CN107422051B - Method for on-line detection of pyrolysis gas-phase components of tobacco additive or tobacco material at different temperatures - Google Patents
Method for on-line detection of pyrolysis gas-phase components of tobacco additive or tobacco material at different temperatures Download PDFInfo
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Abstract
The invention discloses a method for on-line detecting gas phase components of tobacco additives or tobacco materials cracked at different temperatures, which comprises the steps of heating and cracking the tobacco additives or the tobacco materials in a multi-step sequence; collecting the tobacco additive or tobacco material cracking product obtained by cracking in each step, and then carrying out desorption sample injection; and carrying out qualitative and quantitative detection on the sample injection sample by a gas chromatography-mass spectrometer. Compared with the conventional method, the method provided by the invention adopts a multi-step sequential heating cracking mode, is simple to operate and advanced in technology, can truly reflect the cracking conditions of the tobacco additive or the tobacco material at different cracking temperatures, comprehensively detects the cracking products of the tobacco additive and the tobacco material, can be used for controlling the formation of harmful components of cigarettes in the future and improving the health of consumers.
Description
Technical Field
The invention belongs to the technical field of a method for detecting gas-phase components released by cracking organic matters on line, and particularly relates to a method for detecting the gas-phase components of tobacco additives or tobacco materials on line at different temperatures.
Background
The combustion of cigarettes (including tobacco additives or tobacco materials) is a very complex and unpredictable chemical and physical process, and the cigarettes are subjected to a series of physical and chemical reactions such as distillation, condensation, cracking synthesis and the like in the incomplete combustion process to form a large number of new substances, and the chemical components of the new substances are complex and are a complex process. The relationship between the variation of various organic substances in tobacco with temperature, the relationship between the variation of various substances in smoke with temperature and the mechanism of cigarette combustion are not completely clear.
At present, a great number of scholars research cigarette combustion mechanism, influence of combustion temperature on chemical components of smoke and interrelation between the chemical components of the cigarette and the chemical components of the smoke, wherein cracking is the most common technical means, but the cracking technology adopted at present is the conventional cracking method (including isothermal cracking-GC/MS technology and temperature programming-GC/MS technology), the relation among the cracking temperature, the chemical components and cracking products cannot be well revealed, and the reaction mechanism and the reaction change rule are difficult to truly reveal. Baker et al have studied several stages that may be experienced in the combustion process of a cigarette using a single-step pyrolysis technique, and have also speculated the reaction sequence in the combustion process of a cigarette using an isotope-coupled pyrolysis technique. In addition, experts and scholars in the field of domestic and foreign tobacco adopt methods such as thermogravimetry, thermogravimetry-infrared combined technology and the like to simulate the combustion process of the cigarette and measure the relationship between gas-phase components released by the combustion of the tobacco and the temperature, so that the combustion mechanism of the cigarette is presumed. Qin, China and Xin, and the like, study the combustion behavior and combustion characteristics of tobacco biomass by adopting a thermogravimetry-differential scanning calorimetry (TG-DSC) method. The King Honghou wave and the like analyze the weightlessness behaviors of the tobacco in the combustion process by means of a thermogravimetric analyzer, and presume the possible behaviors of the cigarette in each temperature area.
The isothermal cracking-GC/MS technology provides cracking information of a sample at a specific temperature point, and in the actual cigarette combustion process, tobacco pyrolysis is not completed instantly, but is subjected to a relatively long-time temperature continuous change process, so that the isothermal cracking-GC/MS technology cannot reflect the cracking behavior of the sample and the continuous change condition of a formed product in the whole temperature rising process. The temperature programming cracking-GC/MS technology can not reflect the actual situation of cigarette combustion, is a final simulation result, can not predict the stage and change process in the cigarette combustion process, and can not study the behavior and mechanism of cigarette combustion. Thermogravimetry/differential thermal analysis (TG/DTA) is a thermal analysis technology which applies a thermobalance to measure the mass and temperature change of a sample under the programmed temperature, can provide weight loss behavior or thermal decomposition information of the sample under the programmed temperature condition, but cannot determine products formed in the heating process, so that the relationship between precursor and products in tobacco cannot be established, and the mechanism of cigarette combustion cannot be researched, and the TG/DTA can only be used as an auxiliary means. The escaping components can be analyzed to a certain extent by the instrument combination technology of thermogravimetry, infrared spectroscopy, mass spectrometry and the like, but for the pyrolysis reaction with relatively complex products, because the escaping components directly enter a subsequent detection system in the form of a mixture without chromatographic separation, the qualitative and semi-quantitative analysis of the cracked products is relatively difficult, and therefore, the combustion behavior or the cracking mechanism of the cigarettes cannot be really researched.
Therefore, a method capable of detecting gas phase components of the tobacco additive or the tobacco material cracked at different temperatures needs to be designed, chemical components at different cracking temperatures can be measured, and a corresponding behavior relation between cracking components and cracking temperature changes is established, so that a cracking mechanism of the tobacco additive or the tobacco material can be presumed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for on-line detecting the cracking gas phase components of tobacco additives or tobacco materials at different temperatures, which overcomes the problem that the existing detection method cannot reflect the cracking behavior and reaction products in the whole combustion process.
In order to achieve the above objects or other objects, the present invention is achieved by the following technical solutions:
a method for on-line detecting pyrolysis gas-phase components of tobacco additives or tobacco materials at different temperatures comprises the following steps:
cracking: carrying out multi-step sequential heating cracking on the tobacco additive or the tobacco material;
collecting and sampling: collecting the tobacco additive or tobacco material cracking product obtained by cracking in each step, and then carrying out desorption sample injection;
and (3) determination: and carrying out qualitative and quantitative detection on the sample injection sample by a gas chromatography-mass spectrometer.
The on-line detection refers to that a sample is analyzed and determined by a cracking instrument, a sample collecting and feeding device and a gas chromatography-mass spectrometer which are connected into a closed whole through pipelines.
Further, the multi-step sequential heating cracking specifically includes: weighing a sample of the tobacco additive or the tobacco material, fixing the sample in a cracking quartz tube by using quartz wool, putting the sample into a cracking instrument, and heating by a platinum wire heating program in multiple steps under a gas atmosphere so as to carry out heating cracking. After cracking in each step, collecting a cracking product, carrying out desorption sample injection, and carrying out qualitative and quantitative detection; and carrying out next cracking after detection and analysis are completed.
Further, the cleavage conditions were: the cracking gas is selected from a mixed gas of oxygen and nitrogen, or one or two mixed gases of air, nitrogen, helium and other inert gases; the flow rate of the cracking gas is 20-100 ml/min; the temperature of the cracking chamber is 280 ℃; the transmission line temperature is 280 ℃.
Preferably, the cracking gas is selected from a mixed gas of oxygen and nitrogen, and the volume ratio of the oxygen to the nitrogen is 9: 91.
Preferably, the cracked gas flow rate is 70 ml/min.
Preferably, the cracker is a CDS5250T thermal cracker.
Further, the sample is fixed in a cracking quartz tube of a CDS5250T thermal cracker in a way that a cracking quartz rod is placed in the cracking quartz tube, quartz wool is filled in the central position above the cracking quartz rod, a tobacco additive or tobacco material sample is weighed and placed above the quartz wool, then the quartz wool is filled in the sample and compacted, and the cracking quartz tube is placed in the cracking cracker.
Further, the temperature raising procedure of the multi-step sequence is as follows:
firstly, the initial temperature is 100 ℃, the temperature is kept for 5s-10s, the temperature is raised to 150 ℃ at the speed of 20-50 ℃/s, and the temperature is kept for 5s-60 s;
secondly, keeping the initial temperature at 150 ℃ for 5-10 s, heating to 200 ℃ at the speed of 20-50 ℃/s, and keeping the temperature for 5-60 s;
thirdly, keeping the initial temperature at 200 ℃ for 5-10 s, heating to 250 ℃ at the speed of 20-50 ℃/s, and keeping the temperature for 5-60 s;
fourthly, the initial temperature is 250 ℃, the temperature is kept for 5s to 10s, the temperature is raised to 300 ℃ at the speed of 20 to 50 ℃/s, and the temperature is kept for 5s to 60 s;
fifthly, keeping the initial temperature at 300 ℃ for 5-10 s, heating to 400 ℃ at the speed of 20-50 ℃/s, and keeping the temperature for 5-60 s;
sixthly, keeping the initial temperature at 400 ℃ for 5-10 s, heating to 500 ℃ at the temperature of 20-50 ℃/s, and keeping the temperature for 5-60 s;
seventhly, keeping the initial temperature at 500 ℃ for 5-10 s, heating to 600 ℃ at the temperature of 20-50 ℃/s, and keeping the temperature for 5-60 s;
eighthly, keeping the initial temperature at 600 ℃ for 5-10 s, heating to 700 ℃ at the temperature of 20-50 ℃/s, and keeping the temperature for 5-60 s;
ninth, keeping the initial temperature at 700 ℃ for 5-10 s, heating to 800 ℃ at 20-50 ℃/s, and keeping the temperature for 5-60 s;
the tenth step, the initial temperature is 800 ℃, the temperature is kept for 5s-10s, the temperature is raised to 900 ℃ at the speed of 20-50 ℃/s, and the temperature is kept for 5s-60 s.
Further, the trapping mode of trapping the cracking products in the sample injection is one of the following modes:
(a) cold trap and liner tube, the liner tube is filled with sorbent;
(b) the cold trap and the liner tube are filled with non-adsorbent fillers;
(c) the liner tube is filled with an adsorbent.
Preferably, the cold source of the cold trap is liquid nitrogen or other cold source.
Preferably, the adsorbent filled in the liner in the trapping modes (a) and (c) is one adsorbent, and can also be a composite adsorbent formed by filling a plurality of adsorbents in any proportion in the liner.
Preferably, in the trapping modes (a) and (C), the adsorbent is one or more of Carbotrap B, Carbotrap C and TENAX.
More preferably, the adsorbent in trapping means (a) and (C) is Carbotrap B or Carbotrap C or TENAX.
Preferably, the temperature of the cold trap in the trapping way (a) and the trapping way (b) is-196-30 ℃.
The non-adsorbent filler in the trapping mode (b) is glass wool.
More preferably, the cold trap temperature is from-180 ℃ to-40 ℃.
The principle of trapping is as follows: the cold trap coated outside the liner tube and the liner tube can be filled with adsorbents for trapping, wherein the adsorbents are used for adsorbing required gas phase components, and a plurality of adsorbents can be used together for adsorbing more required gas phase components; meanwhile, the required gas phase components can be trapped by using different cold trap temperatures during trapping, so that the trapping efficiency is improved. The choice of which capture means to use depends on the nature of the lysate and the nature of the substance produced by the lysis. The cold trap is used alone to trap gas phase components, the lining pipe is not filled with an adsorbent and is only filled with glass wool, and the temperature of the cold trap which needs to be used is lower; the adsorbent is used for trapping independently, the cold trap does not work, the trapping temperature is 30 ℃ at room temperature, the temperature programming and sample injection initial temperature is 30 ℃ at room temperature, and the trapping effect on micromolecular gas-phase components below six carbons is poor; the cold trap and the adsorbent are used for trapping together, the trapping effect is best, and basically all small molecule gas phase components generated by cracking (except carbon monoxide and the like) can be trapped.
Furthermore, the desorption sampling condition in the capture sampling is to keep for 1-6min at 200-330 ℃.
Further, the qualitative detection is to determine the composition of the cracked gas-phase components by map database retrieval; the quantitative detection is to determine the relative content of the cracked gas-phase components by adopting a peak area normalization method.
The qualitative detection means that the thermal cracking product is integrated by adopting an RTE integration mode, the peak area is 0.1% larger than the maximum peak area, and a mass spectrum library is applied to retrieval and qualitative determination. The mass spectrum database is a willey 7n and a Nist98 spectrum database.
The quantitative detection adopts peak area normalization to calculate, and the average value of two parallel determinations is taken as a determination result. Wherein the semi-quantitative data result formula (1) is calculated:
Xi＝Mi/ΣMi…………………………………(1)
in the formula:
Xi-peak area normalization percentage of a thermal cracking product;
Mi-peak area of a thermal cracking product;
ΣMi-total integrated area of thermal cracking products.
Further, the conditions of the gas chromatograph-mass spectrometer are as follows:
gas chromatography conditions: a chromatographic column: 30 m.times.0.25 mm.times.0.25 μm (DB-5MS elastic capillary column); carrier gas flow: 1.0 mL/min; the split ratio is as follows: 30: 1; temperature rising procedure: the initial temperature is 40 ℃, the temperature is kept for 3min, the temperature is increased to 240 ℃ at 5 ℃/min, then the temperature is increased to 280 ℃ at 10 ℃/min, and the temperature is kept for 10 min; sample inlet temperature: 250 ℃;
mass spectrum conditions: mass spectrometry transmission line temperature: 280 ℃; ion source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃; an ionization mode: electron impact ionization (EI); electron energy: 70 eV; mass scan range: 29 to 450 amu; solvent delay time: 1.5 min.
When the tobacco additive or the tobacco material is cracked at the temperature below 250 ℃, only few substances, mainly free nicotine, other alkaloids and neophytadiene can be directly transferred from tobacco leaves to smoke. 300-500 ℃ cracking is a cracking stage of precursors such as carbohydrates, amino acids, pigments, pigment long-chain fatty acid esters, open-chain isoprenes and siberian alkanes substances in tobacco and is a main temperature zone formed by most volatile and semi-volatile substances; the main products of the tobacco additive or the tobacco material cracked at 600 ℃ are benzene series, polycyclic aromatic hydrocarbon and nitrile substances, and when cracked at 700-900 ℃, carbonized tobacco and oxygen are mainly combusted to form simple gases such as carbon dioxide, carbon monoxide and the like.
The method provided by the invention adopts multi-step sequential temperature rising cracking, is different from a constant temperature or program temperature rising method in a conventional method, can truly reflect the cracking conditions of the tobacco additive or the tobacco material at different cracking temperatures, better determines the change behavior of the combustion or cracking product of the tobacco along with the temperature, clearly shows the formation relationship of the cracking product and the temperature, clearly knows the relationship of each cracking component and the tobacco precursor, the change relationship of the tobacco precursor along with the temperature and the temperature area formed by each harmful component, and thus provides a basis for researching the combustion behavior or combustion mechanism of the tobacco additive or the tobacco material.
In the invention, the cold trap is adopted for trapping besides the adsorbent, so that the trapping efficiency of the cracking component is improved. The invention adopts different sample introduction conditions and gas-mass combined measurement conditions, and can effectively and comprehensively detect the components in the tobacco additive and the tobacco material cracking product. The method can not only determine the semi-volatile components formed in the additive cracking process, but also determine a plurality of low molecular weight gas phase harmful components in the cracking products, and can comprehensively evaluate the harmfulness of the tobacco additive and the tobacco material cracking products.
Compared with the traditional method, the method is simple to operate, advanced in technology, capable of automatically analyzing after inputting an operation program, capable of improving working efficiency, small in sample amount required by the research, free of organic solvent, capable of saving raw materials, low in research cost, high in safety and environment-friendly. The method can be well applied in industry, can be used for controlling the formation of harmful ingredients of cigarettes in the future and improving the health of consumers.
Drawings
FIG. 1 is a schematic of an on-line multi-step sequential cracking-cold trap and adsorbent trap-GC/MS of the present invention;
FIG. 2 is a schematic of an on-line multi-step sequential cracking-cold trap trapping-GC/MS of the present invention;
FIG. 3 is a schematic of an on-line multi-step sequential cracking-adsorbent trapping-GC/MS of the present invention;
FIG. 4 is a temperature programmed cracking chromatogram of Honghe tobacco leaves;
FIG. 5 is a temperature programmed cracking chromatogram of Lijiang B22 Tao tobacco leaves;
FIG. 6 is a multi-step cracking chromatogram of Honghe tobacco leaves;
FIG. 7 is a sucrose multi-step cleavage chromatogram;
FIG. 8 is a chromatogram of a multistep cleavage of proline;
FIG. 9 is a multi-step cracking chromatogram of Zimbabwe C10 tobacco leaf;
FIG. 10 is a multi-step cleavage chromatogram of Brazil M02 tobacco leaves;
FIG. 11 is a multi-step cracking chromatogram of Tanshanbaofeng tobacco leaves;
description of the element reference numerals
1: cracking chamber I: and (3) cold trap II: a liner and an adsorbent filled in the liner.
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
The materials selected in this example include the following:
instrument for measuring the position of a moving object
CDS5250T thermal cracker (CDS Analytical, USA), cracked quartz tube (CDSAnalytical, USA), cracked quartz rod (CDS Analytical, USA), Agilent 7890-.
Samples and reagents
Quartz wool (pesticide residue grade, CDS Analytical, usa), adsorbent: TENAX (Gerstel, Germany), non-adsorbent packing: glass wool (Gerstel, Germany), sucrose, proline, Honghe tobacco leaf, Lijiang B22 Tao tobacco leaf, Zimbabwe C10 tobacco leaf, Brazil M02 tobacco leaf, Taiwan mountain Baofeng tobacco leaf.
Comparative example 1
1. Carrying out programmed heating cracking on the Honghe tobacco:
sample preparation: putting a cracked quartz tube into a cracked quartz rod, filling a proper amount of pesticide residue grade quartz cotton (the dosage is 1 +/-0.10 mg, winding into a mass) at the central position, weighing a 1mg +/-0.05 mg red river tobacco powder sample, putting the red river tobacco powder sample on the quartz cotton, filling 1mg +/-0.10 mg quartz cotton at the upper end of the sample, compacting, preventing the sample from being blown into a cracking cavity by air flow used in cracking, and putting the cracked quartz tube into a cracking instrument to be cracked.
Sample lysis conditions: cracking atmosphere: mixed gas of oxygen and nitrogen (9: 91, volume ratio); cracking gas flow rate: 70 mL/min; cracking temperature rise procedure: the temperature was maintained at 300 ℃ for 5 seconds, and then raised to 900 ℃ at 30 ℃/s for 5 seconds. Temperature of the valve box: 280 ℃; transmission line temperature: 280 ℃;
cleavage product trapping conditions: adopting a cold trap for trapping, wherein the temperature of the cold trap is-60 ℃;
thermal desorption sample introduction conditions are as follows: the temperature of the trap is increased from-60 ℃ to 280 ℃, and the desorption is completed within 3 min.
Carrying out qualitative and quantitative detection on the gas phase components subjected to trapping and sample injection through a gas chromatography-mass spectrometer;
GC conditions: a chromatographic column: DB-5MS elastic capillary column (30m 0.25mm 0.25 μm); carrier gas flow: 1.0 mL/min; temperature programming: the initial temperature is 40 ℃, the temperature is kept for 3min, the temperature is increased to 240 ℃ at 5 ℃/min, then the temperature is increased to 280 ℃ at 10 ℃/min, and the temperature is kept for 10 min; ion source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃; sample inlet temperature: 250 ℃; mass spectrometry transmission line temperature: 280 ℃; an ionization mode: electron impact ionization (EI); electron energy: 70 eV; mass scan range: 29 to 450 amu; solvent delay time: 1.5 min; the split ratio is as follows: 100: 1.
2. results and discussion
The pyrolysis gas phase component of the Honghe tobacco is analyzed by using the programmed heating pyrolysis method in the comparative example 1, fig. 4 is a chromatogram measured by a gas chromatograph-mass spectrometer, the relationship between the formation of a pyrolysis product and the pyrolysis temperature cannot be seen from fig. 4, the relationship between a precursor and a corresponding pyrolysis product cannot be obtained, and the relationship between the pyrolysis temperature and the formation of harmful components cannot be inferred, so that the mechanism of pyrolysis or combustion of the tobacco cannot be inferred according to the pyrolysis condition.
Comparative example 2
1. Lijiang B22 isothermal cracking of tobacco leaves
Sample preparation: taking one cracked quartz tube, putting a cracked quartz rod into the cracked quartz tube, filling a proper amount of pesticide residue grade quartz cotton (the dosage is 1 +/-0.10 mg, winding the quartz tube into a cluster) at the central position, weighing 1mg +/-0.05 mg of Lijiang B22 sample of tobacco powder, putting the tobacco powder sample on the quartz cotton, filling 1mg +/-0.10 mg of quartz cotton at the upper end of the sample, compacting the quartz cotton to prevent the sample from being blown into a cracking cavity by airflow used in cracking, and putting the cracked tube into a cracking instrument to be cracked.
Sample lysis conditions: cracking atmosphere: mixed gas of oxygen and nitrogen (9: 91, volume ratio); cracking gas flow rate: 70 mL/min; cracking temperature rise procedure: cracking at 300 deg.C, 450 deg.C, 600 deg.C, 750 deg.C, 900 deg.C for 40 s. Temperature of the valve box: 280 ℃; transmission line temperature: 280 ℃;
cleavage product trapping conditions: adopting a cold trap for trapping, wherein the temperature of the cold trap is-60 ℃;
thermal desorption sample introduction conditions are as follows: the temperature of the trap is increased from-60 ℃ to 280 ℃, and the desorption is completed within 3 min.
Carrying out qualitative and quantitative detection on the gas phase components subjected to trapping and sample injection through a gas chromatography-mass spectrometer;
GC conditions: a chromatographic column: DB-5MS elastic capillary column (30m 0.25mm 0.25 μm); carrier gas flow: 1.0 mL/min; temperature programming: the initial temperature is 40 ℃, the temperature is kept for 3min, the temperature is increased to 240 ℃ at 5 ℃/min, then the temperature is increased to 280 ℃ at 10 ℃/min, and the temperature is kept for 10 min; ion source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃; sample inlet temperature: 250 ℃; mass spectrometry transmission line temperature: 280 ℃; an ionization mode: electron impact ionization (EI); electron energy: 70 eV; mass scan range: 29 to 450 amu; solvent delay time: 1.5 min; the split ratio is as follows: 100: 1.
2. results and discussion
The method comprises the steps of carrying out isothermal cracking on Lijiang B22 selected tobacco, wherein the cracking temperatures are respectively 300 ℃, 450 ℃, 600 ℃, 750 ℃ and 900 ℃, the cracking temperatures are respectively 40s, and fig. 5 is a chromatogram measured by a gas chromatograph-mass spectrometer, wherein only the cracking temperature can be seen to influence the formation of a cracking product in fig. 5, but the formation of the cracking product is very complex, the cracking behavior of a precursor along with the temperature cannot be seen, and the relationship between the precursor and the corresponding cracking product at different temperatures cannot be seen, so that the combustion or cracking mechanism of the tobacco cannot be well inferred according to the isothermal cracking condition.
Example 1
1. Multistep sequential cracking of Honghe tobacco powder
Sample preparation: putting a cracked quartz tube into a cracked quartz rod, filling a proper amount of pesticide residue grade quartz cotton (the dosage is 1 +/-0.10 mg, and the quartz rod is wound into a cluster) at the central position, weighing a 1mg +/-0.05 mg sample of the Honghe tobacco leaf powder, putting the sample on the quartz cotton, filling 1mg +/-0.10 mg of quartz cotton at the upper end of the sample, compacting, preventing the sample from being blown into a cracking cavity by air flow used in cracking, and putting the cracking tube into a cracking instrument to be cracked.
The temperature raising program of the multi-step sequential cracking is as follows:
firstly, the initial temperature is 100 ℃, the temperature is kept for 5s, the temperature is raised to 150 ℃ at the speed of 50 ℃/s, and the temperature is kept for 60 s; step two, keeping the initial temperature at 150 ℃ for 5s, heating to 200 ℃ at the speed of 50 ℃/s, and keeping the temperature for 60 s; step three, the initial temperature is 200 ℃, the temperature is kept for 5s, the temperature is increased to 250 ℃ at the speed of 50 ℃/s, and the temperature is kept for 60 s; fourthly, the initial temperature is 250 ℃, the temperature is kept for 5s, the temperature is increased to 300 ℃ at the speed of 50 ℃/s, and the temperature is kept for 60 s; fifthly, keeping the initial temperature at 300 ℃ for 5s, heating to 400 ℃ at a speed of 50 ℃/s, and keeping the temperature for 60 s; sixthly, keeping the initial temperature at 400 ℃ for 5s, heating to 500 ℃ at the speed of 50 ℃/s, and keeping the temperature for 60 s; seventhly, keeping the initial temperature at 500 ℃ for 5s, heating to 600 ℃ at the temperature of 50 ℃/s, and keeping the temperature for 60 s; eighthly, keeping the initial temperature at 600 ℃ for 5s, heating to 700 ℃ at the temperature of 50 ℃/s, and keeping the temperature for 60 s; ninth, the initial temperature is 700 ℃, the temperature is kept for 5s, the temperature is increased to 800 ℃ at the speed of 50 ℃/s, and the temperature is kept for 60 s; the tenth step, the initial temperature is 800 ℃, the temperature is kept for 5s, the temperature is increased to 900 ℃ at the speed of 50 ℃/s, and the temperature is kept for 60 s.
Cracking atmosphere: helium gas; cracking gas flow rate: 70 mL/min; temperature of the valve box: 280 ℃; transmission line temperature: 280 ℃;
cleavage product trapping conditions: adopting liquid nitrogen and an adsorbent TENAX to carry out trapping together, wherein the trapping temperature is-196 ℃;
thermal desorption sample introduction conditions are as follows: the temperature of the trap is increased from-60 ℃ to 290 ℃, and the desorption is completed within 5 min.
GC conditions: a chromatographic column: DB-5MS elastic capillary column (30m 0.25mm 0.25 μm); carrier gas flow: 1.0 mL/min; the split ratio is as follows: 30: 1; temperature rising procedure: the initial temperature is 40 ℃, the temperature is kept for 3min, the temperature is increased to 240 ℃ at 5 ℃/min, then the temperature is increased to 280 ℃ at 10 ℃/min, and the temperature is kept for 10 min; sample inlet temperature: 250 ℃; mass spectrometry transmission line temperature: 280 ℃; ion source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃; an ionization mode: electron impact ionization (EI); electron energy: 70 eV; mass scan range: 29 to 450 amu; solvent delay time: 1.5 min.
2. Results and discussion
And (2) carrying out multi-step sequential cracking on the Honghe tobacco powder, wherein after ten steps of cracking, a cracked sample quartz tube obtained after each step of cracking is still remained in a cracking cavity, collecting cracked components in the first step, carrying out thermal desorption and sample injection, and after the analysis of a gas chromatography-mass spectrometer is completed, carrying out a second cracking procedure until all cracking procedures are executed, separated and identified.
Tables 1-7 show cracked gas phase components detected by multi-step cracking of the Honghe tobacco leaves, fig. 6 shows chromatograms measured by a multi-step cracking and gas chromatograph-mass spectrometer of the Honghe tobacco leaves, and through a multi-step sequential cracking method, several stages in the tobacco cracking process can be clearly seen from fig. 6, the influence of temperature on the formation of cracking products can be clearly seen, and the corresponding relationship between each cracking product of the tobacco and each precursor of the tobacco can be clearly known; the prevailing temperature at which the tobacco noxious substances are formed can also be clearly seen.
TABLE 1 major volatile products detected in the lysis of Honghe tobacco leaves at 150 ℃
TABLE 2 major volatile products formed during 200 ℃ pyrolysis of tobacco leaves
As can be seen from tables 1 and 2, only the presence of nicotine, myosmine, nicotinene and neophytadiene was detected in tobacco leaves at 150 ℃ and 200 ℃ when the compounds in tobacco were volatilized mainly by distillation.
TABLE 3 major volatile products formed during the 250 ℃ pyrolysis of tobacco leaves
It can be seen in table 3 that when the cracking temperature reaches 250 ℃, the release of nicotine is very significantly increased and other alkaloids such as maciten, nicotinene and 2,3' -bipyridine are released again, since the bound nicotine salt in tobacco begins to crack. In addition, no neophytadiene was detected when the cleavage was carried out at 250 ℃, indicating that the free neophytadiene had completely volatilized.
Some products formed by carbohydrate degradation begin to appear, such as: DDMP, hydroxymaltol, maltol, furfural, furfuryl alcohol, 2, 5-difurfural, etc., but 5-methylfurfural and 5-hydroxymethylfurfural have not yet been formed, and products such as levoglucosone, levoglucosan, 1, 6-anhydro- α -D-galactofuranose, 1,4:3, 6-dianhydro- α -D-glucopyranose, etc., formed by dehydration of glucose, fructose and sucrose, have not been formed.
When the tobacco is cracked at 250 ℃, the existence of solanone is detected, the solanone is a very important aroma component in the tobacco, and is a degradation product of siberian substances in the tobacco, and meanwhile, the siberian substances can form solanol, norsolanedione, spiroragone, 6-methyl-2, 5-heptanedione and the like during degradation.
TABLE 4 major volatile products formed during 300 ℃ pyrolysis of tobacco leaves
The tobacco leaf cracking forms flavor compounds mainly at 300-600 ℃, and the content of the flavor compounds formed by the tobacco cracking at 300-600 ℃ is far higher than that of flavor substances generated by distillation. Before 300 ℃, only a few substances such as nicotine and other alkaloids are directly transferred from tobacco shreds to smoke, and when the temperature rises to 300 ℃ and 500 ℃, many substances in the tobacco shreds, such as terpenes, phytosterols such as stigmasterol, paraffin, saccharides, amino acids, celluloses and many other components, undergo violent and complex chemical reactions (mainly comprising thermal decomposition, cracking synthesis, dry distillation, polymerization, condensation, free radical and other reactions) in the temperature zone to form a large amount of volatile and semi-volatile gas and liquid and solid substances, and about 5000 fragrant substances in the smoke are formed in a cracking/distillation zone at the rear end of a combustion zone, which is a main stage for forming tobacco fragrant substances.
At 300 ℃, the amount of furfural, furfuryl alcohol, 5-methylfurfural, DDMP, 5-hydroxy maltol, 5-hydroxymethylfurfural and the like formed by the cracking of carbohydrates in tobacco leaves begins to increase. At the same time, megastigmatrienone, 3-hydroxy-beta-damascenone, 3-oxo-alpha-ionol began to be produced.
The temperature of 400 ℃ and 500 ℃ are the main stages of tobacco leaf cracking and are also the most severe stages of carbohydrate cracking, amino acid degradation, Maillard reaction and flavor precursor degradation. When tobacco leaves are cracked at 400 ℃ and 500 ℃, a large amount of flavor compounds such as farnesyl acetone, geranyl acetone, geranial, farnesal, farnesol and the like are formed, the compounds are formed by cracking open-chain isoprene compounds in tobacco, the open-chain isoprene compounds in the tobacco mainly comprise solanesol, phytene, neophytadiene and the like, and the compounds form a large amount of important aroma components such as 6-methyl-5-heptene-2-one, geranyl acetone, geraniol, 6-methyl-3, 5-heptadiene-2-one, farnesyl acetone, farnesol and the like in the degradation process, and the important aroma components can endow the flue-cured tobacco with good fresh and sweet aroma.
The materials such as pyridine, pyrrole, picoline, methyl pyrrole and the like are formed by cracking at 400-500 ℃. These substances may be products of the degradation of alkaloids and amino acids in tobacco.
TABLE 5 major volatile products formed during 400 ℃ pyrolysis of tobacco leaves
TABLE 6 major volatile products formed upon 500 ℃ pyrolysis of tobacco leaves
As shown in Table 7, the tobacco leaves are cracked at 600 ℃ to form a large amount of benzene, toluene, ethylbenzene, xylene, naphthalene and other condensed ring aromatic compounds, and nitrile substances. Meanwhile, the tobacco material is cracked at 600 ℃ to form a large amount of nitrogen-containing heterocyclic compounds, such as picoline, methylpyrrole, lutidine, dimethylpyrrole compounds and the like. Nitrogenous heterocyclic compounds such as picoline, methylpyrrole, lutidine and the like and nitrile compounds formed by the cracking of tobacco leaves at 600 ℃ can be from the degradation of proteins in the tobacco.
TABLE 7 major volatile products formed upon 600 ℃ pyrolysis of tobacco leaves
The tobacco is cracked at the temperature of 700 ℃ and 900 ℃, and the temperature of the tobacco is equivalent to the temperature of a burning zone of the cigarette. When tobacco is cracked at 700 ℃, 800 ℃ and 900 ℃, basically no new products appear, and simple gases may be generated by cracking, and the gas components cannot be detected under experimental analysis conditions. This shows that the tobacco leaves are cracked at 600 deg.C, and basically completely, and carbon is left after cracking, and in the cracking at 700 deg.C, 800 deg.C and 900 deg.C, carbon and oxygen form simple gases, such as carbon dioxide, carbon monoxide, water, hydrogen, methane and other compounds, at the high temperature of 700 deg.C and 900 deg.C due to the existence of oxygen.
Therefore, by utilizing multi-step sequential cracking, the influence of the cracking temperature on volatile and semi-volatile substances released by the cracking of the tobacco leaves can be well researched, so that the method is used for revealing the relationship between the substances released during the burning and smoking of the cigarettes and the reaction path and mechanism during the burning of the cigarettes.
Example 2
The cracking sample is sucrose, the temperature raising procedure and method for cracking is the same as example 1, but different from example 1: cracking atmosphere: 10% O2And 90% He mixed gas; cracking gas flow rate: 50 mL/min; cleavage product trapping conditions: adopting liquid nitrogen and an adsorbent Carbotrap C for trapping, wherein the trapping temperature is-100 ℃; thermal desorption sample introduction conditions are as follows: raising the temperature of the trap from-100 ℃ to 300 ℃, completing desorption within 6min, and cracking to the eighth step. The other conditions were the same as in example 1.
FIG. 7 is a chromatogram measured by a GC-MS apparatus. As can be seen from FIG. 7, the temperature dependence of sucrose cleavage can be well revealed by the multi-step sequential cleavage method, and the cleavage process or cleavage mechanism can be inferred from the products formed by each step of cleavage. However, if only a single step of cleavage is used, the route or mechanism of sucrose cleavage cannot be revealed.
Example 3
The cleaved sample was proline, in the same manner as in example 1. Different from example 1, from the multi-step sequential cracking to the seventh step, the cracking atmosphere: 10% O2And 90% He mixed gas; cracking gas flow rate: 50 mL/min; cleavage product trapping conditions: using liquid nitrogen and adsorbent Carbotrap B, trapping at-60 deg.C; thermal desorption sample introduction conditions are as follows: the temperature of the trap is increased from-60 ℃ to 280 ℃, and the desorption is completed within 3 min.
FIG. 8 is a chromatogram measured by a corresponding GC, and it can be seen from FIG. 8 that the relationship of proline cleavage with temperature can be clearly seen by using a multi-step sequential cleavage method, the temperature region of the cleavage product is mainly 400 ℃ and 500 ℃, the cleavage products in other temperature regions are relatively less, but the cleavage process or the cleavage mechanism can be estimated according to the products formed by cleavage in each temperature region. If only a single cleavage is used, the pathway followed by proline cleavage cannot be revealed or the cleavage mechanism cannot be presumed.
Example 4
Cracking the sample: zimbabwe C10 tobacco leaf. The specific procedure is the same as in example 1. Different from the example 1, the temperature rising rate in the temperature rising procedure of the multi-step sequential cracking is 20 ℃/s, and the temperature is kept for 30s at the corresponding cracking temperature after temperature rising; cracking gas flow rate: 40 mL/min; cleavage product trapping conditions: adopting liquid nitrogen and a Carbotrap C and TENAX adsorbent with the mass ratio of 1:1 for trapping, wherein the trapping temperature is-180 ℃; thermal desorption sample introduction conditions are as follows: the temperature of the trap is increased from-150 ℃ to 250 ℃, and the desorption is completed within 2 min.
FIG. 9 is a chromatogram measured by the corresponding GC-MS, and it can be seen from the chromatogram that the relationship of the cracked products with temperature when cracking Zimbabwe C10 tobacco leaves can be well elucidated by adopting the multi-step sequential cracking, and because the temperature distribution range inside tobacco cigarettes is also between 150 ℃ and 950 ℃ when the tobacco is burned, the multi-step sequential cracking can be better seen to show that the products formed by the tobacco cracking in each temperature range can be interpreted as to which precursors are likely to form, so as to calculate the degradation temperature and the degradation mechanism of the tobacco precursor, and further to predict the change or mechanism generated in the combustion process of the tobacco. The mechanism of combustion of Zimbabwe C10 tobacco leaves is difficult to predict by the single-step temperature-variable cracking or isothermal cracking method.
Example 5
Cracking the sample: brazil M02 tobacco leaf. The specific procedure is the same as in example 1. In contrast to example 1, the temperature program for the multi-stage sequential cleavage was:
firstly, the initial temperature is 100 ℃, the temperature is kept for 10s, the temperature is increased to 150 ℃ at the speed of 30 ℃/s, and the temperature is kept for 5 s; secondly, keeping the initial temperature at 150 ℃ for 10s, heating to 200 ℃ at the speed of 30 ℃/s, and keeping the temperature for 5 s; thirdly, the initial temperature is 200 ℃, the temperature is kept for 10s, the temperature is increased to 250 ℃ at the speed of 30 ℃/s, and the temperature is kept for 5 s; fourthly, the initial temperature is 250 ℃, the temperature is kept for 10s, the temperature is increased to 300 ℃ at the speed of 30 ℃/s, and the temperature is kept for 5 s; fifthly, keeping the initial temperature at 300 ℃ for 10s, raising the temperature to 400 ℃ at 30 ℃/s, and keeping the temperature for 5 s; sixthly, keeping the initial temperature at 400 ℃ for 10s, raising the temperature to 500 ℃ at 30 ℃/s, and keeping the temperature for 5 s; seventhly, keeping the initial temperature at 500 ℃ for 10s, heating to 600 ℃ at the temperature of 30 ℃/s, and keeping the temperature for 5 s; eighthly, keeping the initial temperature at 600 ℃ for 10s, heating to 700 ℃ at the temperature of 30 ℃/s, and keeping the temperature for 5 s; ninth, the initial temperature is 700 ℃, the temperature is kept for 10s, the temperature is increased to 800 ℃ at the speed of 30 ℃/s, and the temperature is kept for 5 s; the tenth step, the initial temperature is 800 ℃, the temperature is kept for 10s, the temperature is increased to 900 ℃ at the speed of 30 ℃/s, and the temperature is kept for 5 s.
Cracking gas flow rate: 40 mL/min; cleavage product trapping conditions: adopting an adsorbent TENAX for trapping, wherein the trapping temperature is 30 ℃; thermal desorption sample introduction conditions are as follows: the temperature of the trap is increased from 30 ℃ to 300 ℃, and the desorption is completed within 3 min.
FIG. 10 is a chromatogram measured by the corresponding GC-MS, and it can be seen from FIG. 10 that the relationship between the cracked products of the cracking of the Brazilian M02 tobacco leaves with temperature can be well elucidated by the multi-step sequential cracking, and since the temperature distribution range of the tobacco in the tobacco is also 150-950 ℃ during the combustion, the products formed by the tobacco cracking can be better seen by the multi-step sequential cracking, and the products possibly formed by the precursors can be interpreted, so as to calculate the degradation temperature and the degradation mechanism of the tobacco precursor, and further to predict the change or mechanism generated during the combustion of the tobacco. The mechanism of combustion of Brazilian M02 tobacco leaves is difficult to predict by the single-step temperature-variable cracking or isothermal cracking method.
Example 6
Cracking the sample: flattop mountain baofeng tobacco leaf. The specific procedure is the same as in example 1. In contrast to example 1, the temperature program for the multi-stage sequential cleavage was:
firstly, the initial temperature is 100 ℃, the temperature is kept for 7s, the temperature is increased to 150 ℃ at the speed of 40 ℃/s, and the temperature is kept for 20 s; step two, keeping the initial temperature at 150 ℃ for 7s, heating to 200 ℃ at 40 ℃/s, and keeping the temperature for 20 s; step three, the initial temperature is 200 ℃, the temperature is kept for 7s, the temperature is increased to 250 ℃ at the speed of 40 ℃/s, and the temperature is kept for 20 s; fourthly, the initial temperature is 250 ℃, the temperature is kept for 7s, the temperature is increased to 300 ℃ at the speed of 40 ℃/s, and the temperature is kept for 20 s; fifthly, keeping the initial temperature at 300 ℃ for 7s, heating to 400 ℃ at 40 ℃/s, and keeping the temperature for 20 s; sixthly, keeping the initial temperature at 400 ℃ for 7s, raising the temperature to 500 ℃ at 40 ℃/s, and keeping the temperature for 20 s; seventhly, keeping the initial temperature at 500 ℃ for 7s, heating to 600 ℃ at 40 ℃/s, and keeping the temperature for 20 s; eighthly, keeping the initial temperature at 600 ℃ for 7s, heating to 700 ℃ at 40 ℃/s, and keeping the temperature for 20 s; ninth, the initial temperature is 700 ℃, the temperature is kept for 7s, the temperature is increased to 800 ℃ at 40 ℃/s, and the temperature is kept for 20 s; the tenth step, the initial temperature is 800 ℃, the temperature is kept for 7s, the temperature is increased to 900 ℃ at 40 ℃/s, and the temperature is kept for 20 s.
Cracking atmosphere: air; cracking gas flow rate: 20 mL/min; cleavage product trapping conditions: adopting cold trap and carbon B, carbon C and TENAX adsorbents with the mass ratio of 1:1:1 to jointly trap, wherein the temperature of the cold trap is-60 ℃; thermal desorption sample introduction conditions are as follows: the temperature of the trap is increased from-60 ℃ to 280 ℃, and the desorption is completed within 6 min.
FIG. 11 is a chromatogram measured by the corresponding GC-MS, and it can be seen from FIG. 11 that the behavior of the cracked product of the Tanshanbaofeng tobacco leaves along with the temperature change can be well elucidated by the multi-step sequential cracking, and it can be clearly seen that the products formed by the tobacco cracking can be interpreted by excluding the products formed by the preceding temperature cracking in the temperature range of each step of the sequential cracking, and the products formed by the tobacco cracking can be interpreted as being possibly formed by the precursors, so as to calculate the degradation temperature and the degradation mechanism of the tobacco precursor, and further to predict the change or mechanism generated in the combustion process of the tobacco. However, the mechanism of the combustion of the flattop mountain Baofeng tobacco leaves is difficult to be speculated by a single-step temperature-variable cracking method or an isothermal cracking method.
In summary, the multi-step sequential heating cracking method provided by the invention can detect gas phase components obtained by cracking at different cracking temperatures, and can be used for researching the influence of the cracking temperature on volatile and semi-volatile substances released by the cracking of the tobacco additive or the tobacco material, thereby revealing the relationship between the substances released during the combustion of the tobacco additive or the tobacco material and the temperature, and providing a basis for researching the combustion behavior or the combustion mechanism of the tobacco additive or the tobacco material.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (6)
1. A method for on-line detecting pyrolysis gas-phase components of tobacco additives or tobacco materials at different temperatures is characterized by comprising the following steps:
cracking: carrying out multi-step sequential heating cracking on the tobacco additive or the tobacco material;
collecting and sampling: collecting the tobacco additive or tobacco material cracking product obtained by cracking in each step, and then carrying out desorption sample injection;
and (3) determination: carrying out qualitative and quantitative detection on the sample introduction sample by a gas chromatography-mass spectrometer;
in the multi-step sequential heating cracking, after each step of cracking is finished, a cracking product is captured, desorbed and injected, and qualitative and quantitative detection is carried out; after the analysis is finished, the next step of cracking is carried out;
the cracking conditions are as follows:
the cracking gas is selected from mixed gas of oxygen and nitrogen, or one or two of air, nitrogen and helium;
the flow rate of the cracking gas is 20-100 ml/min;
the temperature of a valve box of the cracking instrument is 250-300 ℃;
the temperature of the transmission line is 250 ℃ and 300 ℃;
the temperature rising program of the multi-step sequence is as follows:
firstly, the initial temperature is 100 ℃, the temperature is kept for 5s-10s, the temperature is raised to 150 ℃ at the speed of 20-50 ℃/s, and the temperature is kept for 5s-60 s;
secondly, keeping the initial temperature at 150 ℃ for 5-10 s, heating to 200 ℃ at the speed of 20-50 ℃/s, and keeping the temperature for 5-60 s;
thirdly, keeping the initial temperature at 200 ℃ for 5-10 s, heating to 250 ℃ at the speed of 20-50 ℃/s, and keeping the temperature for 5-60 s;
fourthly, the initial temperature is 250 ℃, the temperature is kept for 5s to 10s, the temperature is raised to 300 ℃ at the speed of 20 to 50 ℃/s, and the temperature is kept for 5s to 60 s;
fifthly, keeping the initial temperature at 300 ℃ for 5-10 s, heating to 400 ℃ at the speed of 20-50 ℃/s, and keeping the temperature for 5-60 s;
sixthly, keeping the initial temperature at 400 ℃ for 5-10 s, heating to 500 ℃ at the temperature of 20-50 ℃/s, and keeping the temperature for 5-60 s;
seventhly, keeping the initial temperature at 500 ℃ for 5-10 s, heating to 600 ℃ at the temperature of 20-50 ℃/s, and keeping the temperature for 5-60 s;
eighthly, keeping the initial temperature at 600 ℃ for 5-10 s, heating to 700 ℃ at the temperature of 20-50 ℃/s, and keeping the temperature for 5-60 s;
ninth, keeping the initial temperature at 700 ℃ for 5-10 s, heating to 800 ℃ at 20-50 ℃/s, and keeping the temperature for 5-60 s;
tenth step, keeping the initial temperature at 800 ℃ for 5-10 s, heating to 900 ℃ at the speed of 20-50 ℃/s, and keeping the temperature for 5-60 s;
a chromatographic column: DB-5MS elastic capillary column 30m × 0.25mm × 0.25 μm; carrier gas flow: 1.0 mL/min; the split ratio is as follows: 30: 1; temperature rising procedure: the initial temperature is 40 ℃, the temperature is kept for 3min, the temperature is increased to 240 ℃ at 5 ℃/min, then the temperature is increased to 280 ℃ at 10 ℃/min, and the temperature is kept for 10 min; sample inlet temperature: 250 ℃; mass spectrometry transmission line temperature: 280 ℃; ion source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃; an ionization mode: electron bombardment ionization; electron energy: 70 eV; mass scan range: 29 to 450 amu; solvent delay time: 1.5 min.
2. The method of claim 1, wherein: the multistep sequential heating cracking specifically comprises the following steps: weighing a sample of the tobacco additive or the tobacco material, fixing the sample in a cracking quartz tube by using quartz wool, putting the sample into a cracking instrument, and heating by a platinum wire heating program in multiple steps under a gas atmosphere so as to carry out heating cracking.
3. The method of claim 1, wherein: the trapping mode for trapping the cracking products in the sample injection is one of the following modes:
(a) cold trap and liner tube, the liner tube is filled with sorbent;
(b) the cold trap and the liner tube are filled with non-adsorbent fillers;
(c) the liner is filled with an adsorbent.
4. The method of claim 3, wherein: further comprising one or more of the following features:
the temperature of cold traps in the trapping modes (a) and (b) is-196-30 ℃;
the adsorbent in the trapping modes (a) and (C) is Carbotrap B or Carbotrap C or TENAX;
the non-adsorbent filler in the trapping mode (b) is glass wool.
5. The method of claim 1, wherein: the desorption and sample injection conditions in the capture sample injection are that the temperature is kept for 1-6min at 200-330 ℃.
6. The method of claim 1, wherein: the qualitative detection is to determine the composition of the cracked gas phase components through map database retrieval; the quantitative detection is to determine the relative content of the cracked gas-phase components by adopting a peak area normalization method.
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| CN113109483B (en) * | 2021-05-07 | 2023-05-16 | 上海烟草集团有限责任公司 | Analysis method of pyrolysis aroma components of latent aroma type aroma raw materials for cigarettes |
| CN116577432A (en) * | 2023-05-19 | 2023-08-11 | 云南省烟草质量监督检测站 | Analysis and detection method for organic acid substances in tobacco |
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