CN216926708U - Real-time online analytical equipment of pyrolysis of material - Google Patents
Real-time online analytical equipment of pyrolysis of material Download PDFInfo
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Abstract
The utility model discloses a real-time online analysis device for material pyrolysis, which comprises: the device comprises a pyrolysis system (1), a trapping system (2), a test system (3) and a control system (4); the pyrolysis system (1), the trapping system (2) and the testing system (3) are connected with the control system (4); the trapping system (2) is internally provided with a cooling cavity (22) and a heating cavity (23), the temperature range of the cooling cavity (22) is from room temperature to 200 ℃ below zero, and the temperature range of the heating cavity (23) is from room temperature to 1000 ℃. The apparatus of the present invention can provide real-time on-line pyrolysis, capture, separation and analysis of a substance at multiple temperature points or temperature ranges.
Description
Technical Field
The utility model belongs to the technical field of detection, and particularly relates to a real-time online analysis device for pyrolysis of a substance.
Background
Many inorganic and organic substances undergo decomposition reactions when heated to some extent. There are many organic pyrolysis processes of industrial significance, often referred to by different names depending on the particular process. Pyrolysis reaction carried out in the absence of air, called dry distillation, such as coal dry distillation, wood dry distillation; the pyrolysis of methane to produce carbon black is known as thermal decomposition; the pyrolysis of alkylbenzenes or alkylnaphthalenes to produce benzene or naphthalene is often referred to as thermal dealkylation; the production of ketene from acetone is called acetone cleavage or the like. Pyrolysis of hydrocarbons is often distinguished by thermal cracking and cracking. The real-time online understanding of the product conditions obtained in the pyrolysis process is of great significance to control of the reaction process, optimization of the reaction conditions and change of reaction substances. For example, tobacco is a biomass with complex components, and the pyrolysis products of the biomass have a crucial influence on the quality of cigarettes. Research shows that about 1/3 chemical components in the smoke come from tobacco directly, and the rest is generated by a series of complex processes such as distillation, cracking, combustion, polymerization and the like in the combustion process of cigarettes; therefore, a suitable mode system for pyrolyzing the tobacco biomass needs to be established, and the pyrolysis rule and migration condition of each component of the tobacco at any temperature are deeply researched.
In the prior art, the tobacco pyrolysis process is mainly researched by adopting a thermogravimetric analysis method (TG/DTA) and a transient cracking method (Py-GC/MS). The instant cracking method (Py-GC/MS) mainly aims at performing rapid cracking on a substance at one temperature point, and then performing analysis on a cracking product, so that the whole pyrolysis process condition of the substance along with the temperature change cannot be inspected. The obtained matters (such as saccharides, amino acids, polyphenol and the like) which are difficult to volatilize in the tobacco are cracked products at a single temperature; with this information it is difficult to find out the pyrolysis behaviour of a compound at a specific temperature. And the content of the cracked product obtained by thermal cracking is very low, generally in nanogram level, even lower than the residual substance, and the cracked product enters gas chromatography-mass spectrometry analysis, which causes inaccurate qualification and quantification.
The thermogravimetric analysis (TG/DTA) can provide stable reaction conditions under the condition of temperature programming, and is the most ideal experimental tool in the research of tobacco pyrolysis, but a single thermogravimetric analysis method cannot obtain specific substances and contents of the tobacco pyrolysis, and the thermogravimetric escaping components must be analyzed in a combined way. However, an effective combined device is still lacked in the aspect of thermogravimetric escaping component analysis at present, and the application of the thermogravimetric analysis method in the tobacco pyrolysis research is severely restricted. Currently commercialized combined systems are still difficult to play a key role in tobacco pyrolysis research due to: analysis of overlapping mass spectrum peaks has not been achieved by thermogravimetry-mass spectrometry (TG-MS); the thermogravimetry-infrared (TG-FTIR) or the thermogravimetry-infrared-mass spectrometry (TG-FTIR-MS) also has difficulty in identifying compounds with the same functional group, and the infrared peak collection is a substance existing in the whole substance pyrolysis process, and the real-time substance collection at a certain temperature point or temperature section cannot be realized. In the prior art, if the pyrolysis of a substance is to be researched at any temperature point or temperature section, an experimental condition needs to be set for the temperature point to carry out an independent experiment, for example, the whole process of pyrolysis of a certain substance is divided into 8 temperature points or temperature sections to carry out product content analysis, and 8 experiments need to be carried out respectively, which wastes time and energy and causes resource waste.
It has been reported that switching using a six-way valve or an eight-way valve is proposed to specifically trap the pyrolysis substance for subsequent analysis. However, the escaping gas decomposed by the substance after being heated has a certain temperature, the pyrolytic escaping substance is easy to be condensed in the valve to cause the pollution of the valve by adopting the switching of the valve at normal temperature, and the trapped substance can also be the substance condensed in a plurality of experiments, so the analysis result is unreliable.
The online analysis of complex escaping components in the pyrolysis of substances through a plurality of temperature points or temperature sections in one experiment is a key problem to be solved urgently in the pyrolysis research of the current substances.
The present invention has been made to solve the above problems.
SUMMERY OF THE UTILITY MODEL
The utility model provides a real-time online analysis device for substance pyrolysis.A trapping system of the device is provided with a cooling cavity and a heating cavity, wherein the cooling cavity can condense, adsorb and trap a pyrolysis product at a set temperature point or temperature section, and the heating cavity can heat the pyrolysis product for thermal desorption and then carry out real-time online separation and analysis.
The technical scheme of the utility model is as follows:
the utility model discloses a real-time online analysis device for substance pyrolysis, which comprises: the system comprises a pyrolysis system 1, a capture system 2, a test system 3 and a control system 4; pyrolysis system 1, entrapment system 2 and test system 3 connection control system 4, control system 4 controls the pyrolysis of the material of whole device, the entrapment and the real-time separation and the analysis of pyrolysis product, have cooling chamber 22 and heating chamber 23 in the entrapment system 2, the temperature range of cooling chamber 22 is room temperature to 200 ℃ below zero, and the temperature range of heating chamber 23 is room temperature to 1000 ℃.
Preferably, the trapping system 2 comprises the following components:
a horizontal movement groove 21;
a cooling chamber 22 disposed at one end of the horizontal moving bath 21; a cooling pipe 221 is arranged in the cooling cavity 22, and the cooling pipe 221 is connected with a cooling gas device 222; the cooling cavity 22 is hermetically connected with the pyrolysis system 1 through a gas path pipe 5; cooling chamber 22 has a length no less than the length of one collection tube 241;
a heating chamber 23 disposed at the other end of the horizontal moving slot 21; a heating pipe 231 is arranged in the heating cavity 23; the heating cavity 23 is hermetically connected with the test system 3 through an air path pipe 5; the length of the heating chamber 23 is no less than the length of one collection tube 241;
a rotary collector 24 arranged on the horizontal moving groove 21 between the cooling cavity 22 and the heating cavity 23 and capable of sliding along the horizontal moving groove 21 towards the cooling cavity 22 or the heating cavity 23 for a distance not less than the length of one collecting pipe 241; the rotating collector 24 is provided with a plurality of collecting tubes 241, and the plurality of collecting tubes 241 are arranged on the radius of the rotating collector 24; the rotation collector 24 can rotate clockwise or counterclockwise by 360 degrees;
a purge gas pipe 25 connected to the rotary collector 24; the purge gas pipe 25 is connected to a purge gas cylinder 251.
Preferably, the cooling gas device 222 is filled with liquid nitrogen, and the cooling temperature ranges from room temperature to 200 ℃ below zero; the heating tube 231 is at a temperature ranging from room temperature to 1000 deg.C and at a heating rate ranging from 1 deg.C/s to 300 deg.C/s.
Preferably, the pyrolysis system 1 comprises a pyrolysis device 11 capable of providing a programmed temperature; introducing gas serving as carrier gas into the pyrolysis device 11, wherein the gas serving as the carrier gas is one or more of air, nitrogen, oxygen, helium and argon, and the gas flow is 0-2000 mL/min; the pyrolysis system 1 can acquire the change programs of the thermal weight loss, the heat flow, the heat enthalpy and the like in real time, and preferably selects a comprehensive thermal analyzer; the pyrolysis system 1 can set a plurality of temperature points or temperature intervals according to the pyrolysis temperature of the substance, and the setting program is set by the control system 4.
Preferably, the test system 3 comprises separation means 31 and detection means 32; one end of the separation device 31 is hermetically connected with the heating cavity 23 through the air path pipe 5, and the other end is connected with the detection device 32.
Preferably, the separation device 31 includes, but is not limited to, a gas chromatograph; the detection device 32 includes, but is not limited to, a mass spectrometer.
Preferably, the purge gas in the purge gas pipe 25 is one of nitrogen, helium or argon; the gas flow is 0-2000 mL/min.
Preferably, the collection tubes 241 are not less than eight.
The utility model discloses a method for real-time online analysis of pyrolysis of substances, which uses the device and comprises the following steps:
placing a substance to be analyzed in a pyrolysis device 11, and carrying out programmed heating under the control of a control system 4 to reach a set temperature point or temperature interval, wherein the substance is heated at the set temperature point or temperature interval to carry out pyrolysis;
the rotary collector 10 moves towards the cooling cavity 22 along the horizontal moving groove 21, a collection pipe 241 carried by the rotary collector completely extends into the cooling cavity 22, the pyrolysis product is carried into the collection pipe 241 by the carrier gas, and the cooling pipe 221 cools the carrier gas to condense and adsorb the pyrolysis product in the collection pipe 241; after the temperature point or the thermal pyrolysis product is collected, the collecting pipe 241 is rotated by 180 degrees by the rotary collector 10 and then moves to the heating cavity 23 along the horizontal moving groove 21;
the collection pipe 241 collected with the pyrolysis product is completely extended into the heating cavity 23, the heating pipe 231 heats the heating cavity 23, the pyrolysis product condensed and adsorbed in the collection pipe 241 is heated for thermal desorption, the purge gas in the purge gas pipe 25 is sent into the separation device 31, the separation is carried out by the separation device 31, the separated matter enters the detection device 32, and the detection device 32 carries out on-line analysis on the pyrolysis product;
then performing pyrolysis on substances at other temperature points or temperature sections; and repeating the steps to perform real-time online analysis on the pyrolysis of the substances at a plurality of set temperature points or temperature intervals.
The utility model has the following beneficial effects:
1. the device can provide real-time on-line capture, separation and analysis of a plurality of temperature points or temperature sections for the one-time pyrolysis of the substance. The device can detect the real-time change condition of the primary pyrolysis product of the analyzed substance, including the change condition of the content of the pyrolysis product along with the temperature change.
2. The device provided by the utility model rapidly collects pyrolysis products in the pyrolysis process of the substance in a cooling mode, and then separates and analyzes the pyrolysis products through thermal desorption, so that the whole processes of full-closed integrated experiment and temperature programmed pyrolysis, cold trap collection, online thermal desorption, automatic sample introduction, separation and analysis are realized, the pyrolysis condition of the substance at a slower temperature rise rate can be researched, the qualitative and relative quantitative analysis of the components of the pyrolysis products of the substance can be realized, and the real-time change rule of the pyrolysis components is obtained.
3. The utility model adopts a plurality of rotatable collecting pipes to carry out cold trap trapping on pyrolysis products of substances at a plurality of temperature points or temperature sections, and then the pyrolysis products are sent into a separation system and a detection system through high-temperature thermal desorption. The cold trap is adopted for trapping, so that the secondary reaction of the pyrolysis product in the high-temperature process in the trapping stage is effectively avoided. The high-temperature thermal desorption is utilized to effectively avoid the condensation of pyrolysis products in the analysis stage in a conveying pipe or a switching valve, so that the reliability of trapping and analyzing substances is greatly improved, and the accuracy of the analysis method is greatly improved.
4. The device can be used for monitoring the pyrolysis rule of the substance, combing and analyzing the thermochemical reaction of the substance by combining the kinetic study of the programmed temperature rise of the pyrolysis device, establishing a thermochemical reaction model, intervening the thermochemical reaction from the aspects of controlling the reaction process, optimizing the reaction condition, changing the reaction substance and the like, and realizing that the thermochemical reaction is carried out in a controllable state according to a beneficial direction.
Drawings
FIG. 1 is a schematic view of a real-time on-line analyzer for pyrolysis of substances according to the present invention; the direction of the arrow in the pyrolysis system is the carrier gas advancing direction.
FIG. 2 is a graph of the thermogravimetric, thermal flux and thermogravimetric microchips of a certain brand of smoking tobacco material A of example 1.
FIG. 3 is a total ion flow diagram of pyrolysate of example 1 brand of cigarette tobacco material A heated to 31 deg.C-90 deg.C.
FIG. 4 is a graph of the temperature dependence of the content of the major pyrolysis material of example 1 brand of smoking tobacco material A as it increases from 30 ℃ to 900 ℃.
FIG. 5 is a graph of the thermogravimetric, thermal flux and thermogravimetric microchips of a certain brand of cigarette tobacco material B of example 2.
FIG. 6 is a total ion flow diagram of the major pyrolysates of example 2 brand B of smoking tobacco material rising from 71 ℃ to 120 ℃.
FIG. 7 is a graph of the temperature dependence of the content of the major pyrolysis material of example 2 brand B tobacco material rising from 30 ℃ to 600 ℃.
FIG. 8 is a total ion flow graph of major pyrolysis material of comparative example 2 brand Nicotiana tabacum material B warmed from 30 ℃ to 600 ℃.
The reference signs are: 1. a pyrolysis system; 11. a pyrolysis device; 2. a capture system; 21. a horizontal moving tank; 22. a cooling chamber; 221. a cooling tube; 222. a cooling gas device; 23. a heating cavity; 231. heating a tube; 24. rotating the collector; 241. a collection tube; 25. a purge gas pipe; 251. purging the gas cylinder; 3. testing the system; 31. a separation device; 32. a detection device; 4. a control system; 5. an air passage pipe.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited to these examples. The experimental methods not specified in the examples are generally commercially available according to the conventional conditions and the conditions described in the manual, or according to the general-purpose equipment, materials, reagents and the like used under the conditions recommended by the manufacturer, unless otherwise specified. The starting materials required in the following examples and comparative examples are all commercially available.
The real-time on-line analysis device for the pyrolysis of substances of the utility model as shown in fig. 1 comprises: the system comprises a pyrolysis system 1, a capture system 2, a test system 3 and a control system 4; pyrolysis system 1, entrapment system 2 and test system 3 connection control system 4, control system 4 controls the pyrolysis of the material of whole device, the entrapment and the real-time separation and the analysis of pyrolysis product, have cooling chamber 22 and heating chamber 23 in the entrapment system 2, the temperature range of cooling chamber 22 is room temperature to 200 ℃ below zero, and the temperature range of heating chamber 23 is room temperature to 1000 ℃.
Wherein the trapping system 2 comprises the following components: a horizontal movement groove 21; a cooling chamber 22 disposed at one end of the horizontal moving bath 21; a cooling pipe 221 is arranged in the cooling cavity 22, and the cooling pipe 221 is connected with a cooling gas device 222; the cooling cavity 22 is hermetically connected with the pyrolysis system 1 through a gas path pipe 5; cooling chamber 22 has a length no less than the length of one collection tube 241; a heating chamber 23 disposed at the other end of the horizontal moving slot 21; a heating pipe 231 is arranged in the heating cavity 23; the heating cavity 23 is hermetically connected with the test system 3 through an air path pipe 5; the length of the heating chamber 23 is no less than the length of one collection tube 241; a rotary collector 24 arranged on the horizontal moving groove 21 between the cooling cavity 22 and the heating cavity 23 and capable of sliding along the horizontal moving groove 21 towards the cooling cavity 22 or the heating cavity 23 for a distance not less than the length of one collecting pipe 241; the rotary collector 24 is provided with a plurality of collecting tubes 241, the plurality of collecting tubes 241 are arranged on the radius of the rotary collector 24, and preferably, the number of the collecting tubes 241 is not less than eight; the rotation collector 24 can rotate clockwise or counterclockwise by 360 degrees; a purge gas pipe 25 connected to the rotary collector 24; the purge gas pipe 25 is connected to a purge gas cylinder 251.
Wherein, the cooling gas device 222 is filled with liquid nitrogen, and the cooling temperature ranges from room temperature to 200 ℃ below zero; the heating tube 231 is at a temperature ranging from room temperature to 1000 deg.C and at a heating rate ranging from 1 deg.C/s to 300 deg.C/s.
Wherein the pyrolysis system 1 comprises a pyrolysis device 11 capable of providing a programmed temperature; introducing gas serving as carrier gas into the pyrolysis device 11, wherein the gas serving as the carrier gas is one or more of air, nitrogen, oxygen, helium and argon, and the gas flow is 0-2000 mL/min; the pyrolysis system 1 can acquire the change programs of the thermal weight loss, the heat flow, the heat enthalpy and the like in real time, and preferably selects a comprehensive thermal analyzer; the pyrolysis system 1 can set a plurality of temperature points or temperature intervals according to the pyrolysis temperature of the substance, and the setting program is set by the control system 4.
Wherein the test system 3 comprises a separation device 31 and a detection device 32; one end of the separation device 31 is hermetically connected with the heating cavity 23 through the air path pipe 5, and the other end is connected with the detection device 32; preferably, the separation device 31 includes, but is not limited to, a gas chromatograph; the detection device 32 includes, but is not limited to, a mass spectrometer.
Wherein, the purge gas in the purge gas pipe 25 is one of nitrogen, helium or argon; the gas flow is 0-2000 mL/min.
The method for performing real-time online analysis on the pyrolysis of substances by using the device comprises the following steps:
placing a substance to be subjected to pyrolysis analysis in a pyrolysis device 11, and carrying out temperature programming under the control of a control system 4 to reach a set temperature point or temperature range, wherein the substance is heated at the set temperature point or temperature range to be subjected to pyrolysis;
the rotary collector 10 moves towards the cooling cavity 22 along the horizontal moving groove 21, a collection pipe 241 carried by the rotary collector completely extends into the cooling cavity 22, the pyrolysis product is carried into the collection pipe 241 by the carrier gas, and the cooling pipe 221 cools the carrier gas to condense and adsorb the pyrolysis product in the collection pipe 241; after the temperature point or the thermal pyrolysis product is collected, the collecting pipe 241 is rotated by 180 degrees by the rotary collector 10 and then moves to the heating cavity 23 along the horizontal moving groove 21;
the collection pipe 241 collected with the pyrolysis product is completely extended into the heating cavity 23, the heating pipe 231 heats the heating cavity 23, the pyrolysis product condensed and adsorbed in the collection pipe 241 is heated for thermal desorption, the purge gas in the purge gas pipe 25 is sent into the separation device 31, the separation is carried out by the separation device 31, the separated matter enters the detection device 32, and the detection device 32 carries out on-line analysis on the pyrolysis product;
then performing pyrolysis on substances at other temperature points or temperature sections; and repeating the steps to perform real-time online analysis on the pyrolysis of the substances at a plurality of set temperature points or temperature intervals.
Example 1: the device is used for carrying out real-time online analysis on the pyrolysis of a certain brand of cigarette tobacco material A.
Before the material pyrolysis analysis, keeping the pyrolysis device 11 at 800 ℃ for 10min to completely discharge impurities in the pyrolysis device 11; weighing 5.00mg of a certain brand of cigarette tobacco material A and placing the cigarette tobacco material A in a pyrolysis device 11; the temperature-raising program is: the initial temperature is increased from 30 ℃ to 900 ℃ at a speed of 10 ℃/min and kept for 10 min; air is used as carrier gas, and the flow rate of the carrier gas is 50 mL/min. The thermogravimetric, heat flow and thermogravimetric microchecker diagram of a certain brand of cigarette tobacco material A is shown in figure 2.
The acquisition procedure for setting sixteen temperature segments in combination with the major significant thermal weight loss step of the tobacco material in fig. 2 is shown in table 1, sixteen acquisition tubes are set, and sixteen groups of pyrolysis products are acquired according to the temperature segments in the whole temperature-raising procedure; and (3) rapidly cooling the pyrolysis substances in the collection pipe by using liquid nitrogen, wherein the cooling temperature is-80 ℃.
TABLE 1 tobacco material A Capture tube number and temperature segment
Sixteen pyrolysis products gather complete back, through rotatory collector 360 rotations and horizontal migration, will gather the pipe and send into the heating chamber and carry out the thermal desorption in, utilize nitrogen gas as the sweep gas, gas flow and heat weight heavy flow keep unanimously as: 50 mL/min; the starting thermal desorption temperature-rising program comprises the following steps: from room temperature, the temperature was raised to 900 ℃ at 20 ℃/s.
The separation device 31 is a chromatograph: the chromatographic column is a DB-5MS capillary column (30m × 0.25mm, 0.25 μm), and the injection port temperature is 250 ℃; carrier gas: helium gas; the flow rate is 0.8 mL/min; sample introduction amount: 1 mu L of the solution; the split ratio is as follows: 5: 1; temperature programming conditions: the initial temperature was 50 ℃ for 10min, and the temperature was increased to 280 ℃ at 10 ℃/min for 10 min.
The detection device 32 is a mass spectrometer; the ion source is an EI source, the ion source temperature: 230 ℃; solvent delay time: 7.5min, the mass spectrum scanning range is 30-450 amu; energy of electrons: 70 eV; the detection mode is as follows: and (4) full scanning.
The total ion flow diagram of pyrolysis substances of a certain brand of cigarette tobacco material A heated to 31-90 ℃ is shown in figure 3; the change in the content of the main pyrolysis products with temperature from 30 ℃ to 900 ℃ is shown in fig. 4.
Therefore, the device can detect and analyze the real-time change of the pyrolysis product in a certain temperature section, including the content change of the pyrolysis product along with the temperature change. The above effects are not achieved by the prior art and have unique advantages.
Example 2: the device of the utility model is used for carrying out real-time online analysis on the pyrolysis of a certain brand of cigarette tobacco material B.
Before the material pyrolysis analysis, keeping the pyrolysis device 11 at 800 ℃ for 10min to completely discharge impurities in the pyrolysis device 11; weighing 5.00mg of cigarette tobacco material B of a certain brand and placing the cigarette tobacco material B in a pyrolysis device 11; the temperature rising procedure is as follows: the initial temperature is increased from 30 ℃ to 600 ℃ at a speed of 5 ℃/min and kept for 10 min; air is used as carrier gas, and the flow rate of the carrier gas is 40 mL/min. The thermogravimetric, thermal flux and thermogravimetric microcharary of a certain brand of cigarette tobacco material B is shown in fig. 5.
The cigarette tobacco material B has four thermal weight loss steps with the combination of figure 5, and the weight loss proportion of each step is different: 3.6 percent of weight loss at 30.3-106.3 ℃, 17.9 percent of weight loss at 106.6-219.3 ℃, 44.2 percent of weight loss at 219.3-392 ℃ and 26 percent of weight loss at 392.2-500 ℃. The collection procedure for setting eight temperature zones is shown in table 2, eight collection tubes are set, and eight sets of pyrolysis products are collected according to the temperature zones in the whole temperature rise procedure. And (3) rapidly cooling the pyrolysis substances in the collection pipe by using liquid nitrogen, wherein the cooling temperature is-40 ℃.
TABLE 2 tobacco material B Capture tube Collection number and temperature segment
Eight pyrolysis products gather complete back, through rotatory collector 360 rotations and horizontal migration, will gather the pipe and send into and carry out the thermal desorption in the heating chamber, utilize nitrogen gas as the sweep gas, gas flow and heat weight heavy flow keep unanimous as: 40 mL/min; the starting thermal desorption temperature-rising program comprises the following steps: from room temperature, the temperature was raised to 900 ℃ at 10 ℃/s.
The separation device 31 is a chromatograph: the conditions are as follows: the chromatographic column is a DB-5MS capillary column (30m × 0.25mm, 0.25 μm), and the injection port temperature is 250 ℃; carrier gas: helium gas; the flow rate is 0.8 mL/min; sample introduction amount: 1 mu L of the solution; the split ratio is as follows: 5: 1; temperature programming conditions: the initial temperature is 50 deg.C, maintained for 10min, increased to 230 deg.C at 2 deg.C/min, increased to 250 deg.C at 10 deg.C/min, and maintained for 10 min.
The detection device 32 is a mass spectrometer; the ion source is an EI source, the ion source temperature: 230 ℃; quadrupole temperature: 150 ℃; delaying insolubilizing agent, and scanning the mass spectrum within the range of 30-450 amu; electron energy: 70 eV; the detection mode is as follows: and (4) full scanning.
As the cigarette material B of the brand cigarette adopts the cold trap trapping, the thermal desorption and the thermal purging, 83 pyrolysis products such as aldehyde ketone, ester, organic acid, pyrazine, furanone, phenol and the like are detected in the whole pyrolysis process. Wherein the total ion flow diagram of the pyrolysis material at 71-120 ℃ is shown in FIG. 6; nine representative substances with larger content are selected from 83 pyrolysis products, and the content change from 30 ℃ to 600 ℃ is shown in FIG. 7.
Therefore, it can be seen that, with the real-time online analysis device of the present invention, the pyrolysis product is captured and analyzed according to four major weight loss sections of thermogravimetry, and the pyrolysis product of the tobacco material B is also mainly divided into four major regions, region one: the limonene is produced mainly by pyrolysis at the temperature of 121-210 ℃; and area two: the nicotine and the diene nicotine are produced mainly by pyrolysis at 211-230 ℃; and (3) area three: 5-methylfuran aldehyde, benzyl alcohol and isomenthone are produced mainly by pyrolysis at 231-320 ℃; and area four: the benzoic acid, the isoeugenol and the phytol are produced by pyrolysis at the temperature of 401-500 ℃, namely, the main pyrolysis products in the maximum weight loss section are the benzoic acid, the isoeugenol and the phytol.
With the device of the utility model, it is clear from the process to the result what the main pyrolysis products of the four main weight loss sections of the tobacco material B are respectively, and the change of the substances along with the temperature. This is not achievable by the prior art.
Comparative example: thermogravimetric-gas chromatography-mass spectrometry analysis of a certain brand of cigarette tobacco material B in the prior art.
Before the material pyrolysis analysis, keeping the pyrolysis device 11 at 800 ℃ for 10min to completely discharge impurities in the pyrolysis device 11; weighing 5.00mg of cigarette tobacco material B of a certain brand and placing the cigarette tobacco material B in a pyrolysis device 11; the temperature-raising program is: the initial temperature is increased from 30 ℃ to 600 ℃ at a speed of 5 ℃/min and kept for 10 min; air is used as carrier gas, and the flow rate of the carrier gas is 40 mL/min. The thermogravimetric, heat flow and thermogravimetric microchecker diagram of a certain brand of cigarette tobacco material B is shown in FIG. 5.
The thermogravimetric pyrolysis product is directly subjected to gas chromatography-mass spectrometry for separation and analysis, and the total ion flow diagram is shown in fig. 8. The conditions are as follows: chromatograph and mass spectrometer, as in example 2; the pyrolysis materials are shown in table 3.
TABLE 3 tobacco material B Total pyrolysis Mass from 30 ℃ to 600 ℃
As can be seen from the thermogravimetric, heat flow and thermogravimetric differential quotient graph of the tobacco material B in fig. 5, the cigarette tobacco material B has four thermal weight loss steps, and the weight loss proportion of each step is inconsistent: 3.6 percent of weight loss at 30.3-106.3 ℃, 17.9 percent of weight loss at 106.6-219.3 ℃, 44.2 percent of weight loss at 219.3-392 ℃ and 26 percent of weight loss at 392.2-500 ℃. The tobacco material does not have an obvious weight loss section, except that the weight loss rate of the first stage is less, and the weight loss rate of the last three stages is maintained at 20-45%. Indicating that a significant amount of volatile material was produced in the remaining three different temperature zones, except for the first temperature zone, which may be the volatilization of moisture.
Thermogravimetry-gas chromatography-mass spectrometry analysis is carried out on pyrolysis products of tobacco substances by utilizing the prior art, all pyrolysis substances in the whole pyrolysis process are conveyed into a GC/MS for analysis, the obtained total ion flow diagram of the whole pyrolysis process is shown in figure 8, and the obtained pyrolysis substances are shown in table 3. By utilizing thermogravimetry-gas chromatography-mass spectrometry in the prior art, a plurality of pyrolysis products are low in content and are brought into a separation detection system by carrier gas in the pyrolysis process, a part of the pyrolysis products are condensed at each interface and pipeline of the system, and a part of the pyrolysis products are lost to the lower limit of a detection limit when being conveyed to the detection system, so that an instrument cannot identify the pyrolysis products. Only 23 species were detected, much lower than the pyrolysis products detected by the present invention.
Meanwhile, the comparative example does not carry out respective trapping and analysis on pyrolysis products in 4 weight loss stages, namely 4 temperature stages, and can not obtain what the main pyrolysis products are in the four main weight loss stages of the substance and the change conditions of the products along with the temperature.
Therefore, the prior art of the comparative example is only for the capture and analysis of all pyrolysis materials, and the capture and analysis of pyrolysis materials at any temperature point and temperature section cannot be carried out, and the monitoring of the variation of pyrolysis product content with the temperature variation cannot be carried out. The device of the utility model can detect and analyze the real-time change condition of the pyrolysis product at a certain temperature point or a certain temperature section, including the content change condition of the pyrolysis product along with the temperature change. The above effects are not achieved by the prior art and have unique advantages. It can be seen that the technical advantages of the present invention are very significant.
The foregoing shows and describes the general principles, principal features, and advantages of the utility model. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the utility model as claimed. The scope of the utility model is defined by the appended claims and equivalents thereof.
Claims (5)
1. A real-time on-line analysis device for pyrolysis of substances, comprising: the device comprises a pyrolysis system (1), a capture system (2), a test system (3) and a control system (4); the pyrolysis system (1), the capture system (2) and the test system (3) are connected with a control system (4); a cooling cavity (22) and a heating cavity (23) are arranged in the trapping system (2), the temperature range of the cooling cavity (22) is from room temperature to 200 ℃ below zero, and the temperature range of the heating cavity (23) is from room temperature to 1000 ℃;
the trapping system (2) comprises the following components:
a horizontal movement groove (21);
a cooling chamber (22) disposed at one end of the horizontal moving bath (21); a cooling pipe (221) is arranged in the cooling cavity (22), and the cooling pipe (221) is connected with a cooling gas device (222); the cooling cavity (22) is hermetically connected with the pyrolysis system (1) through an air path pipe (5);
a heating chamber (23) disposed at the other end of the horizontal moving groove (21); a heating pipe (231) is arranged in the heating cavity (23); the heating cavity (23) is hermetically connected with the test system (3) through an air path pipe (5);
a rotary collector (24) arranged on a horizontal moving groove (21) between the cooling cavity (22) and the heating cavity (23), and capable of sliding along the horizontal moving groove (21) towards the direction of the cooling cavity (22) or the heating cavity (23); the rotary collector (24) is provided with a plurality of collecting pipes (241), and the plurality of collecting pipes (241) are arranged on the radius of the rotary collector (24);
a purge gas pipe (25) connected to the rotary collector (24);
the pyrolysis system (1) comprises a pyrolysis device (11) capable of providing a programmed temperature; introducing gas serving as carrier gas into the pyrolysis device (11), wherein the gas serving as the carrier gas is one or more of air, nitrogen, oxygen, helium and argon, and the gas flow is 0-2000 mL/min;
the test system (3) comprises a separation device (31) and a detection device (32); one end of the separation device (31) is hermetically connected with the heating cavity (23) through the air passage pipe (5), and the other end of the separation device is connected with the detection device (32).
2. The real-time on-line analysis device for substance pyrolysis as claimed in claim 1, wherein the cooling gas device (222) is liquid nitrogen, and the cooling temperature is in a range from room temperature to 200 ℃ below zero; the temperature range of the heating pipe (231) is from room temperature to 1000 ℃, and the temperature rise rate range is 1 ℃/s to 300 ℃/s.
3. The real-time on-line analysis device for pyrolysis of matter according to claim 1, wherein the separation device (31) is a gas chromatograph; the detection device (32) is a mass spectrometer.
4. The real-time online analysis device for substance pyrolysis according to claim 1, characterized in that the purge gas in the purge gas pipe (25) is one of nitrogen, helium or argon; the gas flow rate is 0-2000 mL/min.
5. The apparatus for real-time on-line analysis of mass pyrolysis according to claim 1, wherein the number of collection tubes (241) is not less than eight.
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| CN202220098483.3U CN216926708U (en) | 2022-01-14 | 2022-01-14 | Real-time online analytical equipment of pyrolysis of material |
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