WO2023115636A1 - 物质热解实时在线分析装置及其使用方法 - Google Patents

物质热解实时在线分析装置及其使用方法 Download PDF

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WO2023115636A1
WO2023115636A1 PCT/CN2021/143565 CN2021143565W WO2023115636A1 WO 2023115636 A1 WO2023115636 A1 WO 2023115636A1 CN 2021143565 W CN2021143565 W CN 2021143565W WO 2023115636 A1 WO2023115636 A1 WO 2023115636A1
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pyrolysis
temperature
real
gas
cooling
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PCT/CN2021/143565
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English (en)
French (fr)
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杨继
刘春波
刘志华
刘劲芸
唐石云
朱瑞芝
司晓喜
张凤梅
蒋薇
李振杰
缪明明
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云南中烟工业有限责任公司
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Priority to EP21948695.8A priority Critical patent/EP4227677A4/en
Priority to JP2022564509A priority patent/JP7434603B1/ja
Priority to US18/163,142 priority patent/US11740250B2/en
Publication of WO2023115636A1 publication Critical patent/WO2023115636A1/zh

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/88Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/00584Control arrangements for automatic analysers
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/62Detectors specially adapted therefor
    • G01N30/72Mass spectrometers
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/02Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor using a plurality of sample containers moved by a conveyor system past one or more treatment or analysis stations
    • G01N35/025Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor using a plurality of sample containers moved by a conveyor system past one or more treatment or analysis stations having a carousel or turntable for reaction cells or cuvettes
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40Concentrating samples
    • G01N1/4022Concentrating samples by thermal techniques; Phase changes
    • G01N2001/4033Concentrating samples by thermal techniques; Phase changes sample concentrated on a cold spot, e.g. condensation or distillation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N30/12Preparation by evaporation
    • G01N2030/125Preparation by evaporation pyrolising
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/88Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8886Analysis of industrial production processes
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N2035/00346Heating or cooling arrangements
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/02Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor using a plurality of sample containers moved by a conveyor system past one or more treatment or analysis stations
    • G01N35/04Details of the conveyor system
    • G01N2035/0439Rotary sample carriers, i.e. carousels
    • G01N2035/0441Rotary sample carriers, i.e. carousels for samples
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/12Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using combustion

Definitions

  • the invention belongs to the technical field of detection, and in particular relates to a material pyrolysis real-time on-line analysis device and a method thereof.
  • thermogravimetric analysis TG/DTA
  • instant pyrolysis Py-GC/MS
  • the instantaneous pyrolysis method is mainly aimed at the rapid pyrolysis of substances at a temperature point, and then analyzes the pyrolysis products, which cannot investigate the whole process of pyrolysis of substances with temperature changes.
  • the pyrolysis products at a single temperature are obtained; it is difficult to find the pyrolysis behavior of the compound at a specific temperature by using this information.
  • the content of pyrolysis products obtained by thermal cracking is very low, generally at the nanogram level, even lower than the residual substances, and the pyrolysis products will be analyzed by gas chromatography mass spectrometry, which will cause qualitative and quantitative inaccuracies.
  • thermogravimetric analysis can provide stable reaction conditions under programmed temperature rise conditions, and is the most ideal experimental tool in tobacco pyrolysis research, but a single thermogravimetric analysis method cannot obtain the specific substances and contents of tobacco pyrolysis. It must be used to analyze thermogravimetric escape components. However, there is still a lack of an effective combined device for the analysis of escaped components by thermogravimetry, which seriously restricts the application of thermogravimetric analysis in tobacco pyrolysis research. At present, it is still difficult for commercialized coupled systems to play a key role in tobacco pyrolysis research.
  • thermogravimetry-mass spectrometry has not yet achieved the analysis of overlapping mass spectral peaks; thermogravimetry-infrared (TG-MS) FTIR) or thermogravimetric-infrared-mass spectrometry (TG-FTIR-MS) is still difficult to identify compounds with the same functional groups, and the infrared peak collection is the existence of the entire material pyrolysis process, which cannot be achieved at a certain temperature point or real-time material acquisition in temperature segments.
  • the existing technology wants to study the pyrolysis of a substance at any temperature point or temperature range, it is necessary to set up experimental conditions for this temperature point and carry out a separate experiment. For example, it is necessary to divide the whole process of a certain substance into 8 temperature points or To analyze the content of the product in one section, it is necessary to carry out 8 experiments respectively, which is time-consuming and labor-intensive, resulting in a waste of resources.
  • the invention provides a real-time on-line analysis device for pyrolysis of substances.
  • the trapping system of the device has a cooling chamber and a heating chamber.
  • the pyrolysis product can be heated for thermal desorption, and then real-time on-line separation and analysis.
  • the first aspect of the present invention discloses a material pyrolysis real-time online analysis device, including: pyrolysis system 1, capture system 2, test system 3 and control system 4; the pyrolysis system 1, capture system 2 and test System 3 is connected to control system 4, and control system 4 controls the material pyrolysis of the entire device, the capture of pyrolysis products, and real-time separation and analysis.
  • the capture system 2 has a cooling chamber 22 and a heating chamber 23.
  • the cooling chamber The temperature range of 22 is from room temperature to minus 200°C, and the temperature range of the heating chamber 23 is from room temperature to 1000°C.
  • the capture system 2 includes the following components:
  • the cooling chamber 22 is arranged at one end of the horizontal moving tank 21; there is a cooling pipe 221 in the cooling chamber 22, and the cooling pipe 221 is connected to the cooling gas device 222; 5 airtight connection; the length of the cooling cavity 22 is not less than the length of a collection tube 241;
  • the heating chamber 23 is arranged at the other end of the horizontal moving tank 21; a heating tube 231 is arranged in the heating chamber 23; the heating chamber 23 is airtightly connected with the test system 3 through the air pipe 5; the length of the heating chamber 23 is not less than the length of one collection tube 241;
  • Rotary collector 24 which is arranged on the horizontal moving groove 21 between the cooling chamber 22 and the heating chamber 23, can slide along the horizontal moving groove 21 to the direction of the cooling chamber 22 or the heating chamber 23, and the sliding distance is not Less than the length of one collection tube 241; multiple collection tubes 241 are arranged on the rotary collector 24, and multiple collection tubes 241 are arranged on the radius of the rotary collector 24; the rotary collector 24 can carry out 360 ° clockwise or counterclockwise hour hand rotation;
  • the purge gas pipe 25 is connected to the rotary collector 24; the purge gas pipe 25 is connected to the purge gas bottle 251.
  • the cooling gas device 222 is filled with liquid nitrogen, and the cooling temperature ranges from room temperature to minus 200°C; the temperature range of the heating tube 231 is from room temperature to 1000°C, and the heating rate ranges from 1°C/s to 300°C/s s.
  • the pyrolysis system 1 includes a pyrolysis device 11 capable of providing programmed temperature rise; gas is introduced into the pyrolysis device 11 as a carrier gas, and the gas as a carrier gas is air, nitrogen, oxygen, helium, argon One or several types of gas, the gas flow rate is 0-2000mL/min; the pyrolysis system 1 can collect the change programs of its thermal weight loss, heat flow, and heat enthalpy in real time, and the comprehensive thermal analyzer is preferably selected; the pyrolysis system 1 can be based on The pyrolysis temperature of the substance is set at multiple temperature points or temperature intervals, and the setting procedure is set by the control system 4 .
  • the test system 3 includes a separation device 31 and a detection device 32 ; one end of the separation device 31 is airtightly connected to the heating chamber 23 through the gas pipe 5 , and the other end is connected to the detection device 32 .
  • the separation device 31 includes but not limited to a gas chromatograph; the detection device 32 includes but not limited to a mass spectrometer.
  • the purge gas in the purge gas pipe 25 is one of nitrogen, helium or argon; the gas flow rate is 0-2000mL/min.
  • the second aspect of the present invention discloses a method for real-time online analysis of material pyrolysis, using the aforementioned device, including the following steps:
  • the substance to be analyzed is placed in the pyrolysis device 11, and when the temperature is programmed to rise to a set temperature point or temperature range under the control of the control system 4, the substance is heated and pyrolyzed at the set temperature point or temperature range;
  • the rotary collector 10 moves toward the cooling cavity 22 along the horizontal moving trough 21, and a collecting tube 241 carried by it is completely inserted into the cooling cavity 22, and the pyrolysis product is brought into the collecting tube 241 by the carrier gas, and the cooling tube 221 Cool the carrier gas so that the pyrolysis product is condensed and adsorbed in the collection tube 241; after collecting the temperature point or temperature pyrolysis product, the collection tube 241 is rotated 180° by the rotary collector 10, and then moves along the horizontal movement tank 21 to The heating chamber 23 moves;
  • the collection tube 241 with the pyrolysis product collected is completely inserted into the heating chamber 23, the heating tube 231 heats the heating chamber 23, and the pyrolysis product condensed and adsorbed in the collection tube 241 is heated for thermal desorption, and is purged
  • the purging gas in the air pipe 25 is sent into the separation device 31, and after being separated by the separation device 31, the separated matter enters the detection device 32, and the pyrolysis product is analyzed online by the detection device 32;
  • the device of the present invention can provide real-time on-line capture, separation and analysis of multiple temperature points or temperature segments for primary pyrolysis of substances.
  • the device of the invention can detect the real-time change of the primary pyrolysis product of the analyzed substance, including the change of the content of the pyrolysis product as the temperature changes.
  • the device of the present invention adopts a cooling method to quickly capture the pyrolysis products in the pyrolysis process of substances, and then separate and analyze them through thermal desorption, so as to realize fully enclosed integrated experiments and programmed temperature pyrolysis, cold trap capture, and online
  • the whole process of thermal desorption, automatic sampling, separation, and analysis can study the pyrolysis of substances at a slower heating rate, and can realize qualitative and relative quantitative analysis of the pyrolysis product components of substances, and obtain real-time changes in pyrolysis components law.
  • the present invention adopts several rotatable collection tubes to collect the pyrolysis products of substances at several temperature points or temperature ranges in cold traps, and then sends them to the separation system and detection system through high-temperature thermal desorption.
  • the use of cold trap trapping effectively avoids the secondary reaction of pyrolysis products during the high temperature process of the trapping stage.
  • the use of high-temperature thermal desorption effectively avoids the condensation of pyrolysis products in the delivery pipe or switching valve during the analysis stage, greatly improves the reliability of trapping and analyzing substances, and greatly improves the accuracy of the analysis method.
  • the device of the present invention can comb and analyze the thermochemical reaction of the substance by combining the kinetic research of the temperature program of the pyrolysis device, and establish a thermochemical reaction model, from controlling the reaction process to optimizing
  • the pyrolysis chemical reaction is intervened in the aspects of reaction conditions, changing the reacting substances, etc., so that the pyrolysis reaction can be carried out in a beneficial direction under controllability.
  • Fig. 1 is a schematic diagram of a real-time online analysis device for pyrolysis of substances according to the present invention; the direction of the arrow in the pyrolysis system is the forward direction of the carrier gas.
  • Fig. 2 is the thermogravimetry, heat flow and thermogravimetric differential quotient diagram of a cigarette tobacco material A of a certain brand in Example 1.
  • Fig. 3 is a total ion flow diagram of pyrolyzed substances heated to 31° C. to 90° C. of tobacco material A of a certain brand of cigarette in Example 1.
  • FIG. 3 is a total ion flow diagram of pyrolyzed substances heated to 31° C. to 90° C. of tobacco material A of a certain brand of cigarette in Example 1.
  • Fig. 4 is a graph showing the variation of the content of main pyrolyzed substances with temperature when the tobacco material A of a certain brand of cigarette is heated from 30°C to 900°C in Example 1.
  • Fig. 5 is the diagram of thermogravimetric, heat flow and thermogravimetric derivative of cigarette tobacco material B of a certain brand in Example 2.
  • Fig. 6 is a total ion chromatogram of the main pyrolyzed substances in the tobacco material B of a certain brand of cigarette in Example 2 when the temperature is raised from 71°C to 120°C.
  • Fig. 7 is a graph showing the variation of the content of main pyrolyzed substances with temperature when the tobacco material B of a certain brand of cigarette is heated from 30°C to 600°C in Example 2.
  • Fig. 8 is a total ion chromatogram of main pyrolyzed substances of cigarette tobacco material B of a certain brand in Comparative Example 2 when the temperature was raised from 30°C to 600°C.
  • Reference signs are: 1. Pyrolysis system; 11. Pyrolysis device; 2. Capture system; 21. Horizontal moving tank; 22. Cooling chamber; 221. Cooling pipe; 222. Cooling gas device; 23. Heating chamber; 231. Heating pipe; 24. Rotary collector; 241. Collection pipe; 25. Purge air pipe; 251. Purge gas cylinder; 3. Test system; 31. Separation device; 32. Detection device; 4. Control system; 5 , Air pipe.
  • the substance pyrolysis real-time online analysis device of the present invention as shown in Figure 1 comprises: pyrolysis system 1, capture system 2, test system 3 and control system 4; Described pyrolysis system 1, capture system 2 and test System 3 is connected to control system 4, and control system 4 controls the material pyrolysis of the entire device, the capture of pyrolysis products, and real-time separation and analysis.
  • the capture system 2 has a cooling chamber 22 and a heating chamber 23.
  • the cooling chamber The temperature range of 22 is from room temperature to minus 200°C, and the temperature range of the heating chamber 23 is from room temperature to 1000°C.
  • the capture system 2 includes the following components: a horizontal moving tank 21; a cooling chamber 22 arranged at one end of the horizontal moving tank 21; a cooling pipe 221 is arranged in the cooling chamber 22, and the cooling pipe 221 and the cooling gas device 222 connection; the cooling chamber 22 is airtightly connected with the pyrolysis system 1 through the gas pipe 5; the length of the cooling chamber 22 is not less than the length of a collection pipe 241; the heating chamber 23 is arranged at the other end of the horizontal moving tank 21 There is a heating pipe 231 in the heating chamber 23; the heating chamber 23 is airtightly connected with the test system 3 through the gas pipe 5; the length of the heating chamber 23 is not less than the length of a collection pipe 241; the rotating collector 24 is arranged On the horizontal moving groove 21 between the cooling chamber 22 and the heating chamber 23, it can slide along the horizontal moving groove 21 to the direction of the cooling chamber 22 or the heating chamber 23, and the sliding distance is not less than one collecting tube 241 Length; there are a plurality of collection tubes 24
  • the cooling gas device 222 is filled with liquid nitrogen, and the cooling temperature ranges from room temperature to minus 200°C; the temperature range of the heating tube 231 is from room temperature to 1000°C, and the heating rate ranges from 1°C/s to 300°C/s .
  • the pyrolysis system 1 includes a pyrolysis device 11 capable of providing programmed temperature rise; gas is introduced into the pyrolysis device 11 as a carrier gas, and the gas as a carrier gas is air, nitrogen, oxygen, helium, argon One or several of them, the gas flow rate is 0-2000mL/min; the pyrolysis system 1 can collect the change programs of its thermal weight loss, heat flow, and heat enthalpy in real time, and it is preferred to choose a comprehensive thermal analyzer; the pyrolysis system 1 can be based on the material
  • the pyrolysis temperature is set at multiple temperature points or temperature intervals, and the setting program is set by the control system 4 .
  • the test system 3 includes a separation device 31 and a detection device 32; one end of the separation device 31 is airtightly connected to the heating chamber 23 through the gas pipe 5, and the other end is connected to the detection device 32; preferably, the separation device 31 includes but It is not limited to a gas chromatograph; the detection device 32 includes but not limited to a mass spectrometer.
  • the purge gas in the purge gas pipe 25 is one of nitrogen, helium or argon; the gas flow rate is 0-2000mL/min.
  • the method for performing real-time online analysis of material pyrolysis using the device of the present invention comprises the following steps:
  • the substance to be pyrolyzed is placed in the pyrolysis device 11, and the temperature is programmed to rise under the control of the control system 4.
  • the substance is heated at the set temperature point or temperature range for heating.
  • the rotary collector 10 moves toward the cooling cavity 22 along the horizontal moving trough 21, and a collecting tube 241 carried by it is completely inserted into the cooling cavity 22, and the pyrolysis product is brought into the collecting tube 241 by the carrier gas, and the cooling tube 221 Cool the carrier gas so that the pyrolysis product is condensed and adsorbed in the collection tube 241; after collecting the temperature point or temperature pyrolysis product, the collection tube 241 is rotated 180° by the rotary collector 10, and then moves along the horizontal movement tank 21 to The heating chamber 23 moves;
  • the collection tube 241 with the pyrolysis product collected is completely inserted into the heating chamber 23, the heating tube 231 heats the heating chamber 23, and the pyrolysis product condensed and adsorbed in the collection tube 241 is heated for thermal desorption, and is purged
  • the purging gas in the air pipe 25 is sent into the separation device 31, and after being separated by the separation device 31, the separated matter enters the detection device 32, and the pyrolysis product is analyzed online by the detection device 32;
  • Example 1 Real-time on-line analysis of the pyrolysis of tobacco material A of a certain brand of cigarettes using the device of the present invention.
  • thermogravity, heat flow and thermogravimetric micro-quotient diagram of a certain brand of cigarette tobacco material A are shown in Figure 2.
  • the collection program of sixteen temperature sections is set as shown in Table 1, and the collection tubes are set to sixteen, and the whole heating program collects sixteen groups of pyrolysis products according to the temperature section; Liquid nitrogen was used to rapidly cool the pyrolyzed substance in the collection tube, and the cooling temperature was -80°C.
  • Table 1 Collecting number and temperature section of tobacco material A collecting tube
  • the collection tube was sent into the heating chamber for thermal desorption through 360° rotation and horizontal movement of the rotary collector. Nitrogen was used as the purge gas, and the gas flow rate and the thermogravimetric flow rate were kept consistent as : 50mL/min; start thermal desorption temperature rise program: from room temperature, according to 20 °C / s, the temperature is raised to 900 °C.
  • the separation device 31 is a chromatograph: the chromatographic column is a DB-5MS capillary column (30m ⁇ 0.25mm, 0.25 ⁇ m), the temperature of the injection port is 250°C; the carrier gas: helium; the flow rate is 0.8mL/min; the injection volume: 1 ⁇ L ; Split ratio: 5:1; Temperature programming conditions: initial temperature 50°C, keep for 10min, increase to 280°C at 10°C/min, keep for 10min.
  • the detection device 32 is a mass spectrometer; the ion source is an EI source, the temperature of the ion source is 230°C; the solvent delay time is 7.5min, the scanning range of the mass spectrometer is 30-450amu; the electron energy is 70eV; the detection method is full scan.
  • Figure 3 shows the total ion chromatogram of the pyrolyzed substances of tobacco material A of a certain brand of cigarette heated to 31°C-90°C; Show.
  • the device of the present invention can detect and analyze the real-time change of pyrolysis products in a certain temperature range, including the change of content of pyrolysis products with temperature changes.
  • Example 2 Real-time online analysis of the pyrolysis of tobacco material B of a certain brand of cigarettes using the device of the present invention.
  • thermogravity, heat flow and thermogravimetric micro-quotient diagram of a certain brand of cigarette tobacco material B are shown in Figure 5.
  • the cigarette tobacco material B has four thermal weight loss steps, and the weight loss ratio of each step is inconsistent: 3.6% weight loss at 30.3-106.3°C, 17.9% weight loss at 106.6-219.3°C, 44.2% weight loss at 219.3-392°C, 44.2% weight loss at 392.2-500°C °C weight loss 26%.
  • the collection program for setting eight temperature sections is shown in Table 2. Eight collection tubes are set, and eight groups of pyrolysis products are collected according to the temperature section in the entire heating program. Liquid nitrogen was used to rapidly cool the pyrolyzed substances in the collection tube, and the cooling temperature was -40°C.
  • Table 2 Collecting number and temperature section of tobacco material B collecting tube
  • the collection tube is sent into the heating chamber for thermal desorption through 360° rotation and horizontal movement of the rotary collector.
  • Nitrogen is used as the purge gas, and the gas flow rate and the thermogravimetric flow rate are kept consistent as follows: 40mL/min; start the thermal desorption temperature rise program: from room temperature, according to 10 °C / s, the temperature is raised to 900 °C.
  • the separation device 31 is a chromatograph: the conditions are: the chromatographic column is a DB-5MS capillary column (30m ⁇ 0.25mm, 0.25 ⁇ m), the temperature of the injection port is 250°C; the carrier gas: helium; the flow rate is 0.8mL/min; Volume: 1 ⁇ L; split ratio: 5:1; temperature program conditions: initial temperature 50°C, hold for 10 minutes, rise to 230°C at 2°C/min, then rise to 250°C at 10°C/min, hold for 10 minutes.
  • the detection device 32 is a mass spectrometer; the ion source is an EI source, the ion source temperature: 230°C; the quadrupole temperature: 150°C; the non-solvent delay, the mass spectrometer scanning range is 30-450amu; the electron energy: 70eV; the detection method: full scan.
  • the ion source is an EI source, the ion source temperature: 230°C; the quadrupole temperature: 150°C; the non-solvent delay, the mass spectrometer scanning range is 30-450amu; the electron energy: 70eV; the detection method: full scan.
  • the pyrolysis products are collected and analyzed according to the four main weight loss sections of thermogravimetry, and the pyrolysis products of the tobacco material B are also mainly divided into four main areas, Zone 1: Limonene is mainly produced by pyrolysis at 121-210 °C; Zone 2: Nicotine and diene nicotine are mainly produced by pyrolysis at 211-230 °C; Zone 3: 5-methylfuran aldehyde, benzyl alcohol, iso Menthone is mainly produced by pyrolysis at 231-320°C; Zone 4: Benzoic acid, isoeugenol, and phytol are mainly produced by pyrolysis at 401-500°C, that is, the main pyrolysis products in the maximum weight loss section are benzoic acid, Isoeugenol, Phytol.
  • thermogravity, heat flow and thermogravimetric micro-quotient diagram of a certain brand of cigarette tobacco material B are shown in Figure 5.
  • thermogravimetric pyrolysis product was directly separated and analyzed by gas chromatography-mass spectrometry, and the total ion flow diagram is shown in Figure 8.
  • the conditions are: chromatograph and mass spectrometer, the same as in Example 2; pyrolyzed substances are shown in Table 3.
  • thermogravimetry, heat flow and thermogravimetric differential quotient diagram of the tobacco material B in Fig. 5 that the cigarette tobacco material B has four thermal weight loss steps, and the weight loss ratio of each step is inconsistent: 30.3-106.3 ° C weight loss 3.6% , 17.9% weight loss at 106.6-219.3 °C, 44.2% weight loss at 219.3-392 °C, and 26% weight loss at 392.2-500 °C.
  • Tobacco material does not have a significant weight loss period, except that the weight loss rate in the first stage is less, and the next three stages are maintained at 20-45%. It shows that in addition to the volatilization of water in the first temperature range, a large amount of volatile substances are generated in the other three different temperature ranges.
  • thermogravimetry-gas chromatography-mass spectrometry analysis many pyrolysis products are low in content, and are brought into the separation and detection system by the carrier gas during the pyrolysis process, and a part of the pyrolysis products condenses at various interfaces and pipes of the system At , a part of the pyrolysis product has been lost to the lower limit of the detection limit when it is transported to the detection system, and the instrument cannot identify it. Therefore, only 23 substances are detected, which is much lower than the pyrolysis products detected by the present invention.
  • the comparative example did not capture and analyze the pyrolysis products of the four weight loss stages, that is, the four temperature ranges, and it is impossible to draw the main pyrolysis products of the four main weight loss stages of the substance and the temperature of these products. changes.
  • the prior art of the comparative example is only aimed at the capture and analysis of all pyrolysis substances, and cannot capture and analyze pyrolysis substances at any temperature point and temperature range, let alone the change of pyrolysis product content Monitoring of changes in temperature.
  • the device of the present invention can detect and analyze the real-time change of the pyrolysis product at a certain temperature point or a certain temperature range, including the change of the content of the pyrolysis product as the temperature changes.

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Abstract

一种物质热解实时在线分析装置及使用物质热解实时在线分析装置进行物质热解实时在线分析的方法,物质热解实时在线分析装置包括:热解系统(1)、捕集系统(2)、测试系统(3)和控制系统(4);热解系统(1)、捕集系统(2)和测试系统(3)连接控制系统(4);捕集系统(2)内有冷却腔(22)和加热腔(23),冷却腔(22)的温度范围为室温至零下200℃,加热腔(23)的温度范围为室温至1000℃。物质热解实时在线分析装置能对物质提供多个温度点或温度范围的实时在线热解、捕集、分离和分析。

Description

物质热解实时在线分析装置及其使用方法 技术领域
本发明属于检测技术领域,具体涉及一种物质热解实时在线分析装置及其方法。
背景技术
许多无机物质和有机物质被加热到一定程度时都会发生分解反应。具有工业意义的有机物热解过程很多,常因具体工艺过程而有不同的名称。在隔绝空气下进行的热解反应,称为干馏,如煤干馏、木材干馏;甲烷热解生成炭黑称为热分解;烷基苯或烷基萘热解生成苯或萘常称为热脱烷基;由丙酮制乙烯酮称为丙酮裂解等。烃类的热解过程常区别为热裂化和裂解。实时在线了解在热解过程中得到的产物情况对控制反应进程、优化反应条件、改变反应物质具有重大的意义。例如烟草是一种成分复杂的生物质,其热解产物对卷烟品质有着至关重要的影响。研究表明,烟气中的化学组分约1/3直接来自于烟草,其余则是在卷烟燃烧过程中,通过蒸馏、裂解、燃烧、聚合等一系列复杂的过程产生的;因此,有必要建立一种适用的烟草生物质热解的模式体系,深入研究烟草各成分在任意温度下的热解规律和迁移情况。
现有技术主要采用热重分析法(TG/DTA)和瞬间裂解法(Py-GC/MS)来研究烟草热解过程。瞬间裂解法(Py-GC/MS)主要是针对一个温度点进行物质快速裂解,后进行裂解产物分析,无法考察物质随温度变化的热解全过程情况。对于烟草中的难挥发物质(如糖类、氨基酸、多酚等等)得到的是单一温度下的裂解产物;利用这些信息难以发现化合物在某一具体温度下的热解行为。且热裂解得到的裂解产物含量很低,一般都在纳克级,甚至比残留物质还低,裂解产物进入气相色谱质谱分析,会造成定性和定量不准确。
热重分析法(TG/DTA)可以提供程序升温条件下稳定的反应条件,是烟草热解研究中最为理想的实验工具,但单一的热重分析法无法得到烟草热解的具体物质及含量,必须经过联用来分析热重逸出组分。但目前热重逸出组分分析方面尚 缺少一种行之有效的联用装置,严重制约了热重分析法在烟草热解研究中的应用。目前商品化的联用系统仍难以在烟草热解研究中发挥关键作用,原因在于:热重-质谱联用(TG-MS)尚未实现重叠质谱峰的解析;热重-红外联用(TG-FTIR)或者热重-红外-质谱(TG-FTIR-MS)联用还难以辨识具有相同官能团的化合物,且红外峰采集是整个物质热解过程的存在的物质,未能实现在某个温度点或温度段的实时物质采集。现有的技术若要在任意温度点或温度段对物质热解进行研究,需要针对该温度点设置实验条件开展单独的实验,例如要对某一物质热解全过程分8个温度点或温度段进行产物含量分析,需要分别开展8次实验,费时费力,造成资源的浪费。
有报道提出利用六通阀或八通阀进行切换针对性地捕集热解物质进行后续分析。但物质经过升温分解出的逸出气体具有一定的温度,在常温下采用阀的切换极易造成热解逸出物质冷凝在阀内,造成阀的污染,捕集到的物质也可能是多次实验冷凝的物质,因此分析结果不可靠。
通过一次实验分若干温度点或温度段进行物质热解复杂逸出组分在线分析是当前物质热解研究亟需解决的关键问题。
为了解决以上问题,提出本发明。
发明内容
本发明提供了一种物质热解实时在线分析装置,该装置的捕集系统有冷却腔和加热腔,冷却腔能冷凝吸附捕集在设定的温度点或温度段的热解产物,加热腔可以将热解产物受热进行热脱附,然后进行实时在线分离和分析。
本发明的技术方案如下:
本发明第一方面公开了一种物质热解实时在线分析装置,包括:热解系统1、捕集系统2、测试系统3和控制系统4;所述热解系统1、捕集系统2和测试系统3连接控制系统4,控制系统4对整个装置的物质热解、热解产物的捕集和实时分离和分析进行控制,所述捕集系统2内有冷却腔22和加热腔23,冷却腔22的温度范围为室温至零下200℃,加热腔23的温度范围为室温至1000℃。
优选地,所述捕集系统2包括如下部件:
水平移动槽21;
冷却腔22,布置在所述水平移动槽21的一端;所述冷却腔22内有冷却管221,冷却管221与冷却气体装置222连接;所述冷却腔22与热解系统1通过气路管5密闭连接;冷却腔22的长度不小于一个采集管241的长度;
加热腔23,布置在所述水平移动槽21的另一端;所述加热腔23内有加热管231;所述加热腔23与测试系统3通过气路管5密闭连接;加热腔23的长度不小于一个采集管241的长度;
旋转采集器24,其布置在所述冷却腔22和加热腔23之间的水平移动槽21上,其能够沿所述水平移动槽21向冷却腔22或加热腔23的方向滑动,滑动距离不少于一个采集管241的长度;所述旋转采集器24上有多个采集管241,多个采集管241布置在旋转采集器24的半径上;旋转采集器24可以进行360°顺时针或逆时针旋转;
吹扫气管25,其连接在所述旋转采集器24上;吹扫气管25连接吹扫气瓶251。
优选地,所述冷却气体装置222内为液氮,冷却温度范围为室温至零下200℃;所述加热管231的温度范围为室温至1000℃,升温速率范围为1℃/s~300℃/s。
优选地,所述热解系统1包括能提供程序升温的热解装置11;所述热解装置11中通入气体作为载气,作为载气的气体为空气、氮气、氧气、氦气、氩气中的一种或几种,气体流量为0~2000mL/min;热解系统1可以实时采集其热失重、热流、热焓等变化程序,优选选择综合热分析仪;热解系统1可以根据物质热解温度进行多个温度点或温度区间的设定,其设定程序由控制系统4进行设定。
优选地,所述测试系统3包括分离装置31和检测装置32;所述分离装置31一端通过气路管5与加热腔23密闭连接,另一端与检测装置32连接。
优选地,所述分离装置31包括但不限于气相色谱仪;所述检测装置32包括但不限于质谱仪。
优选地,所述吹扫气管25中的吹扫气为氮气、氦气或氩气中的一种;气体流量为0-2000mL/min。
优选地,所述采集管241不少于八个。
本发明第二方面公开了一种物质热解实时在线分析的方法,使用前述的装置, 包括如下步骤:
将准备分析的物质放置在热解装置11中,在控制系统4控制下进行程序升温到达一个设定的温度点或温度区间时,物质在此设定的温度点或温度区间受热进行热解;
旋转采集器10沿水平移动槽21向冷却腔22移动,将其携带的一个采集管241完全伸入到冷却腔22中,热解产物由所述载气带入采集管241中,冷却管221对载气进行冷却使热解产物冷凝吸附在采集管241中;采集完该温度点或温度热解产物后,该采集管241被旋转采集器10旋转180°后,再沿水平移动槽21向加热腔23移动;
将采集有热解产物的该采集管241完全伸入到加热腔23中,加热管231对加热腔23进行加热,冷凝吸附在采集管241中的热解产物受热进行热脱附,由吹扫气管25中的所述吹扫气将其送入分离装置31中,经分离装置31的分离,分离物进入检测装置32中,由检测装置32对热解产物进行在线分析;
然后进行其他温度点或温度段的物质进行热解;重复上述步骤,即可以对多个设定的温度点或温度区间的物质热解的实时在线分析。
本发明具有以下有益效果:
1、本发明的装置能对物质一次热解提供多个温度点或温度段的实时在线捕集、分离和分析。本发明的装置可以检测分析物质一次热解产物实时变化情况,包括随温度变化热解产物含量的变化情况。
2、本发明的装置采用冷却方式快速捕集物质热解过程中的热解产物,然后经热脱附进行分离和分析,实现全封闭一体化实验和程序升温热解、冷阱捕集、在线热脱附、自动进样、分离、分析全过程,可以研究物质在较慢升温速率下的热解情况,能实现对物质热解产物成分的定性和相对定量分析,得到热解成分的实时变化规律。
3、本发明采用可旋转的若干个采集管对若干温度点或温度段物质热解产物进行冷阱捕集,后经高温热脱附送入分离系统和检测系统。采用冷阱捕集有效避免了在捕集阶段高温过程中热解产物二次反应的发生。利用高温热脱附有效避免了分析阶段热解产物冷凝在输送管或切换阀中,极大地提高了捕集和分析物质的 可靠性,大大提高了分析方法的准确性。
4、本发明的装置在监测物质热解规律的同时,通过结合热解装置的程序升温的动力学研究,可以梳理和解析物质的热化学反应,建立热化学反应模型,从控制反应进程、优化反应条件、改变反应物质等方面对热解化学反应进行干预,实现热解反应在可控状态下按照有益的方向进行。
附图说明
图1为本发明的物质热解实时在线分析装置示意图;热解系统中的箭头方向为载气前进方向。
图2为实施例1某品牌卷烟烟草材料A的热重、热流和热重微商图。
图3为实施例1某品牌卷烟烟草材料A加热至31℃~90℃的热解物质的总离子流图。
图4为实施例1某品牌卷烟烟草材料A从30℃升温至900℃主要热解物质含量随温度变化图。
图5为实施例2某品牌卷烟烟草材料B的热重、热流和热重微商图。
图6为实施例2某品牌卷烟烟草材料B从71℃升温至120℃的主要热解物质的总离子流图。
图7为实施例2某品牌卷烟烟草材料B从30℃升温至600℃主要热解物质含量随温度变化图。
图8为对比例2某品牌卷烟烟草材料B从30℃升温至600℃主要热解物质的总离子流图。
附图标记为:1、热解系统;11、热解装置;2、捕集系统;21、水平移动槽;22、冷却腔;221、冷却管;222、冷却气体装置;23、加热腔;231、加热管;24、旋转采集器;241、采集管;25、吹扫气管;251、吹扫气瓶;3、测试系统;31、分离装置;32、检测装置;4、控制系统;5、气路管。
具体实施方式
下面对本发明通过实施例作进一步说明,但不仅限于本实施例。实施例中未注明具体条件的实验方法,通常按照常规条件以及手册中所述的条件,或按照制 造厂商所建议的条件所用的通用设备、材料、试剂等,如无特殊说明,均可从商业途径得到。以下实施例和对比例中所需要的原料均为市售。
如图1所示的本发明的物质热解实时在线分析装置,包括:热解系统1、捕集系统2、测试系统3和控制系统4;所述热解系统1、捕集系统2和测试系统3连接控制系统4,控制系统4对整个装置的物质热解、热解产物的捕集和实时分离和分析进行控制,所述捕集系统2内有冷却腔22和加热腔23,冷却腔22的温度范围为室温至零下200℃,加热腔23的温度范围为室温至1000℃。
其中,所述捕集系统2包括如下部件:水平移动槽21;冷却腔22,布置在所述水平移动槽21的一端;所述冷却腔22内有冷却管221,冷却管221与冷却气体装置222连接;所述冷却腔22与热解系统1通过气路管5密闭连接;冷却腔22的长度不小于一个采集管241的长度;加热腔23,布置在所述水平移动槽21的另一端;所述加热腔23内有加热管231;所述加热腔23与测试系统3通过气路管5密闭连接;加热腔23的长度不小于一个采集管241的长度;旋转采集器24,其布置在所述冷却腔22和加热腔23之间的水平移动槽21上,其能够沿所述水平移动槽21向冷却腔22或加热腔23的方向滑动,滑动距离不少于一个采集管241的长度;所述旋转采集器24上有多个采集管241,多个采集管241布置在旋转采集器24的半径上,优选所述采集管241不少于八个;旋转采集器24可以进行360°顺时针或逆时针旋转;吹扫气管25,其连接在所述旋转采集器24上;吹扫气管25连接吹扫气瓶251。
其中,所述冷却气体装置222内为液氮,冷却温度范围为室温至零下200℃;所述加热管231的温度范围为室温至1000℃,升温速率范围为1℃/s~300℃/s。
其中,所述热解系统1包括能提供程序升温的热解装置11;所述热解装置11中通入气体作为载气,作为载气的气体为空气、氮气、氧气、氦气、氩气中的一种或几种,气体流量为0~2000mL/min;热解系统1可以实时采集其热失重、热流、热焓等变化程序,优选选择综合热分析仪;热解系统1可以根据物质热解温度进行多个温度点或温度区间的设定,其设定程序由控制系统4进行设定。
其中,所述测试系统3包括分离装置31和检测装置32;所述分离装置31一端通过气路管5与加热腔23密闭连接,另一端与检测装置32连接;优选所述 分离装置31包括但不限于气相色谱仪;所述检测装置32包括但不限于质谱仪。
其中,所述吹扫气管25中的吹扫气为氮气、氦气或氩气中的一种;气体流量为0-2000mL/min。
使用本发明的装置进行物质热解实时在线分析的方法包括如下步骤:
将准备热解分析的物质放置在热解装置11中,在控制系统4控制下进行程序升温到达一个设定的温度点或温度区间时,物质在此设定的温度点或温度区间受热进行热解;
旋转采集器10沿水平移动槽21向冷却腔22移动,将其携带的一个采集管241完全伸入到冷却腔22中,热解产物由所述载气带入采集管241中,冷却管221对载气进行冷却使热解产物冷凝吸附在采集管241中;采集完该温度点或温度热解产物后,该采集管241被旋转采集器10旋转180°后,再沿水平移动槽21向加热腔23移动;
将采集有热解产物的该采集管241完全伸入到加热腔23中,加热管231对加热腔23进行加热,冷凝吸附在采集管241中的热解产物受热进行热脱附,由吹扫气管25中的所述吹扫气将其送入分离装置31中,经分离装置31的分离,分离物进入检测装置32中,由检测装置32对热解产物进行在线分析;
然后进行其他温度点或温度段的物质进行热解;重复上述步骤,即可以对多个设定的温度点或温度区间的物质热解的实时在线分析。
实施例1:使用本发明的装置对某品牌卷烟烟草材料A的热解实时在线分析。
物质热解分析前,将热解装置11在800℃条件下保持10min,以使热解装置11内杂质排净;称取5.00mg的某品牌卷烟烟草材料A置于热解装置11内;升温程序为:初始温度从30℃以10℃/min升至900℃,保持10min;空气为载气,载气流量为50mL/min。某品牌卷烟烟草材料A的热重、热流和热重微商图如图2所示。
结合图2中该烟草材料主要明显的热失重台阶设置十六个温度段的采集程序如表1所示,设置采集管为十六个,整个升温程序按温度段采集十六组热解产物;利用液氮对采集管中的热解物质实现快速冷却,冷却温度为-80℃。
表1烟草材料A捕集管采集个数和温度段
Figure PCTCN2021143565-appb-000001
十六个热解产物采集完全后,经旋转采集器360°旋转和水平移动,将采集管送入加热腔中进行热脱附,利用氮气作为吹扫气,气体流量和热重流量保持一致为:50mL/min;启动热脱附升温程序为:从室温起,按照20℃/s,升温至900℃。
分离装置31为色谱仪:色谱柱为DB-5MS毛细管柱(30m×0.25mm,0.25μm),进样口温度250℃;载气:氦气;流速为0.8mL/min;进样量:1μL;分流比:5:1;程序升温条件:初始温度50℃,保持10min,以10℃/min升至280℃,保持10min。
检测装置32为质谱仪;离子源为EI源,离子源温度:230℃;溶剂延迟时间:7.5min,质谱扫描范围30~450amu;电子能量:70eV;检测方式:全扫描。
某品牌卷烟烟草材料A加热至31℃~90℃的热解物质的总离子流图如图3所示;从30℃升至900℃主要热解产物随温度变化的含量变化情况如图4所示。
由此可见,利用本发明的装置可以检测分析某一温度段热解产物实时变化情况,包括随温度变化的热解产物含量变化情况。上述效果是现有技术所不能达到的,具有独特的优势。
实施例2:使用本发明的装置对某品牌卷烟烟草材料B的热解实时在线分析。
物质热解分析前,将热解装置11在800℃条件下保持10min,以使热解装置11内杂质排净;称取5.00mg的某品牌卷烟烟草材料B置于热解装置11内;升温程序为:初始温度从30℃以5℃/min升至600℃,保持10min;空气为载气,载气流量为40mL/min。某品牌卷烟烟草材料B的热重、热流和热重微商图如图5所示。
结合图5该卷烟烟草材料B有四个热失重台阶,每个台阶失重比例均不一致:30.3~106.3℃失重3.6%,106.6~219.3℃失重17.9%,219.3~392℃失重44.2%, 392.2~500℃失重26%。设置八个温度段的采集程序如表2所示,设置采集管为八个,整个升温程序按温度段采集八组热解产物。利用液氮对采集管中的热解物质实现快速冷却,冷却温度为-40℃。
表2烟草材料B捕集管采集个数和温度段
Figure PCTCN2021143565-appb-000002
八个热解产物采集完全后,经旋转采集器360°旋转和水平移动,将采集管送入加热腔中进行热脱附,利用氮气作为吹扫气,气体流量和热重流量保持一致为:40mL/min;启动热脱附升温程序为:从室温起,按照10℃/s,升温至900℃。
分离装置31为色谱仪:条件为:色谱柱为DB-5MS毛细管柱(30m×0.25mm,0.25μm),进样口温度250℃;载气:氦气;流速为0.8mL/min;进样量:1μL;分流比:5:1;程序升温条件:初始温度50℃,保持10min,以2℃/min升至230℃,后以10℃/min升至250℃,保持10min。
检测装置32为质谱仪;离子源为EI源,离子源温度:230℃;四级杆温度:150℃;不溶剂延迟,质谱扫描范围30~450amu;电子能量:70eV;检测方式:全扫描。
该品牌卷烟烟草材料B由于采用本发明的冷阱捕集和热脱附和热吹扫,整个热解过程总共检测到醛酮、酯类、有机酸、吡嗪、呋喃酮类、酚类等83种热解产物。其中71℃~120℃的热解物质的总离子流图如图6所示;从83种热解产物中,选取含量较大的九种代表性物质,从30℃升至600℃的含量变化情况如图7所示。
因此可以看出,利用本发明的实时在线分析装置,根据热重的四个主要失重段进行热解产物的捕集和分析,该烟草材料B的热解产物也主要分为四个主要区域,区域一:柠檬烯主要在121~210℃热解产出;区域二:烟碱、二烯烟碱主要在211~230℃热解产出;区域三:5-甲基呋喃醛、苄醇、异薄荷酮主要在231~320℃热解产出;区域四:苯甲酸、异丁香酚、叶绿醇主要在401~500℃热解产出,即最大失重段主要的热解产物为苯甲酸、异丁香酚、叶绿醇。
利用本发明的装置,从过程到结果明确了该烟草材料B四个主失重段的主要热解产物分别是什么物质,且这些物质随着温度的变化情况。这是现有技术无 法达到的。
对比例:某品牌卷烟烟草材料B现有技术的热重-气相色谱-质谱分析。
物质热解分析前,将热解装置11在800℃条件下保持10min,以使热解装置11内杂质排净;称取5.00mg的某品牌卷烟烟草材料B置于热解装置11内;升温程序为:初始温度从30℃以5℃/min升至600℃,保持10min;空气为载气,载气流量为40mL/min。某品牌卷烟烟草材料B的热重、热流和热重微商图如图5所示。
将热重热解产物直接进行气相色谱-质谱进行分离分析,总离子流图如图8所示。条件为:色谱仪和质谱仪,同实施例2;热解物质如表3所示。
表3烟草材料B从30℃至600℃全部热解物质
Figure PCTCN2021143565-appb-000003
由图5的该烟草材料B的热重、热流和热重微商图可以看出,该卷烟烟草 材料B有四个热失重台阶,每个台阶失重比例均不一致:30.3~106.3℃失重3.6%,106.6~219.3℃失重17.9%,219.3~392℃失重44.2%,392.2~500℃失重26%。烟草材料没有一个明显的失重段,除了第一阶段失重率较少,后面三个阶段均维持在20-45%。说明除了第一温度段可能是水分的挥发外,在其余后三个不同的温度段均有大量的挥发性物质生成。
利用现有技术进行热重-气相色谱-质谱分析烟草物质的热解产物,将整个热解过程的全部热解物质全部输送进GC/MS分析,得到的是整个热解过程的总离子流图如图8所示,热解物质如表3所示。利用现有技术热重-气相色谱-质谱分析,很多热解产物由于含量较低,且在热解过程中由载气带入进入分离检测系统,一部分热解产物冷凝在系统的各个接口和管道处,一部分热解产物输送到检测系统时已流失到检出限的下限,仪器无法识别。因此只检测出23种物质,大大低于本发明所检测出的热解产物。
同时,对比例未对4个失重阶段即4个温度段的热解产物进行分别的捕集和分析,不能得出该物质四个主要失重阶段主要的热解产物分别是什么和这些产物随温度的变化情况。
由此可见,对比例的现有技术只是针对全部热解物质的捕集和分析,不能进行任意温度点和温度段的热解物质的捕集和分析,更不能进行热解产物含量的变化情况随温度变化的监测。而利用本发明的装置可以检测分析某一温度点或某一温度段的热解产物实时变化情况,包括随温度变化的热解产物含量变化情况。上述效果是现有技术所不能达到的,具有独特的优势。可见本发明的技术优势非常明显。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (9)

  1. 一种物质热解实时在线分析装置,其特征在于,包括:热解系统(1)、捕集系统(2)、测试系统(3)和控制系统(4);所述热解系统(1)、捕集系统(2)和测试系统(3)连接控制系统(4);所述捕集系统(2)内有冷却腔(22)和加热腔(23),冷却腔(22)的温度范围为室温至零下200℃,加热腔(23)的温度范围为室温至1000℃。
  2. 根据权利要求1所述的物质热解实时在线分析装置,其特征在于,所述捕集系统(2)包括如下部件:
    水平移动槽(21);
    冷却腔(22),布置在所述水平移动槽(21)的一端;所述冷却腔(22)内有冷却管(221),冷却管(221)与冷却气体装置(222)连接;所述冷却腔(22)与热解系统(1)通过气路管(5)密闭连接;
    加热腔(23),布置在所述水平移动槽(21)的另一端;所述加热腔(23)内有加热管(231);所述加热腔(23)与测试系统(3)通过气路管(6)密闭连接;
    旋转采集器(24),其布置在所述冷却腔(22)和加热腔(23)之间的水平移动槽(21)上,其能够沿所述水平移动槽(21)向冷却腔(22)或加热腔(23)的方向滑动;所述旋转采集器(24)上有多个采集管(241),多个采集管(241)布置在旋转采集器(24)的半径上;
    吹扫气管(25),其连接在所述旋转采集器(24)上。
  3. 根据权利要求2所述的物质热解实时在线分析装置,其特征在于,所述冷却气体装置(222)内为液氮,冷却温度范围为室温至零下200℃;所述加热管(231)的温度范围为室温至1000℃,升温速率范围为1℃/s~300℃/s。
  4. 根据权利要求1所述的物质热解实时在线分析装置,其特征在于,所述热解系统(1)包括能提供程序升温的热解装置(11);所述热解装置(11)中通入气体作为载气,作为载气的气体为空气、氮气、氧气、氦气、氩气中的一种或几种,气体流量为0~2000mL/min。
  5. 根据权利要求2所述的物质热解实时在线分析装置,其特征在于,所述测试系统(3)包括分离装置(31)和检测装置(32);所述分离装置(31)一端通过气路管(5)与加热腔(23)密闭连接,另一端与检测装置(32)连接。
  6. 根据权利要求5所述的物质热解实时在线分析装置,其特征在于,所述分离装置(31)为气相色谱仪;所述检测装置(32)为质谱仪。
  7. 根据权利要求2所述的物质热解实时在线分析装置,其特征在于,所述吹扫气管(25)中的吹扫气为氮气、氦气或氩气中的一种;气体流量为0~2000mL/min。
  8. 根据权利要求2所述的物质热解实时在线分析装置,其特征在于,所述采集管(241)不少于八个。
  9. 一种物质热解实时在线分析的方法,其特征在于,使用权利要求1-8任一所述的装置,包括如下步骤:
    将准备分析的物质放置在热解装置(11)中,在控制系统(4)控制下进行程序升温到达一个设定的温度点或温度区间时,物质在此设定的温度点或温度区间受热进行热解;
    旋转采集器(10)沿水平移动槽(21)向冷却腔(22)移动,将其携带的一个采集管(241)完全伸入到冷却腔(22)中,热解产物由所述载气带入采集管(241)中,冷却管(221)对载气进行冷却使热解产物冷凝吸附在采集管(241)中;采集完该温度点或温度热解产物后,该采集管(241)被旋转采集器(10)旋转180°后,再沿水平移动槽(21)向加热腔(23)移动;
    将采集有热解产物的该采集管(241)完全伸入到加热腔(23)中,加热管(231)对加热腔(23)进行加热,冷凝吸附在采集管(241)中的热解产物受热进行热脱附,由吹扫气管(25)中的所述吹扫气将其送入分离装置(31)中,经分离装置(31)的分离,分离物进入检测装置(32)中,由检测装置(32)对热解产物进行在线分析;
    然后进行其他温度点或温度段的物质进行热解;重复上述步骤,即可以对多个设定的温度点或温度区间的物质热解的实时在线分析。
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