, and the heating module is in a high-temperature mode;
when the pneumatic device is not communicated with carrier gas, the two symmetrical sub-metal blocks move oppositely, so that the two symmetrical sub-metal blocks are attached to the adsorption tube, the heating module is controlled to stop working, and the pneumatic device is in a low-temperature mode.
16. An on-line measurement and analysis method for the chemical components and concentrations of atmospheric particulates by using the enrichment resolution device of any one of claims 1 to 9 or the detection equipment of any one of claims 10 to 15.
17. The method of claim 16, comprising
Sampling, purging, analyzing and shunting, and measuring; wherein the content of the first and second substances,
a sampling step: introducing a sample to be detected into an enrichment and desorption device to enrich particulate matters in the enrichment and desorption device;
a purging step: carrying out carrier gas purging on the enrichment analysis device and the transmission line thereof or the detection equipment and the transmission line thereof to remove redundant gas;
analyzing and shunting steps: enabling the particles adsorbed in the enrichment desorption device to be subjected to high-temperature thermal desorption and divided into one, two or three gas flows, wherein the divided gas flows enter an organic matter focusing component for secondary capture and/or enter an OCEC (oxygen-based fuel cell) oxidation furnace, and/or the divided gas flows enter a capillary sample inlet pipe;
a measurement step: thermally analyzing the granular organic matters secondarily enriched in the organic matter focusing component again after being shunted, and entering a GCMS detector for sortingSeparating and measuring; and/or the sample entering the OCEC oxidizing furnace after being divided is oxidized into CO 2 Then CO 2 Enters an OCEC reducing furnace to be reduced into CH 4 After, CH 4 Entering an FID detector for quantitative detection; and/or the particles after the shunting enter a mass spectrometer through a capillary sampling tube to directly detect the substance characteristic ion signals.
CN202211683200.2A 2022-12-27 2022-12-27 Enrichment analysis device, detection equipment and detection method for measuring chemical components and concentration of atmospheric particulate matters Pending CN115979782A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117929085A (en) * 2024-03-20 2024-04-26 内蒙古蒙嘟嘟科技服务有限公司 Atmospheric particulate matter carbonaceous component enrichment analysis and detection equipment

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117929085A (en) * 2024-03-20 2024-04-26 内蒙古蒙嘟嘟科技服务有限公司 Atmospheric particulate matter carbonaceous component enrichment analysis and detection equipment

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