CN110044663B - Laboratory flame intermediate product sampling system and analysis method - Google Patents
Laboratory flame intermediate product sampling system and analysis method Download PDFInfo
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- CN110044663B CN110044663B CN201910314722.7A CN201910314722A CN110044663B CN 110044663 B CN110044663 B CN 110044663B CN 201910314722 A CN201910314722 A CN 201910314722A CN 110044663 B CN110044663 B CN 110044663B
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
- G01N1/2205—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling with filters
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N1/02—Devices for withdrawing samples
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/66—Thermal conductivity detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
- G01N2030/201—Injection using a sampling valve multiport valves, i.e. having more than two ports
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
- G01N2030/202—Injection using a sampling valve rotary valves
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Abstract
The invention discloses a laboratory flame intermediate product sampling system which comprises a gas sampling module and an online analysis module, wherein the gas sampling module comprises a combustor, a microprobe, a particle filter, a dewatering filter pipe and a microprobe, the microprobe is installed on a five-way pneumatic rotary valve through a first reducing adapter, the five-way pneumatic rotary valve is sequentially connected with the particle filter, the dewatering filter pipe and an online detection system through stainless steel pipes, a first switch valve is arranged on a pipeline for connecting the dewatering filter pipe with the online detection system, and the front end of the online detection system is connected with the stainless steel pipes through a second reducing adapter. The invention also provides an analysis method based on the sampling system, and the laboratory flame gas sampling system and the analysis method can reduce the deviation of the existing device and provide the flame intermediate product on-line sampling system and the analysis method with more accuracy and good reproducibility.
Description
Technical Field
The invention relates to the technical field of quartz probe online sampling, in particular to a laboratory flame intermediate product sampling system and an analysis method.
Background
Currently, the energy consumption in the world is still mainly fossil fuel, and statistically about 85% of the energy consumption is from the combustion of fossil fuel, and the combustion is accompanied by the existence of serious pollution and harmful emission problems, especially carbon dioxide, polycyclic aromatic hydrocarbon and soot particulate matters, so that the reduction of the emission of carbon dioxide and pollutants, the research and the application of clean combustion energy and sustainable energy are urgently needed.
At present, many scientific research workers at home and abroad vigorously develop the combustion research in the aspect, the laboratory flame is utilized to simulate the actual combustion condition, so that the method can be applied to the actual combustion condition, in order to reduce the emission of pollutants such as carbon dioxide and carbon smoke particles, the flame is generated by utilizing one-dimensional laminar flow to a diffusion flame burner, a jet flame burner and the like, a probe sampling system and a gas analysis and detection instrument are utilized to perform related research and analysis on the intermediate components and the generated products of the flame, but still many problems are not solved, according to the reference of related documents and patents, the offline sample detection and analysis is mostly adopted in the research, the collection and storage of the offline sample depend on a plurality of groups of quantitative rings and a plurality of gas injection valves, so that the concentration collection of a plurality of sample points can be performed, although the sample sampling time is saved, the aging phenomenon of the sample collected in the high-temperature flame possibly occurs through the storage, therefore, the deviation of the quantitative result of the polycyclic aromatic hydrocarbon is large, the data is not representative, and the maintenance requirement and the frequency are high; at present, a few researches are turned to an on-line sampling analysis mode, for example, the invention patent with the application number of CN201610445663.3 discloses that the leakage maintenance operation of a plurality of groups of quantitative rings is avoided by utilizing flame real-time sampling analysis, but the sampling contains a large amount of moisture, and the moisture can damage a chromatographic column commonly used for measuring hydrocarbons to a certain extent, so that the chromatographic column can be seriously disabled; the invention with the application number of CN200910057246.1 discloses an on-line chromatographic analysis method, which utilizes a chromatographic column with good water resistance to analyze water to reduce the water entering a system, but still has certain harm, because a capillary chromatographic column used for separating hydrocarbon, particularly non-aromatic hydrocarbon mixtures is generally very sensitive to water, the water can change the polarity of the chromatographic column, the peak trailing is widened, the separation effect is deteriorated, and simultaneously, a series of problems of aggravated column loss, water resistance loss of the chromatographic column, peak bifurcation, base line deterioration, improved detection limit, deteriorated repeatability of quantitative data and the like can be caused, and most of the problems can be analyzed only after being condensed into gas and liquid phases off line; the invention patent with the application number of CN201610577469.0 discloses a quartz probe online sampling system, and provides a laboratory flame quartz probe online sampling system and a sampling method, which can perform online sampling for liquid fuel combustion flame and can accurately control real-time online analysis at different flame positions, but accurate separation of hydrocarbon substances in the flame quartz probe online sampling system and the sampling method are not realized, and the separation effect is poor.
Disclosure of Invention
In view of the above problems, the present invention provides a sampling system and an analysis method for a flame intermediate product in a laboratory, which reduce the deviation of the existing devices and provide a more accurate and reproducible online sampling system and analysis method for flame gas.
In order to achieve the purpose, the invention adopts the technical scheme that: the utility model provides a laboratory flame intermediate product sampling system, includes gaseous sampling module and on-line analysis module, its characterized in that gaseous sampling module includes combustor, microprobe, particulate filter, dewatering filter tube, the microprobe is installed on the pneumatic rotary valve of five-way through first reducing adapter, the pneumatic rotary valve of five-way is connected gradually through nonrust steel pipe with particulate filter, dewatering filter tube, on-line measuring system, be equipped with first ooff valve on the pipeline that dewatering filter tube and on-line measuring system are connected, the front end of on-line measuring system is connected with nonrust steel pipe through second reducing adapter.
Further, the online analysis module comprises a first quantitative ring, a second quantitative ring, a first sampling valve, a second sampling valve, a switch switching valve, a vacuum pump, an analysis instrument and a gas carrying bottle, wherein the first sampling valve and the switch switching valve are six-way valves, the second sampling valve is a ten-way valve, the first sampling valve, the second sampling valve and the switch switching valve are sequentially arranged, the first sampling valve is provided with six interfaces A-F along the clockwise direction, the second sampling valve is provided with ten interfaces G-P along the clockwise direction, the switch switching valve is provided with six interfaces Q-V along the clockwise direction, a sample is introduced from an interface E of the first sampling valve, the first sampling valve and the second sampling valve are connected between the interfaces D and O through a stainless steel pipeline, a pressure sensor is arranged on the stainless steel pipeline between the interfaces D and O, the second sampling valve and the switch switching valve are connected between the interfaces H and Q through a stainless steel pipeline, and a gas carrying bottle is arranged between the second sampling valve and the switch switching valve The first quantitative ring is connected between the interface F and the interface C, the second quantitative ring is connected between the interface P and the interface M, the first filling column is arranged between the interface I and the interface L, the carrier gas bottle is respectively connected with the three carrier gas interfaces A, J and the interface G, the third filling column is arranged between the interface R and the interface S, the interface B is connected with the analytical instrument, the first capillary column is arranged between the interface B and the analytical instrument, the interface T is connected with the analytical instrument, the air inlet end of the vacuum pump is connected with the interface N, a second switch valve and a vacuum pressure gauge are arranged between the vacuum pump and the second sampling valve interface N, and a current limiter is arranged.
Further, the analytical instrument is a gas chromatography mass spectrometer, wherein the interface B is connected with the mass spectrometry detector, and the interface T is connected with the thermal conductivity detector.
Further, on-line analysis module still includes computer, electric heating tape and thermostat, gas chromatography mass spectrograph and computer pass through the electricity and connect, the electric heating tape passes through the electricity with the thermostat and is connected, twines by the electric heating tape from the microprobe to the second ration ring is terminal to be controlled its temperature by the thermostat and sets for.
Furthermore, the circular valve port at the bottom end of the five-way pneumatic rotary valve is connected with a stainless steel pipe, the other four circular valve ports of the five-way pneumatic rotary valve are sequentially connected with the first reducing adapter and the microprobe through the stainless steel pipe respectively, the central lines of the other four circular valve ports of the five-way pneumatic rotary valve are positioned on the same horizontal plane, the central lines of the two adjacent circular valve ports are perpendicular to each other, and the positions are adjusted through external pneumatic control.
Further, the dewatering filter tube is transparent quartz tube, and both ends have respectively to be covered with the filter orifice plate of evenly ventilating aperture, and top department is equipped with sealed entry and is used for filling dewatering material and blocks up sealedly, wherein fills dewatering material, and the dewatering material that the entry end was filled is the silica gel granule drier, and the dewatering material that the exit end was filled is the molecular sieve drier, wherein, what the silica gel granule chooseed for use is the globular silica gel of A type of 5mm diameter, the molecular sieve drier is the 3A molecular sieve that the diameter is 5mm, the aperture of filter orifice plate is < ═ 5 mm.
And the micro probe is fixed on the fixing support through the cross connecting piece.
Further, the device comprises an exhaust gas treatment device which is connected with the outlet end of the vacuum pump through a stainless steel pipe, and a digital flow meter 22 is arranged between the second switch valve 20 and the vacuum pump 21.
Furthermore, the probe is a fused quartz microprobe, and the surface of the probe is coated with a polyimide coating.
The invention also provides a laboratory flame intermediate product sampling analysis method, which comprises the following steps:
s1, after a burner generates stable flame, the tip of a microprobe is deeply inserted to a certain target position in the flame, a gas sample at the target position is extracted by a vacuum pump to respectively enter two channels, wherein one channel is a sample, the sample sequentially enters a first quantitative ring from a point E, F of a first sampling valve, and a point C, D is empty; the other channel is that the sample enters the second quantitative ring from a point O, P of the second sampling valve and is sequentially discharged to a point M, N, so that the replacement and filling of the gas sample in the quantitative ring in the gas sampling valve are realized;
s2, after the two quantitative rings are filled with the sample, when the operation is carried out for 0.01min, the first sampling valve and the second sampling valve rotate clockwise to switch the sites, the first sampling valve is closed when the operation is carried out for 1min, the gas sample introduction action of the first sampling valve channel is completed, the sample gas starts to be sequentially separated through a first capillary column, enters the mass spectrum detector and starts to be analyzed, and the temperature rise program is set as follows when the operation is started: keeping at 60 deg.C for 8min, heating to 100 at 15 deg.C/min for 2min, heating to 150 deg.C at 15 deg.C/min for 10min, and heating to 180 deg.C at 15 deg.C/min for 8 min;
the negative polarity of the thermal conductivity detector is turned on at S3.1.8min, and is turned off at 2.8 min; closing the second sampling valve when 3min is needed, completing the sample introduction of the permanent gas in the channel of the second sampling valve, and simultaneously carrying redundant hydrocarbon components carried by the carrier gas 3 to be discharged to a waste gas discharge pipeline through the first filling column in a back blowing mode; at this point the permanent gas component begins to enter further separation, H2、O2、N2、CH4After the CO sequentially enters a third packed column, H2And O2Has already appeared, and CO2At this point, the carrier gas pressure is set at 35-40 psi;
at S4.3.8min, the switch switching valve is switched to enable CO2Does not enter into the third fillingThe column (molecular sieve column) is filled, directly enters TCD analysis through a site V, U, T of the switch switching valve to generate a peak, and the switch switching valve is closed in 6 minutes, so that CO is prevented from being analyzed by a third packed column2Fails by adsorption, when in CH in the third packed column4And CO are sequentially separated to continue to generate peaks, so that different species of the same flame gas sample are separated and characterized through the two channels;
s5, after obtaining the chromatogram of each substance peak, pre-calibrating light hydrocarbon species and permanent gas species in the flame by standard gas with known components and concentration, calculating the area of each peak by a workstation, establishing a corresponding relation between a peak area response value and known target concentration, establishing a calibration curve by a plurality of points generated by the standard gas with a plurality of concentrations, and further obtaining the concentration value of each sample component by the area response value and the calibration curve of the sample component.
Compared with the prior art, the invention has the beneficial effects that:
1. the pressure sensor is adopted to monitor the pressure in the sampling quantitative ring in real time, so that the consistency of the sampling quantity of each time is ensured;
2. the particle filter and the dewatering filter pipe are adopted to prevent the damage to the chromatographic instrument due to the carbon smoke particles, moisture and the like in the sample;
3. the five-way starting rotary valve is adopted, and the fused quartz microprobe is adopted, so that the replacement frequency of the probe in an experiment is reduced, the repeatability of a sampling point after the probe is replaced is ensured, and meanwhile, the fused quartz microprobe reduces the interference on flame;
4. by adopting the novel analysis method, more substances can be separated without overlapping by adopting the gradient arrangement of time and temperature, various hydrocarbons in the flame including isomers, permanent gases and other intermediate products are analyzed, and a more sufficient and reliable basis is provided for the combustion mechanism analysis of the flame.
Drawings
FIG. 1 is a schematic view of the overall structure of the present invention;
FIG. 2 is a partial schematic view of the probe and the five-way pneumatic rotary valve of the present invention;
FIG. 3 is a schematic view of the water removal filter tube of the present invention;
FIG. 4 is a view A-A of FIG. 3 of the present invention;
FIG. 5 is a three-dimensional view of a five-way pneumatic rotary valve of the present invention;
FIG. 6 is a cross-sectional view of a five-way pneumatic rotary valve of the present invention;
FIG. 7 is a schematic diagram of a fill state structure of a sample injection valve of a line analysis module according to the present invention;
FIG. 8 is a schematic view of a sample injection state structure of a sample injection valve of the line analysis module according to the present invention;
FIG. 9 is a schematic diagram of a line analysis module sample injection valve in a separated state according to the present invention;
in the figure: 1-burner, 101-oxidant end, 102-fuel end, 2-microprobe, 3-first reducing adapter, 4-five-way pneumatic rotary valve, 5-cross connecting piece, 6-particle filter, 7-fixed support, 8-dewatering filter tube, 9-first switch valve, 10-temperature controller, 11-second reducing adapter, 12-gas carrying cylinder, 13-first quantitative ring, 14-pressure sensor, 15-second quantitative ring, 16-first sampling valve, 17-second sampling valve, 18-switch switching valve, 19-vacuum pressure gauge, 20-second switch valve, 21-vacuum pump, 22-digital flowmeter, 23-waste gas processing device, 24-gas chromatograph mass spectrometer, 25-computer, 25-gas chromatography mass spectrometer, 26-flow restrictor, 27-first capillary column, 28-first packed column, 29-second packed column, 30-third packed column.
Detailed Description
The invention provides a laboratory flame intermediate product sampling system and an analysis method. Technical solutions provided by embodiments of the present invention to solve the above technical problems, for better understanding of the above technical solutions, the above technical solutions will be described in detail with reference to the drawings and specific embodiments of the present disclosure.
As shown in fig. 1, laboratory flame intermediate product sampling system includes gaseous sampling module and online analysis module, and wherein gaseous sampling module includes combustor 1, microprobe 2, particle filter 6, dewatering filter tube 8, microprobe 2 is installed on five-way pneumatic rotary valve 4 through first reducing adapter, five-way pneumatic rotary valve 4 and particle filter 6, dewatering filter tube 8, on-line measuring system connect gradually through nonrust steel pipe, be equipped with first ooff valve 9 on the pipeline that dewatering filter tube 8 and on-line measuring system are connected, the front end of on-line measuring system is connected with nonrust steel pipe through second reducing adapter 11.
As shown in fig. 7-9, the online analysis module includes a first quantitative ring 13, a second quantitative ring 15, a first sampling valve 16, a second sampling valve 17, a switch switching valve 18, a vacuum pump 21, an analyzer, and a carrier gas bottle 12, wherein the first sampling valve 16 and the switch switching valve 18 are six-way valves, the second sampling valve 17 is a ten-way valve, the first sampling valve 16, the second sampling valve 17, and the switch switching valve 18 are sequentially arranged, the first sampling valve 16 is provided with six ports a-F in a clockwise direction, the second sampling valve 17 is provided with ten ports G-P in a clockwise direction, the switch switching valve 18 is provided with six ports Q-V in a clockwise direction, a sample is introduced through a port E of the first sampling valve 16, the first sampling valve 16 and the second sampling valve 17 are connected between ports D and O through a stainless steel pipeline, a pressure sensor 14 is disposed on the stainless steel pipeline between the ports D and O, the second sampling valve 17 and the switch switching valve 18 are connected between a connector H and a connector Q through a stainless steel pipeline and are provided with a second filling column, the first quantitative ring 13 is connected between a connector F and a connector C, the second quantitative ring 15 is connected between a connector P and a connector M, a first filling column 28 is arranged between a connector I and a connector L, the gas carrying bottle 12 is respectively connected with three carrier gas connectors A, J and G, a third filling column 30 is arranged between a connector R and a connector S, a first capillary column 27 is arranged between a connector B and a connector analyzer, a connector T is connected with the analyzer, a connector N is connected with the gas inlet end of the vacuum pump 21, a second switch valve 20 and a vacuum pressure gauge 19 are arranged between the vacuum pump 21 and the connector N of the second sampling valve, and a current limiter 26. In the above embodiment, the analyzer is a gas chromatograph mass spectrometer 24, wherein interface B is connected to the mass spectrometer and interface T is connected to the thermal conductivity detector.
In the above embodiment, the first dosing ring has a capacity of 0.25ml and the second dosing ring has a capacity of 1 ml.
Further preferred scheme, on-line analysis module still includes computer 25, electric heating tape and thermostat 10, gas chromatography mass spectrometer 24 and computer 25 are through the electricity connection, the electric heating tape is through the electricity with thermostat 10 being connected, twines by the electric heating tape from microprobe 2 to second ration ring 15 end to by thermostat 10 to control its temperature and set for, heat and the purpose of keeping constant temperature in order to prevent that partial sample component from taking place the condensation in the pipeline, the volume of advancing is inconsistent, influences the analysis result. .
In the above embodiment, the pressure sensor 14 can monitor the pressure between the first quantitative ring 13 and the second quantitative ring 15 in real time and the holding condition thereof, a vacuum pressure gauge 19 and a second switch valve 20 are connected between the second sampling valve 17 and the vacuum pump 21, the vacuum pressure gauge 19 is used for measuring the pressure at the inlet end of the vacuum pump and then connected to one end of the vacuum pump 21, a digital flow meter 22 is installed between the second switch valve 20 and the vacuum pump 21, the digital flow meter 22 is used for judging whether the probe tip is blocked and determining whether other microprobes 3 need to be replaced, and the outlet end of the digital flow meter 22 is connected to the exhaust gas treatment device 23, so that the sample enters the exhaust gas treatment device for treatment.
As shown in fig. 2, 5 and 6, it is further preferable that the circular valve port at the bottom end of the five-way pneumatic rotary valve 4 is connected to a stainless steel pipe, the other four circular valve ports of the five-way pneumatic rotary valve 4 are respectively connected to the first reducing adapter 3 and the microprobe 2 in sequence through the stainless steel pipe, the center lines of the other four circular valve ports of the five-way pneumatic rotary valve 4 are located on the same horizontal plane, the center lines of the two adjacent circular valve ports are perpendicular to each other, and the position is adjusted by external pneumatic control. This gaseous rotary valve of five-way is the probe that leads to in order to avoid accidental factor in the experiment damages, blocks up, melts etc. and causes the probe replacement process of sampling in-process, and then has avoided the change of the micron order of the position in a set of experiment, influences the experimental result. The internal structure is as shown in the above figure, 4 valve sites are provided in total, namely, the probe can be rotatably replaced four times by one-time installation, so that the in-situ sampling can be kept, when the probe at the b site needs to be replaced, the valve utilizes external pneumatic control to adjust the position, the valve body rotates 90 degrees clockwise, namely, the probe at the original b site is replaced by the probe at the a site, and the sampling position point can be kept in the in-situ.
As shown in fig. 3 and fig. 4, a further preferable solution on the basis of the above embodiment is that the water removing filter tube 8 is a transparent quartz tube, two ends of the water removing filter tube are respectively provided with filter pore plates with uniformly-distributed small ventilation holes, a sealing inlet is arranged above the filter tube for filling the water removing material and blocking the sealing, wherein the water removing material is filled in the water removing filter tube, the water removing material filled in the inlet end is silica gel particle desiccant, the water removing material filled in the outlet end is molecular sieve desiccant, wherein the silica gel particles are selected from a type a spherical silica gel with a diameter of 5mm, the molecular sieve desiccant is a 3A molecular sieve with a diameter of 5mm, and the pore diameter of the filter pore plate is less than 5.
In the above embodiment, the water removal filter tube 8 is a quartz tube, which has characteristics of high temperature resistance, inertia, etc., and at the same time, the transparent material is convenient for observing color change and whether the color change needs to be changed, wherein the water removal material filled in the tube is a silica gel particle desiccant on the left side (inlet end), and a molecular sieve desiccant on the right side (outlet end), because the molecular sieve has strong water removal capability and long service time, the silica gel is placed on the left side for preliminary water removal and indicating water absorption saturation, and the silica gel is replaced when the color change is half, and the molecular sieve is placed on the right side for further water removal. Since the sampling system is required to remove moisture from the flame sample gas and simultaneously has no adsorption effect on other hydrocarbons and permanent gases, silica gel particles should be selected from silica gel drying agents and molecular sieve drying agents with proper pore sizes. The silica gel particles in the system are selected from A-type spherical silica gel with the diameter of 5mm, the silica gel has small aperture, large specific surface area and high adsorption speed, and is suitable for the environment with the relative humidity RH of 20-50. In order to facilitate the gas to pass through the drying agent quickly, particles with the diameter of 5mm are selected, therefore, the pore plates on the two sides of the left end are 5mm, and the pore diameter of the system is 4.5 mm. The water absorption capacity of the molecular sieve desiccant is slightly influenced by relative humidity, even when the relative humidity is 10%, the molecular sieve desiccant has high adsorption capacity, a 3A molecular sieve is selected in the system, the pore diameter of the molecular sieve is 3A, and the diameter of water molecules is about 2.6A, so that the molecular sieve desiccant is mainly used for adsorbing water, and does not adsorb any molecules with the diameter larger than 3A in sample gas, and other target species cannot be adsorbed. For convenience of consistency, the molecular sieve is also 5mm, and the pore plate at the outlet at the right end of the dewatering drying pipe is preferably 4.5mm in pore diameter. When measuring light hydrocarbon and permanent gas, the sampling pipeline is not heated, so a silica gel and molecular sieve combined type dewatering mode is used, when measuring aromatic hydrocarbon components, the pipeline needs to be heated to prevent the components from condensing, the temperature is generally set to 150 ℃, the silica gel cannot resist high temperature, and at the moment, the left side and the right side of the dewatering drying pipe are filled with 3A molecular sieve drying agents. The particulate filter 6 may filter soot particles in the sample.
The scheme further optimized on the basis of the embodiment is that the device further comprises a fixing mechanism and an exhaust gas treatment device, wherein the fixing mechanism comprises a cross-shaped connecting piece 5 and a fixing support 7, and the microprobe 2 is fixed on the fixing support 7 through the cross-shaped connecting piece 5 to keep the microprobe 2 stable in the sampling process. The exhaust gas treatment device is connected to the outlet end of the vacuum pump through a stainless steel pipe, and a digital flow meter 22 is installed between the second switching valve 20 and the vacuum pump 21. The digital flow meter 22 is used for judging whether the probe tip is blocked, determining whether other microprobe 2 needs to be replaced, and accessing the waste gas treatment device 23, so that the residual sample enters the waste gas treatment device for treatment.
The scheme of further optimizing on the basis of the embodiment is that the microprobe is a fused quartz microprobe, and the surface of the microprobe is coated with a polyimide coating, so that the toughness of the microprobe is improved.
The invention also provides a laboratory flame intermediate product analysis method, which comprises the following steps:
s1, after a burner generates stable flame, the tip of a microprobe is deeply inserted to a certain target position in the flame, a gas sample at the target position is extracted by a vacuum pump to respectively enter two channels, wherein one channel is that the sample sequentially enters a first quantitative ring from a point E, F of a first sampling valve, and a point C, D is empty; the other channel is that the sample enters the second quantitative ring from a point O, P of the second sampling valve 3 and is sequentially discharged to a point M, N, so that the displacement and filling of the gas sample in the quantitative ring in the gas sample injection valve are realized;
s2, after the two quantitative rings are filled with the sample, when the operation is carried out for 0.01min, the first sampling valve and the second sampling valve rotate clockwise to switch the sites, the first sampling valve is closed when the operation is carried out for 1min, the gas sample introduction action of the first sampling valve channel is completed, the sample gas starts to be sequentially separated through a first capillary column, enters the mass spectrum detector and starts to be analyzed, and the temperature rise program is set as follows when the operation is started: keeping at 60 deg.C for 8min, heating to 100 at 15 deg.C/min for 2min, heating to 150 deg.C at 15 deg.C/min for 10min, and heating to 180 deg.C at 15 deg.C/min for 8 min;
the negative polarity of the thermal conductivity detector is turned on at S3.1.8min, and is turned off at 2.8 min; closing the second sampling valve when the sampling time is 3min, completing the sample introduction of the permanent gas in the channel of the second sampling valve, and simultaneously carrying redundant hydrocarbon components by the carrier gas to be discharged to a waste gas discharge pipeline through the first filling column in a back blowing mode; at this point the permanent gas component begins to enter further separation, H2、O2、N2、CH4After the CO sequentially enters a third packed column, H2And O2Has already appeared, and CO2At this time, the user does not enter;
at S4.3.8min, the switch switching valve is switched to enable CO2The mixture does not enter a third packed column (molecular sieve column), directly enters TCD analysis through a site V, U, T of a switch switching valve to generate a peak, and is closed in 6 minutes, so that CO is prevented from being analyzed by the third packed column2Fails by adsorption, when in CH in the third packed column4And CO are sequentially separated to continue to generate peaks, so that different species of the same flame gas sample are separated and characterized through the two channels;
s5, after obtaining the chromatogram of each substance peak, pre-calibrating light hydrocarbon species and permanent gas species in the flame by standard gas with known components and concentration, calculating the area of each peak by a workstation, establishing a corresponding relation between a peak area response value and known target concentration, establishing a calibration curve by a plurality of points generated by the standard gas with a plurality of concentrations, and further obtaining the concentration value of each sample component by the area response value and the calibration curve of the sample component.
In step S1, the burner is adjusted such that one end of the fused silica microprobe is located between the oxidant end 101 and the fuel end 102 of the burner and is close to the center of the outlet end face of the fuel end, and the outlet end of the burner is focused by the digital cameraAnd the center position is used for finely adjusting the center and the upper and lower positions of the fused quartz microprobe so that the fused quartz microprobe is positioned at the center position of the end face of the outlet. As shown in fig. 7, in the sample filling state diagram, the first quantitative ring 13 and the second quantitative ring 15 are filled with samples, and after the first quantitative ring 13 and the second quantitative ring 15 are filled with samples, the first sampling valve 16 and the second sampling valve 16 are switched to rotate to switch the sites, and are respectively connected with and disconnected from adjacent sites, as shown in fig. 8, the valve 1 is closed at 1min, so that the gas sample introduction action of the first sampling valve channel is completed, and the sample gases start to sequentially separate through the first capillary column and enter the mass spectrometer for analysis; 3.8min, the switch is switched to switch the valve 18 to CO, as shown in FIG. 92The mixture does not enter a third packed column (molecular sieve column), directly enters TCD analysis through a site V, U, T of a switch switching valve to generate a peak, and is closed in 6 minutes, so that CO is prevented from being analyzed by the third packed column2Fails by adsorption, when in CH in the third packed column4And CO are separated in sequence to continue peaking, so that different species of the same flame gas sample are separated and characterized through two channels.
In step S2, in order to ensure effective separation of the low carbon hydrocarbon component (C1-C4) in the first sampling valve channel, the flow rate of the first capillary column is set to 1ml, the split ratio is 20-40, the separation degree and the peak shape are good, the first capillary column only needs to be kept at the normal temperature of 50-60 ℃ for a period of time, and can be separated after 8min, for the C4 isomer and the C4-C7 hydrocarbon component in the column which do not peak, the C1-C7 component can not be completely separated at the normal temperature, in order to avoid the occurrence of overlapping peaks and the like, the temperature is increased to 100 ℃ at the speed of 15 ℃/min, and is kept for 2min, part of the substances are separated in the period of time, for the component after 12.667min, the C1-C7 component is continuously increased to 150 ℃ at the speed of 15 ℃/min, and is kept for 10min, at the moment, the C1-C7 component has separated from the capillary column, and only benzene and toluene are left, in order to save the analysis time, the temperature is continuously raised to 180 ℃ at the speed of 15 ℃/min, and then the benzene and the toluene can be separated from the chromatographic column to obtain the peak. For the separation of the permanent gas component in the channel of the valve 3, the permanent gas component can be separated at normal temperature, namely the permanent gas component can be separated after keeping 12.667min at 35-60 ℃, the carrier gas pressure and the valve event have certain requirements, the carrier gas pressure and the valve switching time are matched to reach the test condition, the carrier gas pressure is set to 35-40psi, when the valve is operated for 3min, the switch switching valve 3 is switched on and off, and other moisture, light hydrocarbon and polycyclic aromatic hydrocarbon components are just blown back completely, so that the permanent gas component cannot enter the subsequent columns 3 and 4 and the thermal conductivity detector, and meanwhile, the target permanent component is ensured to completely enter the column 3. Because there is only one heating column box, the temperature settings integrate the components and conditions of channel 1 and channel 2, and finally, verified, the temperature program is set as: keeping the temperature at 60 ℃ for 8min, heating to 100 at 15 ℃/min for 2min, heating to 150 ℃ at 15 ℃/min for 10min, heating to 180 ℃ at 15 ℃/min, and keeping the temperature for 8min, wherein the analysis time is shortest and the effect is best.
The specific embodiment is as follows:
firstly, adjusting the position of a burner to enable one end of a fused quartz microprobe to be positioned between an oxidant end and a fuel end of the burner and to be close to the center of an outlet end face of the fuel end, focusing the center of the outlet end of the burner by using a digital camera, and finely adjusting the center and the up-and-down position of the fused quartz microprobe to enable the fused quartz microprobe to be positioned at the center of the outlet end face.
1. The standard gas is controlled by a flowmeter to be respectively introduced into a fuel end (permanent gas, light hydrocarbon and fuel) and an oxidant end (oxygen), the protection gas nitrogen is continuously introduced around the circular ring of the combustor (the surrounding air flow is prevented from disturbing the circular ring), the gas in the combustor cavity can be completely replaced after 5min, the outlet end of the combustor cavity is continuously kept to be the flow of the standard gas, and the sampling is carried out at the position 0mm away from the fuel end face.
2. And opening a vacuum pump to perform gas replacement sampling, closing the second switch valve and the vacuum pump when the pressure displayed by a vacuum pressure gauge is reduced to be unchanged after about half a minute, stopping vacuumizing, closing the first switch valve when the pressure displayed by the pressure sensors in the pipeline and the quantitative ring is increased to the initial atmospheric pressure and is unchanged after about 3 minutes, then starting sample introduction, and operating a pre-edited analysis method to perform analysis.
3. And (3) continuously introducing standard gas with different concentrations for 3-5 times in the step 2, and analyzing the standard gas.
4. After 3-5 groups of related spectrograms are obtained after the operation is finished, peak area integration is carried out on the spectrograms, and then the peak areas measured by the gas with different components and different concentrations entering an instrument are obtained to be plotted against the standard component concentration, so that standard curves (straight lines) with different correlation coefficients (RF) are formed.
5. In the experimental working condition, the gas at the fuel end is 50 percent C2H4And 50% N2Oxidant end 20% O2And 80% N9The flame is controlled by a flowmeter respectively, then a polytetrafluoroethylene tube is connected into two ports (the distance between the upper port and the lower port is 8mm) of a combustor, ignition is carried out in the middle of the two ports, and then protective gas of the upper port and the lower port is opened to form stable one-dimensional circular plane flame. And after flame continuously burns until the flame is stable, sampling at a first sampling point (0mm) at the moment, opening a vacuum pump to perform gas replacement sampling, closing a second switch valve and the vacuum pump when the pressure displayed by a vacuum pressure gauge is reduced to be unchanged after about half a minute, stopping vacuumizing, closing the first switch valve when the pressure displayed by a pressure sensor in a pipeline and a quantitative ring is increased to be the initial atmospheric pressure and is unchanged after about 3 minutes, removing a combustor, avoiding the situation that a probe is in a continuous high-temperature environment, then starting to sample, and operating a pre-edited analysis method to analyze. After the point analysis is finished, the sampling points are adjusted to move upwards for a certain distance (the distance is 0.5mm, and 17 sampling points are used in total, and can be set to be different), and then the sampling and analyzing processes are repeated until 17 sampling points are finished. When the flame gas sample is measured, accurate sample injection is needed under the chromatographic condition which is completely the same as that of a drawn standard curve, and the content of the measured component is calculated from the curve according to the obtained peak area (or peak height).
6. The specific calculation method of the external standard quantitative method (ESTD) is as follows:
CS＝Cr×AS/Ar
wherein: cs is the sample concentration;
cr is the standard component concentration;
as is the sample peak area;
ar is the standard component peak area.
The concentration values of the sample and the standard gas and the respective peak areas can be related by utilizing the calculation formula, and when Cr, As and Ar are known, the Cs values of different sampling points, namely the concentration value of the target sample, can be obtained.
In the above implementation, the parameters are set as follows:
in the parameter setting table, the first sampling valve 16 corresponds to the valve 1, the second sampling valve 17 corresponds to the valve 3, and the on-off switching valve 18 corresponds to the valve 2.
In the above experimental procedure, 3 sets of standard gases with different concentrations and one set of samples were measured. The two channels obtain chromatographic information, and finally, hydrocarbon components and permanent gas components in the flame can be respectively detected through integration and data processing, so that qualitative and quantitative results are obtained for research and analysis of the soot generation mechanism. The experimental results obtained are given in the following table:
the calculated relative error values are as follows:
note: "-" indicates that no component is present at the operating flame or the sampling site.
In conclusion, by the laboratory flame intermediate product sampling system and the analysis method provided by the invention, most of hydrocarbon substances can be separated, and the finally measured content error of each substance is small.
The present invention has been described in detail with reference to the specific embodiments, but the present invention is only one of the embodiments, and the present invention is not limited to the specific embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (9)
1. A laboratory flame intermediate product sampling system comprises a gas sampling module and an online analysis module, and is characterized in that the gas sampling module comprises a burner, a microprobe, a particle filter and a dewatering filter pipe, wherein the microprobe is installed on a five-way pneumatic rotary valve through a first reducing adapter, the five-way pneumatic rotary valve is sequentially connected with the particle filter, the dewatering filter pipe and an online detection system through stainless steel pipes, a first switch valve is arranged on a pipeline for connecting the dewatering filter pipe and the online detection system, and the front end of the online detection system is connected with the stainless steel pipes through a second reducing adapter;
the on-line analysis module comprises a first quantitative ring, a second quantitative ring, a first sampling valve, a second sampling valve, a switch switching valve, a vacuum pump, an analysis instrument and a gas carrying bottle, wherein the first sampling valve and the switch switching valve are six-way valves, the second sampling valve is a ten-way valve, the first sampling valve, the second sampling valve and the switch switching valve are sequentially arranged, the first sampling valve is provided with six interfaces A-F along the clockwise direction, the second sampling valve is provided with ten interfaces G-P along the clockwise direction, the switch switching valve is provided with six interfaces Q-V along the clockwise direction, a sample is introduced from an interface E of the first sampling valve, the first sampling valve and the second sampling valve are connected between interfaces D and O through stainless steel pipelines, a pressure sensor is arranged on the stainless steel pipeline between the interfaces D and O, and the second sampling valve and the switch switching valve are connected between interfaces H and Q through the stainless steel pipelines, the device comprises a vacuum pump, a first sampling valve, a first quantitative ring, a second quantitative ring, a third filling column, a first capillary column, a third capillary column and a third capillary column, wherein the first filling column is arranged between H and Q, the first quantitative ring is connected between F and C, the second quantitative ring is connected between F and M, the first filling column is arranged between I and L, a gas carrying bottle is respectively connected with three carrier gas interfaces A, J and G, the third filling column is arranged between R and S, the second capillary column.
2. The laboratory flame intermediate sampling system of claim 1, wherein: the analyzer is a gas chromatograph mass spectrometer, wherein an interface B is connected with a mass spectrometer detector, and an interface T is connected with a thermal conductivity detector.
3. The laboratory flame intermediate sampling system of claim 2, wherein: the online analysis module further comprises a computer, an electric heating belt and a temperature controller, the gas chromatography mass spectrometer is electrically connected with the computer, the electric heating belt is electrically connected with the temperature controller, the end of the second quantitative ring from the microprobe is wound by the electric heating belt, and the temperature of the second quantitative ring is controlled and set by the temperature controller.
4. The laboratory flame intermediate sampling system of claim 1, wherein: the circular valve port at the bottom end of the five-way pneumatic rotary valve is connected with a stainless steel pipe, the other four circular valve ports of the five-way pneumatic rotary valve are sequentially connected with the first reducing adapter and the microprobe through the stainless steel pipe respectively, the central lines of the other four circular valve ports of the five-way pneumatic rotary valve are positioned on the same horizontal plane, the central lines of the two adjacent circular valve ports are mutually vertical, and the positions are adjusted by external pneumatic control.
5. The laboratory flame intermediate sampling system of claim 1, wherein: the dewatering filter tube is transparent quartz tube, and both ends have respectively to be covered with the filtration pore plate of uniform ventilation aperture, and top department is equipped with sealed entry and is used for filling dewatering material and blocks up sealedly, wherein fills dewatering material, and the dewatering material that the entry end was filled is the silica gel granule drier, and the dewatering material that the exit end was filled is the molecular sieve drier, wherein, what the silica gel granule chooseed for use is the globular silica gel of A type of 5mm diameter, the molecular sieve drier is the 3A molecular sieve that the diameter is 5mm, the aperture of filtering pore plate is < ═ 5 mm.
6. The laboratory flame intermediate sampling system of claim 1, wherein: the device also comprises a fixing mechanism, wherein the fixing mechanism comprises a cross connecting piece and a fixing support, and the microprobe is fixed on the fixing support through the cross connecting piece.
7. The laboratory flame intermediate sampling system of claim 1, wherein: still include exhaust treatment device, exhaust treatment device passes through the stainless steel pipe and connects the exit end at the vacuum pump, be equipped with digital flowmeter between vacuum pump exit end and the exhaust treatment device.
8. The laboratory flame intermediate sampling system of claim 1, wherein: the microprobe is a fused quartz microprobe, and the surface of the microprobe is coated with a polyimide coating.
9. A method for analysis of laboratory flame intermediate products using a sampling system according to any of claims 2 or 3, characterized in that it comprises the following steps:
s1, after a burner generates stable flame, the tip of a microprobe is deeply inserted to a certain target position in the flame, a gas sample at the target position is extracted by a vacuum pump to respectively enter two channels, wherein one channel is that the sample sequentially enters a first quantitative ring from a point E, F of a first sampling valve, and a point C, D is empty; the other channel is that the sample enters the second quantitative ring from a point O, P of the second sampling valve and is sequentially discharged to a point M, N, so that the displacement and filling of the gas sample in the quantitative ring in the gas sample injection valve are realized;
s2, after the two quantitative rings are filled with the sample, when the operation is carried out for 0.01min, the first sampling valve and the second sampling valve rotate clockwise to switch the sites, the first sampling valve is closed when the operation is carried out for 1min, the gas sample introduction action of the first sampling valve channel is completed, the sample gas starts to be sequentially separated through a first capillary column, enters the mass spectrum detector and starts to be analyzed, and the temperature rise program is set as follows when the operation is started: keeping at 60 deg.C for 8min, heating to 100 deg.C at 15 deg.C/min for 2min, heating to 150 deg.C at 15 deg.C/min for 10min, heating to 180 deg.C at 15 deg.C/min, and keeping for 8 min;
the negative polarity of the thermal conductivity detector is turned on at S3.1.8min, and is turned off at 2.8 min; closing the second sampling valve when the sampling time is 3min, completing the sample introduction of the permanent gas in the channel of the second sampling valve, and simultaneously carrying redundant hydrocarbon components by the carrier gas to be discharged to a waste gas discharge pipeline through the first filling column in a back blowing mode; at this point the permanent gas component begins to enter further separation, H2、O2、N2、CH4After the CO sequentially enters a third packed column, H2And O2Has already appeared, and CO2At this point, the carrier gas pressure is set at 35-40 psi;
at S4.3.8min, the switch switching valve is switched to enable CO2The mixture directly enters TCD for analysis and peak separation through a site V, U, T of the switch switching valve without entering the third packed column, and the switch switching valve is closed in 6 minutes, so that CO is prevented from being subjected to CO analysis by the third packed column2Fails by adsorption, when in CH in the third packed column4And CO are sequentially separated to continue to generate peaks, so that different species of the same flame gas sample are separated and characterized through the two channels;
s5, after obtaining the chromatogram of each substance peak, pre-calibrating light hydrocarbon species and permanent gas species in the flame by standard gas with known components and concentration, calculating the area of each peak by a workstation, establishing a corresponding relation between a peak area response value and known target concentration, establishing a calibration curve by a plurality of points generated by the standard gas with a plurality of concentrations, and further obtaining the concentration value of each sample component by the area response value and the calibration curve of the sample component.
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| CN113588861A (en) * | 2020-04-30 | 2021-11-02 | 南京理工大学 | Method for researching and regulating generation mechanism of combustion soot of aviation alternative fuel |
| CN112461607A (en) * | 2020-11-12 | 2021-03-09 | 南京理工大学 | Opposite-impact diffusion flame soot particle sampling device and sampling method thereof |
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