CN107422051A - A kind of method that gas phase composition is cracked under on-line checking tobacco additive agent or smoking material different temperatures - Google Patents
A kind of method that gas phase composition is cracked under on-line checking tobacco additive agent or smoking material different temperatures Download PDFInfo
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Abstract
The invention discloses a kind of method that gas phase composition is cracked under on-line checking tobacco additive agent or smoking material different temperatures, the heating that tobacco additive agent or smoking material are carried out to multistep order cracks；By the tobacco additive agent of every step cracking gained or smoking material pyrolysis product after trapping, desorption sample introduction is carried out；Qualitative and quantitative detection is carried out to sample introduction sample by gas chromatography-mass spectrometry.Method provided by the present invention, compared with conventional method, using multistep order heating cracking mode, it is simple to operate, advanced technology, it can really reflect the pyrolysis product of the cracking situation of tobacco additive agent or smoking material under different cracking temperatures, complete detection tobacco additive agent and smoking material, it can be used for the formation control of following cigarette harmful components, improve the health of consumer.
Description
Technical field
The technical field of the method for the gas phase composition discharged the invention belongs to on-line checking organic cracking, more particularly to
A kind of method that gas phase composition is cracked under on-line checking tobacco additive agent or smoking material different temperatures.
Background technology
Cigarette (including tobacco additive agent or smoking material) burning is one extremely complex and be difficult to the chemicals predicted
Reason process, cigarette occur in partial combustion process it is a series of distillation, condensation, cracking with cracking synthesize etc. physical chemistry it is anti-
Should, a large amount of new materials are formed, its chemical composition is very complicated, is a complicated process.Various organic matters in tobacco are with temperature
Various material variation with temperature relations and cigarette burning mechanism in the variation relation of degree, flue gas are not fully understood.
At present, had substantial amounts of scholar to the influence of cigarette burning mechanism, ignition temperature to smoke chemistry composition and
Correlation between cigarette chemical composition and smoke chemistry composition is studied, wherein, cracking is everybody the most frequently used skill
Art means, but currently used cracking technique is all conventional cleavage method (including isothermal cracking-GC/MS technologies and journey
Sequence heating-GC/MS technologies), the relation between cracking temperature, chemical composition and pyrolysis product can not be disclosed well, wherein
Reaction mechanism and reactions change rule be difficult to really be disclosed.Baker et al. have studied volume using single step cracking technique
The several stages that may be undergone in cigarette combustion process, also using isotope combination cracking technique to the reaction during cigarette burning
Order is speculated.In addition, the expert and scholar in terms of also having domestic and international tobacco are using thermogravimetric, ftir Analysis GC-MS
The methods of simulate the relation of the combustion process of cigarette, the gaseous component that is discharged of measure result of combustion of tobacco and temperature, so as to speculate volume
The combustion mechanism of cigarette.The state of Qin is prosperous et al. using thermogravimetric-means of differential scanning calorimetry combination (TG-DSC) method, studies tobacco biomass
Burning behavior and combustion characteristics.Wang Hongbo etc. has been carried out point by thermogravimetric analyzer to the weightless behavior during result of combustion of tobacco
Analysis, thus it is speculated that the behavior that cigarette may occur in each humidity province.
Isothermal cracking-GC/MS technologies provide cracking information of the sample in specified temp point, and the cigarette in reality fires
During burning, the pyrolysis of tobacco is not what moment completed, but experienced temperature consecutive variations relatively long for a period of time
Process, therefore, isothermal cracking-GC/MS technologies are difficult to reflect the fragmentation pathways of sample in whole temperature-rise period and its form product
Consecutive variations situation.Temperature programming cracking-GC/MS technologies can not react the actual conditions of cigarette burning, and it is one
Final analog result, the stage undergone during cigarette burning and change procedure can not be speculated, cigarette burning can not be studied
Behavior and mechanism.Thermogravimetric/differential thermal analysis (TG/DTA) be using thermobalance measured under programed temperature sample quality with
The thermoanalysis technology of temperature change, it is possible to provide the weightless behavior of sample or thermal decomposition information under the conditions of temperature programming, but can not survey
Determine the product formed in heating process, therefore the relation that can not also establish between the precursor in tobacco and product, therefore
The mechanism of cigarette burning can not be studied, it can only be used as a supplementary means.The Instrument crosslinking such as thermogravimetric and infrared spectrum or mass spectrum
Technology can analyze effusion component to a certain extent, but for the relative complex pyrolytic reaction of product, because it escapes component
It is directly entered subsequent detection system, the quantitative and semi-quantitative analysis of its pyrolysis product as a mixture without chromatographic isolation
With regard to relative difficulty, therefore it can not really study the burning behavior or splitting mechanism of cigarette.
Dimension, it is necessary to design it is a kind of can detect gas phase that tobacco additive agent or smoking material crack at different temperatures into
The method divided, can determine the chemical composition under different cracking temperatures, and the corresponding cracking composition of foundation changes row with cracking temperature
For relation, so as to have according to the splitting mechanism for speculating tobacco additive agent or smoking material.
The content of the invention
In view of the above the shortcomings that prior art, it is an object of the invention to provide a kind of on-line checking tobacco additive agent
Or the method that gas phase composition is cracked under smoking material different temperatures, overcome existing detection method can not reflect it is whole burned
The problem of fragmentation pathways and reaction product in journey.
To achieve these goals or other purposes, the present invention is achieved by the following technical solutions：
A kind of method that gas phase composition is cracked under on-line checking tobacco additive agent or smoking material different temperatures, including it is following
Step：
Cracking：The heating that tobacco additive agent or smoking material are carried out to multistep order cracks；
Trap sample introduction：By the tobacco additive agent of every step cracking gained or smoking material pyrolysis product after trapping, taken off
Attached sample introduction；
Measure：Qualitative and quantitative detection is carried out to sample introduction sample by gas chromatography-mass spectrometry.
The on-line checking refers to, by sample by being connected as the cracking instrument of closing one by pipeline, trapping the dress of sample introduction
Put and carry out analysis measure with gas chromatography-mass spectrometry.
Further, the multistep order heating cracking, in particular to：Weigh the sample of tobacco additive agent or smoking material
Product, sample is fixed in cracking silica tube using silica wool, places into cracking instrument, under atmosphere, divide multistep to carry out platinum
Silk heating schedule heating, so as to heat cracking.Often step cracking terminates rear pyrolysis product and carries out desorption sample introduction through trapping, and is determined
Property and quantitative detection；Next step cracking is carried out after the completion of detection and analysis again.
Further, cracking condition is：Cracking gas is selected from the gaseous mixture of oxygen and nitrogen, or air, nitrogen, helium and its
One or both of his inert gas mixed gas；Cracking gas flow is 20-100ml/min；Crack 280 DEG C of room temperature；Pass
Defeated 280 DEG C of line temperature.
Preferably, the volume ratio of gaseous mixture of the cracking gas selected from oxygen and nitrogen, oxygen and nitrogen is 9:91.
Preferably, cracking gas flow is 70ml/min.
Preferably, it is CDS5250T thermal cracking instrument to crack instrument.
Further, sample fixed form in the cracking silica tube of CDS5250T thermal cracking instrument is in cracking quartz
A cracking quartz rod is put into pipe, and silica wool is loaded in cracking quartz rod top center position, weighs tobacco additive agent or cigarette
With material sample, it is placed in above silica wool, silica wool is then loaded on sample and is compacted, cracking silica tube is put into cracking instrument
It is interior.
Further, the heating schedule of multistep order is：
The first step, 100 DEG C of initial temperature, 5s-10s is kept, be warming up to 150 DEG C with 20-50 DEG C/s, keep 5s-60s；
Second step, 150 DEG C of initial temperature, 5s-10s is kept, be warming up to 200 DEG C with 20-50 DEG C/s, keep 5s-60s；
3rd step, 200 DEG C of initial temperature, 5s-10s is kept, be warming up to 250 DEG C with 20-50 DEG C/s, keep 5s-60s；
4th step, 250 DEG C of initial temperature, 5s-10s is kept, be warming up to 300 DEG C with 20-50 DEG C/s, keep 5s-60s；
5th step, 300 DEG C of initial temperature, 5s-10s is kept, be warming up to 400 DEG C with 20-50 DEG C/s, keep 5s-60s；
6th step, 400 DEG C of initial temperature, 5s-10s is kept, be warming up to 500 DEG C with 20-50 DEG C/s, keep 5s-60s；
7th step, 500 DEG C of initial temperature, 5s-10s is kept, be warming up to 600 DEG C with 20-50 DEG C/s, keep 5s-60s；
8th step, 600 DEG C of initial temperature, 5s-10s is kept, be warming up to 700 DEG C with 20-50 DEG C/s, keep 5s-60s；
9th step, 700 DEG C of initial temperature, 5s-10s is kept, be warming up to 800 DEG C with 20-50 DEG C/s, keep 5s-60s；
Tenth step, 800 DEG C of initial temperature, 5s-10s is kept, be warming up to 900 DEG C with 20-50 DEG C/s, keep 5s-60s.
Further, it is one kind in the following manner to trap Trapping ways of the pyrolysis product through trapping in sample introduction：
(a) cold-trap and bushing pipe, adsorbent is loaded in bushing pipe；
(b) cold-trap and bushing pipe, non-adsorbed dose of filler is loaded in bushing pipe；
(c) adsorbent is loaded in bushing pipe.
Preferably, the low-temperature receiver of the cold-trap is liquid nitrogen or other low-temperature receivers.
Preferably, Trapping ways (a) and filling adsorbent in bushing pipe in (c) they are a kind of adsorbent, or in bushing pipe
Load the compound adsorbent that a variety of combination of adsorbents of arbitrary proportion form.
Preferably, in Trapping ways (a) and (c), the adsorbent is in Carbotrap B, Carbotrap C, TENAX
It is one or more.
It is highly preferred that adsorbent is Carbotrap B or Carbotrap C or TENAX in Trapping ways (a) and (c).
It is preferred that condenser temperature is -196~30 DEG C in Trapping ways (a) and (b).
Non-adsorbed dose of filler is mineral wool in Trapping ways (b).
It is highly preferred that condenser temperature is -180 DEG C -- 40 DEG C.
The principle of the trapping is：It can fill out adsorbent by being coated in the cold-trap and bushing pipe outside bushing pipe and trapped,
Wherein, the gas phase composition needed for being adsorbed by adsorbent, can a variety of adsorbents be used in conjunction with adsorb it is more needed for gas phases into
Point；Meanwhile different condenser temperatures can be utilized in trapping, required gas phase composition is trapped, improves arresting efficiency.Selection makes
, be depending on physical property caused by the property of lysate and cracking with which kind of Trapping ways.Cold trap trapping gas is used alone
Phase constituent, adsorbent is not filled with bushing pipe and is only filled with mineral wool, it is necessary to which the condenser temperature used is lower；Absorption is used alone
Agent traps, and cold-trap does not work, and trapping temperature is 30 DEG C of room temperature, and programmed temperature sampling initial temperature is also 30 DEG C of room temperature, to six
Small molecule gas phase composition trapping effect below carbon can be weaker；Cold-trap and adsorbent trap jointly, and trapping effect is best, can be with
Substantially small molecule gas phase composition caused by all cracking is trapped (except carbon monoxide etc.).
Further, it is to keep 1-6min at 200-330 DEG C to trap desorption sampling condition in sample introduction.
Further, the qualitative detection be by spectrum data library searching, it is determined that cracking after gas phase composition composition into
Point；The quantitative detection is that the relative amount of gas phase composition after cracking is determined using peak area normalization method.
The qualitative detection refers to that thermal cracking products use RTE integral ways, and peak area is more than maximum peak peak area
0.1% is integrated, and application mass spectrum spectrum storehouse retrieve it is qualitative.The mass spectrum spectrum storehouse is wiley7n and Nist98 collection of illustrative plates
Database.
The quantitative detection is calculated using peak area normalization, is tied by measure of the average value of parallel determination twice
Fruit.Wherein, semi-quantitative data result formula (1) is calculated：
Xi=Mi/ΣMi…………………………………(1)
In formula：
Xi--- the peak area normalization percentage composition of certain thermal cracking products；
Mi--- the peak area of certain thermal cracking products；
ΣMi--- thermal cracking products total mark area.
Further, the condition of the gas chromatography-mass spectrometry is：
GC conditions：Chromatographic column：30m × 0.25mm × 0.25 μm (DB-5MS elastic capillary-columns)；Carrier gas flux：
1.0mL/min；Split ratio：30：1；Heating schedule：40 DEG C of initial temperature, 3min is kept, rises to 240 DEG C with 5 DEG C/min, then
280 DEG C are risen to 10 DEG C/min, keeps 10min；Injector temperature：250℃；
Mass Spectrometry Conditions：Mass spectrum transmission line temperature：280℃；Ion source temperature：230℃；Quadrupole rod temperature：150℃；Ionization
Mode：Electron impact ionization (EI)；Electron energy：70eV；Mass scan range：29~450amu；The solvent delay time：
1.5min。
When tobacco additive agent or smoking material crack below 250 DEG C, only seldom material, mainly free Ni Gu
Fourth, other alkaloids and neophytadiene directly can be transferred in flue gas from tobacco leaf.300-500 DEG C of cracking, is the carbon in tobacco
The precursors such as hydrate, amino acid, pigment, pigment long-chain fatty acid ester, open chain isoprenoid, the primary alkanes material in west split
In the solution stage, it is most volatility, the major temperature area of half volatile material formation；Tobacco additive agent or smoking material exist
600 DEG C of cracking primary products are benzene homologues, condensed-nuclei aromatics and nitriles substance, when cracking for 700-900 DEG C, the cigarette that is mainly carbonized
Grass and oxygen burn to form the simple gases such as carbon dioxide, carbon monoxide.
Method provided by the present invention, cracked using the heating of multistep order, different from the steady temperature in conventional method
Or programmed temperature method, it can really reflect the cracking situation of tobacco additive agent or smoking material under different cracking temperatures, preferably
Ground determines result of combustion of tobacco or pyrolysis product variation with temperature behavior, clearly finds out the formation relation of pyrolysis product and temperature,
Clearly know the relation and tobacco precursor variation with temperature relation of each cracking composition and tobacco precursor, and each be harmful into
Divide the temperature province formed, so as to provide foundation for the burning behavior or combustion mechanism of research tobacco additive agent or smoking material.
In the present invention in addition to being trapped using adsorbent, also trapped using cold-trap, improve cracking composition
Arresting efficiency.The present invention use different sampling conditions and gas chromatography mass spectrometry condition determination, can effectively, complete detection tobacco add
Composition in agent and smoking material pyrolysis product.The half volatile component formed in additive cracking process can not only be determined, also
Many low molecule amount gas phase hazardous compositions in pyrolysis product can be determined, can comprehensively evaluate tobacco additive agent and smoking material
The harmfulness of lysate.
Compared with conventional method, simple to operate, advanced technology of the invention, it can be divided automatically after input operation program
Analysis, operating efficiency can be improved, while the sample size required for this research is seldom, and without using organic solvent, original can be saved
Material, research cost is reduced, it is safe, it is environment-friendly.The inventive method can be applied industrially well, can be with
Formation for following cigarette harmful components controls, and improves the health of consumer.
Brief description of the drawings
Fig. 1 is online the multistep order cracking-cold-trap and Capture by Sorbents-GC/MS schematic diagrames of the present invention；
Fig. 2 is online multistep order cracking-cold trap trapping-GC/MS schematic diagrames of the present invention；
Fig. 3 is online multistep order cracking-Capture by Sorbents-GC/MS schematic diagrames of the present invention；
Fig. 4 is Red River tobacco leaf temperature programming pyrogram；
Fig. 5 is that Lijing B22 chooses tobacco leaf temperature programming pyrogram；
Fig. 6 is Red River tobacco leaf multistep pyrogram；
Fig. 7 is sucrose multistep pyrogram；
Fig. 8 is proline multistep pyrogram；
Fig. 9 is Zimbabwe C10 tobacco leaf multistep pyrograms；
Figure 10 is Brazilian M02 tobacco leaves multistep pyrogram；
Figure 11 is table mountain Baofeng tobacco leaf multistep pyrogram；
Component label instructions
1：Cracking room I：Cold-trap II：Bushing pipe and its interior adsorbent filled out.
Embodiment
Illustrate embodiments of the present invention below by way of particular specific embodiment, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages and effect of the present invention easily.The present invention can also be by different specific in addition
Embodiment is embodied or practiced, and the various details in this specification can also be based on different viewpoints and application, not carry on the back
Various modifications or alterations are carried out under spirit from the present invention.It should be noted that in the case where not conflicting, following examples and reality
Applying the feature in example can be mutually combined.
It is as follows to include instrument, sample and reagent for the selection of material in the present embodiment：
Instrument
CDS5250T thermal crackings instrument (CDS Analytical companies of the U.S.), cracking silica tube (U.S. CDS
Analytical companies), cracking quartz rod (CDS Analytical companies of the U.S.), Agilent 7890-5975C gas phase colors
Spectrum-GC-MS (GC/MS, Agilent companies of the U.S.), XP603S assay balance (sensibility reciprocals：0.00001g, Switzerland METTLER
TOLEDO companies).
Sample and reagent
Silica wool (the residual level of agriculture, CDS Analytical companies of the U.S.), adsorbent：TENAX (German Gerstel companies),
Non-adsorbed dose of filler：Mineral wool (German Gerstel companies), sucrose, proline, Red River tobacco leaf, Lijing B22 choose tobacco leaf,
Zimbabwe's C10 tobacco leaves, Brazilian M02 tobacco leaves, table mountain Baofeng tobacco leaf.
Comparative example 1
1st, temperature programming cracking is carried out to HongHe tobacco：
Preparation of samples：Cracking silica tube one is taken, a cracking quartz rod is put into cracking silica tube, in middle position
The residual level silica wool of appropriate agriculture (1 ± 0.10mg of dosage, winding are agglomerating) is loaded, weighs 1mg ± 0.05mg HongHe tobacco powder-like
Product are placed on silica wool, then are loaded 1mg ± 0.10mg silica wools in sample upper end and be compacted, and prevent from being used when sample is cleaved
Air-flow be blown into cracking chamber, then by cracking silica tube be put into cracking instrument in wait to crack.
Sample dissociation condition：Crack atmosphere：Oxygen and nitrogen mixture (9：91, volume ratio)；Cracking gas flow：70mL/
min；Crack heating schedule：300 DEG C of holding 5s, are then warming up to 900 DEG C with 30 DEG C/s, keep 5s.Clack box temperature：280℃；Pass
Defeated line temperature：280℃；
Pyrolysis product trap conditions：Using cold trap trapping, -60 DEG C of condenser temperature；
Thermal desorption sampling condition：Collecting trap temperature is risen to 280 DEG C by -60 DEG C, desorption is completed in 3min.
Gas phase composition after trapping sample introduction is subjected to qualitative and quantitative detection by gas chromatography-mass spectrometry；
Gas chromatograph-mass spectrometer condition：Chromatographic column：DB-5MS elastic capillary-columns (30m × 0.25mm × 0.25 μm)；Carrier gas stream
Amount：1.0mL/min；Temperature programming：40 DEG C of initial temperature, 3min is kept, 240 DEG C are risen to 5 DEG C/min, then with 10 DEG C/min
280 DEG C are risen to, keeps 10min；Ion source temperature：230℃；Quadrupole rod temperature：150℃；Injector temperature：250℃；Mass spectrum passes
Defeated line temperature：280℃；Ionization mode：Electron impact ionization (EI)；Electron energy：70eV；Mass scan range：29~
450amu；The solvent delay time：1.5min；Split ratio：100：1.
2nd, result and discussion
Analyzed using cracking gas phase composition of the Program of the comparative example 1 heating cleavage method to HongHe tobacco, Fig. 4 is gas
The chromatogram that matter combined instrument is surveyed, the formation of pyrolysis product and the relation of cracking temperature can not be found out from Fig. 4, can not also obtained
To the relation of precursor pyrolysis product corresponding thereto, can not be inferred to cracking temperature and harmful components formed between relation,
Therefore, according to the cracking situation, tobacco cracking or the mechanism burnt can not be inferred to.
Comparative example 2
1st, Lijing B22 chooses the cracking of tobacco isothermal
Preparation of samples：Cracking silica tube one is taken, a cracking quartz rod is put into cracking silica tube, in middle position
The residual level silica wool of appropriate agriculture (1 ± 0.10mg of dosage, winding are agglomerating) is loaded, the Lijing B22 for weighing 1mg ± 0.05mg chooses tobacco powder
Last sample is placed on silica wool, then is loaded 1mg ± 0.10mg silica wools in sample upper end and be compacted, and prevents institute when sample is cleaved
The air-flow used is blown into cracking chamber, and then cracking tube is put into cracking instrument and waits to crack.
Sample dissociation condition：Crack atmosphere：Oxygen and nitrogen mixture (9：91, volume ratio)；Cracking gas flow：70mL/
min；Crack heating schedule：Respectively in 300 DEG C, 450 DEG C, 600 DEG C, 750 DEG C, 900 DEG C of cracking 40s.Clack box temperature：280℃；Pass
Defeated line temperature：280℃；
Pyrolysis product trap conditions：Using cold trap trapping, -60 DEG C of condenser temperature；
Thermal desorption sampling condition：Collecting trap temperature is risen to 280 DEG C by -60 DEG C, desorption is completed in 3min.
Gas phase composition after trapping sample introduction is subjected to qualitative and quantitative detection by gas chromatography-mass spectrometry；
Gas chromatograph-mass spectrometer condition：Chromatographic column：DB-5MS elastic capillary-columns (30m × 0.25mm × 0.25 μm)；Carrier gas stream
Amount：1.0mL/min；Temperature programming：40 DEG C of initial temperature, 3min is kept, 240 DEG C are risen to 5 DEG C/min, then with 10 DEG C/min
280 DEG C are risen to, keeps 10min；Ion source temperature：230℃；Quadrupole rod temperature：150℃；Injector temperature：250℃；Mass spectrum passes
Defeated line temperature：280℃；Ionization mode：Electron impact ionization (EI)；Electron energy：70eV；Mass scan range：29~
450amu；The solvent delay time：1.5min；Split ratio：100：1.
2nd, result and discussion
Tobacco is chosen to Lijing B22 and carries out isothermal cracking, cracking temperature is 300 DEG C respectively, 450 DEG C, 600 DEG C, 750 DEG C, 900
DEG C, 40s, the chromatogram that Fig. 5 is surveyed by gas chromatograph-mass spectrometer, only it can be seen that cracking temperature produces to cracking from Fig. 5 are cracked respectively
The formation of thing has an impact, but the formation of pyrolysis product is extremely complex, can not find out fragmentation pathways of the precursor with temperature, also without
Method finds out the relation of precursor corresponding pyrolysis product at different temperatures, and therefore, situation about being cracked according to isothermal can not
It is inferred to result of combustion of tobacco or the mechanism of cracking well.
Embodiment 1
1. tobacco leaf powder multistep order in Red River cracks
Preparation of samples：Cracking silica tube one is taken, a cracking quartz rod is put into cracking silica tube, in middle position
The residual level silica wool of appropriate agriculture (1 ± 0.10mg of dosage, winding are agglomerating) is loaded, weighs 1mg ± 0.05mg Red River tobacco leaf powder-like
Product are placed on silica wool, then are loaded 1mg ± 0.10mg silica wools in sample upper end and be compacted, and prevent from being used when sample is cleaved
Air-flow be blown into cracking chamber, then by cracking tube be put into cracking instrument in wait to crack.
Multistep order cracking heating schedule be：
The first step, 100 DEG C of initial temperature, 5s is kept, be warming up to 150 DEG C with 50 DEG C/s, keep 60s；Second step, initial temperature
150 DEG C of degree, 5s is kept, be warming up to 200 DEG C with 50 DEG C/s, keep 60s；3rd step, 200 DEG C of initial temperature, 5s is kept, with 50
DEG C/s is warming up to 250 DEG C, keep 60s；4th step, 250 DEG C of initial temperature, 5s is kept, be warming up to 300 DEG C with 50 DEG C/s, keep
60s；5th step, 300 DEG C of initial temperature, 5s is kept, be warming up to 400 DEG C with 50 DEG C/s, keep 60s；6th step, initial temperature
400 DEG C, 5s is kept, 500 DEG C is warming up to 50 DEG C/s, keeps 60s；7th step, 500 DEG C of initial temperature, 5s is kept, with 50 DEG C/s
600 DEG C are warming up to, keeps 60s；8th step, 600 DEG C of initial temperature, 5s is kept, be warming up to 700 DEG C with 50 DEG C/s, keep 60s；
9th step, 700 DEG C of initial temperature, 5s is kept, be warming up to 800 DEG C with 50 DEG C/s, keep 60s；Tenth step, 800 DEG C of initial temperature,
5s is kept, 900 DEG C is warming up to 50 DEG C/s, keeps 60s.
Crack atmosphere：Helium；Cracking gas flow：70mL/min；Clack box temperature：280℃；Transmission line temperature：280℃；
Pyrolysis product trap conditions：Trapped jointly using liquid nitrogen and adsorbent TENAX, trap -196 DEG C of temperature；
Thermal desorption sampling condition：Collecting trap temperature is risen to 290 DEG C by -60 DEG C, desorption is completed in 5min.
Gas chromatograph-mass spectrometer condition：Chromatographic column：DB-5MS elastic capillary-columns (30m × 0.25mm × 0.25 μm)；Carrier gas stream
Amount：1.0mL/min；Split ratio：30 ︰ 1；Heating schedule：40 DEG C of initial temperature, 3min is kept, rises to 240 DEG C with 5 DEG C/min, so
280 DEG C are risen to 10 DEG C/min afterwards, keeps 10min；Injector temperature：250℃；Mass spectrum transmission line temperature：280℃；Ion gun
Temperature：230℃；Quadrupole rod temperature：150℃；Ionization mode：Electron impact ionization (EI)；Electron energy：70eV；Mass scanning
Scope：29~450amu；The solvent delay time：1.5min.
2nd, result and discussion
Multistep order is carried out to Red River tobacco leaf powder to crack, and is cracked through ten steps, the lysate sample quartz ampoule after often step cracking
Cracking intracavitary is remained in, the first step is cracked into thermal desorption sample introduction after lease making trapping, after the completion of gas chromatography-mass spectrometry analysis,
Then second of cracking program is carried out, by this step until all cracking programs perform and separation, identification finish.
Table 1-7 is the cracking gas phase composition that tobacco leaf multistep cracking in Red River detects, Fig. 6 is the cracking of Red River tobacco leaf multistep, gas
The chromatogram that matter combined instrument is surveyed, by multistep order cleavage method, it can compare from Fig. 6 and can be clearly seen that tobacco cracked
In the several stages undergone in journey, it can with more visible find out the influence that temperature is formed to pyrolysis product, can clearly know,
Corresponding relation between each pyrolysis product of tobacco and each precursor of tobacco；Also it can clearly see the master of tobacco harmful substance formation
Want temperature.
The main volatile product that the Red River tobacco leaf of table 1 detects when cracking for 150 DEG C
The main volatile product formed during 2 tobacco leaf of table, 200 DEG C of cracking
As can be seen from Table 1 and Table 2, tobacco leaf only detects nicotine, myosmine, nicotine in 150 DEG C and 200 DEG C
The presence of alkene and neophytadiene, at this moment the compound in tobacco mainly evaporated in a manner of distillation.
The main volatile product formed during 3 tobacco leaf of table, 250 DEG C of cracking
It can be seen that in table 3, when cracking temperature reaches 250 DEG C, the release of nicotine has again obviously to be increased, its
Its alkaloid, such as the Mace people, nicotryin and 2,3'- bipyridyl discharge again, and reason is reference state in tobacco
Cracking takes place in nicotine salt.In addition, when being cracked at 250 DEG C, neophytadiene is not detected, is illustrated free new
Phytadiene is volatilized completely.
The some products that carbohydrate degradation is formed start to occur, such as：DDMP, hydroxyl maltol, maltol, furfural,
Furfuryl alcohol, the furfurals of 2,5- bis- etc., but 5 methyl furfural and 5 hydroxymethyl furfural are not yet formed, glucose, fructose and sucrose dehydration shape
Into levoglucosenone, levoglucosan, 1,6- dehydration-α-D- galactofuranoses, 1,4:3,6-two dehydration-α-D- pyrans Portugals
The products such as grape sugar are not also formed.
Tobacco detects the presence of solanone when cracking for 250 DEG C, solanone be in tobacco it is a kind of it is very important cause it is fragrant into
Point, it is the catabolite of the primary alkanes material in tobacco Chinese and Western, meanwhile, the primary alkanes material in west can also form somnirol, drop in degraded
The materials such as eggplant diketone, spiral shell vetivone and 6- methyl -2,5- heptadione.
The main volatile product formed during 4 tobacco leaf of table, 300 DEG C of cracking
Tobacco leaf cracks the perfume compound to be formed and occurred mainly between 300 DEG C and 600 DEG C, and tobacco is in 300 DEG C and 600 DEG C
Between the content of the formed perfume compound of cracking be much higher than fragrance matter caused by distillation.Before 300 DEG C, only
The several materials for having nicotine and other alkaloids etc. a small number of are directly transferred in flue gas from pipe tobacco, when temperature rises to 300-
At 500 DEG C, many materials in pipe tobacco, such as terpenes, phytosterol for example stigmasterol, paraffin class, carbohydrate, amino acids,
Cellulose family and many other compositions, acutely complicated chemical reaction is carried out in the humidity province, and (main to include thermal decomposition, cracking is closed
Into the reaction such as, destructive distillation, polymerization, condensation, free radical), form substantial amounts of volatility, half volatile gas and liquid and solid
Material, the fragrance matter of about 5000 or so is formed in cracking/distillation zone of combustion zone rear end in flue gas, and this is cigarette
The Main Stage that careless fragrance matter is formed.
At 300 DEG C, the carbohydrate in tobacco leaf cracks the furfural to be formed, furfuryl alcohol, 5 methyl furfural, DDMP, 5- hydroxyl
The amount of the materials such as base maltol, 5 hydroxymethyl furfural starts to increase.Meanwhile Megastigmatrienone, 3- hydroxy-beta-damascone,
3- oxo-alpha- ionols start to produce.
400 DEG C and 500 DEG C be tobacco leaf cracking Main Stage, and carbohydrate cracking, amino acid degradation, Mei Lade
Reaction and fragrance precursor thing are degraded the most violent stage.Tobacco leaf forms substantial amounts of Acacia base when cracking for 400 DEG C and 500 DEG C
The perfume compounds such as acetone, geranyl acetone, geranial, farnesal, fanesol, these compounds are the open chains in tobacco
The cracking of isoprenoid compound is formed, the open chain isoprenoid material in tobacco mainly include Salanesol, phytene and
Neophytadiene etc., these materials formed during degraded it is substantial amounts of in chain ketone and alcohols material, such as 6- methyl -5- heptan
Alkene -2- ketone, geranyl acetone, geraniol, 6- methyl -3,5- heptadiene -2- ketone, farnesyl acetone, farnesol etc. are important to cause perfume
Composition, these materials can assign flue-cured tobacco good fresh and sweet note.
400~500 DEG C of cracking form the materials such as pyridine, pyrroles, picoline, methylpyrrole.These materials are probably
The product of alkaloid and amino acid degradation in tobacco.
The main volatile product formed during 5 tobacco leaf of table, 400 DEG C of cracking
The main volatile product formed during 6 tobacco leaf of table, 500 DEG C of cracking
Such as table 7, tobacco leaf then forms substantial amounts of benzene, toluene, ethylbenzene, dimethylbenzene, naphthalene and other thick in 600 DEG C of cracking
Ring aromatic compounds, while also form nitriles substance.Meanwhile tobacco material cracks at 600 DEG C, form substantial amounts of nitrogenous
Heterocyclic compound, such as picoline, methylpyrrole, lutidines and dimethyl pyrrole class compound etc..Tobacco leaf is at 600 DEG C
The nitrogen-containing heterocycle compounds such as the formed picoline of cracking, methylpyrrole, lutidines and nitrile compounds all may
The degraded of protein in tobacco.
The main volatile product formed during 7 tobacco leaf of table, 600 DEG C of cracking
Cracking of the tobacco at 700-900 DEG C, temperature of its temperature equivalent to cigarette burning area.When tobacco 700 DEG C, 800
DEG C and during 900 DEG C of cracking, there is no that what new product occurs, it is also possible to cracking generates simple gases, and these
Gas component cannot detect under the conditions of experimental analysis.This explanation tobacco leaf has substantially cracked after 600 DEG C of cracking
Entirely, carbon has been left with after cracking, and when cracking for 700 DEG C, 800 DEG C and 900 DEG C, due to the presence of oxygen, carbon is with oxygen in 700-
At a high temperature of 900 DEG C, simple gases, such as the compound such as carbon dioxide, carbon monoxide, water, hydrogen, methane are formed.
Therefore, cracked using multistep order, cracking temperature can be studied well discharged volatility is cracked to tobacco leaf
With the influence of half volatile material, so as to for disclosing relation and cigarette between the material discharged when cigarette is burnt and sucked and temperature
Reaction path and mechanism during burning.
Embodiment 2
Lysate sample be sucrose, cracking temperature heating schedule and method with embodiment 1, but unlike that embodiment 1 is：
Crack atmosphere：10%O2With 90%He gaseous mixtures；Cracking gas flow：50mL/min；Pyrolysis product trap conditions：Using liquid nitrogen and
Adsorbent Carbotrap C are trapped, and trap -100 DEG C of temperature；Thermal desorption sampling condition：Collecting trap temperature is risen to by -100 DEG C
300 DEG C, 6min is interior to complete desorption, cracks to the 8th step.Other conditions are same as Example 1.
The chromatogram that Fig. 7 is surveyed by gas chromatograph-mass spectrometer., can be with it can be seen from figure 7 that using multistep order cleavage method
Sucrose cracking variation with temperature relation is disclosed well, and its cracking process can be speculated by cracking formed product from each step
Or splitting mechanism.And if cracked only with single step, it is impossible to disclose the approach or mechanism of sucrose cracking.
Embodiment 3
Lysate sample is proline, and specific method is the same as embodiment 1.Different from embodiment 1, multistep order cracking to the
Seven steps, crack atmosphere：10%O2With 90%He gaseous mixtures；Cracking gas flow：50mL/min；Pyrolysis product trap conditions：Using
Liquid nitrogen and adsorbent Carbotrap B trappings, trap -60 DEG C of temperature；Thermal desorption sampling condition：By collecting trap temperature by -60 DEG C
280 DEG C are risen to, desorption is completed in 3min.
The chromatogram that Fig. 8 is surveyed by corresponding gas chromatograph-mass spectrometer, as can be seen from Figure 8, utilize multistep order cracking side
Method, it can be clearly seen that proline cracks variation with temperature relation, and the formation warm area of its pyrolysis product is mainly in 400-500
DEG C, the pyrolysis products of other warm areas compares less, but can crack formed product according to each warm area and can speculate it
Cracking process or splitting mechanism.If cracked only with single step, it is impossible to disclose proline and crack undergone approach or speculate it
Splitting mechanism.
Embodiment 4
Lysate sample：Zimbabwe's C10 tobacco leaves.Specific method is the same as embodiment 1.Different from embodiment 1, multistep order
Heating rate is 20 DEG C/s in the heating schedule of cracking, and 30s is kept under corresponding cracking temperature after heating；Cracking gas flow：
40mL/min；Pyrolysis product trap conditions：Use liquid nitrogen, mass ratio 1:1 Carbotrap C, TENAX Capture by Sorbents,
Trap -180 DEG C of temperature；Thermal desorption sampling condition：Collecting trap temperature is risen to 250 DEG C by -150 DEG C, desorption is completed in 2min.
The chromatogram that Fig. 9 is surveyed by corresponding gas chromatograph-mass spectrometer, it can be seen that using the cracking of multistep order can be with
When illustrating the cracking of Zimbabwe C10 tobacco leaves well, its pyrolysis product variation with temperature relation, because tobacco is in burning,
Temperature distribution range inside its cigarette between 150-950 DEG C, so being cracked using multistep order, can be also best seen from
In each temperature range, tobacco cracks formed product, these products can be probably by which precursor institute shape with interpretation
Into, so as to calculate the degradation temperature of tobacco precursor and mechanism of degradation, and then the change occurred during result of combustion of tobacco is speculated again
Change or mechanism.And the cracking of single step alternating temperature or isothermal cleavage method are all difficult that the mechanism of Zimbabwe's C10 tobacco leaves burning is pushed away
Survey.
Embodiment 5
Lysate sample：Brazilian M02 tobacco leaves.Specific method is the same as embodiment 1.Different from embodiment 1, multistep order cracks
Heating schedule be：
The first step, 100 DEG C of initial temperature, 10s is kept, be warming up to 150 DEG C with 30 DEG C/s, keep 5s；Second step, initial temperature
150 DEG C of degree, 10s is kept, be warming up to 200 DEG C with 30 DEG C/s, keep 5s；3rd step, 200 DEG C of initial temperature, 10s is kept, with 30
DEG C/s is warming up to 250 DEG C, keep 5s；4th step, 250 DEG C of initial temperature, 10s is kept, be warming up to 300 DEG C with 30 DEG C/s, keep
5s；5th step, 300 DEG C of initial temperature, 10s is kept, be warming up to 400 DEG C with 30 DEG C/s, keep 5s；6th step, initial temperature 400
DEG C, 10s is kept, 500 DEG C is warming up to 30 DEG C/s, keeps 5s；7th step, 500 DEG C of initial temperature, 10s is kept, with 30 DEG C/s liters
Temperature keeps 5s to 600 DEG C；8th step, 600 DEG C of initial temperature, 10s is kept, be warming up to 700 DEG C with 30 DEG C/s, keep 5s；9th
Step, 700 DEG C of initial temperature, 10s is kept, be warming up to 800 DEG C with 30 DEG C/s, keep 5s；Tenth step, 800 DEG C of initial temperature, keep
10s, 900 DEG C are warming up to 30 DEG C/s, keeps 5s.
Cracking gas flow：40mL/min；Pyrolysis product trap conditions：Trapped using adsorbent TENAX, trap temperature 30
℃；Thermal desorption sampling condition：Collecting trap temperature is risen to 300 DEG C by 30 DEG C, desorption is completed in 3min.
The chromatogram that Figure 10 is surveyed by corresponding gas chromatograph-mass spectrometer, it can be seen from fig. 10 that being cracked using multistep order
When can illustrate the cracking of Brazilian M02 tobacco leaves well, its pyrolysis product variation with temperature relation, because tobacco is in burning,
Temperature distribution range inside its cigarette between 150-950 DEG C, so being cracked using multistep order, can be also best seen from
In each temperature range, tobacco cracks formed product, these products can be probably by those precursor institute shapes with interpretation
Into, so as to calculate the degradation temperature of tobacco precursor and mechanism of degradation, and then the change occurred during result of combustion of tobacco is speculated again
Change or mechanism.And the cracking of single step alternating temperature or isothermal cleavage method are all difficult that the mechanism of Brazilian M02 tobacco leaves burning is speculated.
Embodiment 6
Lysate sample：Table mountain Baofeng tobacco leaf.Specific method is the same as embodiment 1.Different from embodiment 1, multistep order
The heating schedule of cracking is：
The first step, 100 DEG C of initial temperature, 7s is kept, be warming up to 150 DEG C with 40 DEG C/s, keep 20s；Second step, initial temperature
150 DEG C of degree, 7s is kept, be warming up to 200 DEG C with 40 DEG C/s, keep 20s；3rd step, 200 DEG C of initial temperature, 7s is kept, with 40
DEG C/s is warming up to 250 DEG C, keep 20s；4th step, 250 DEG C of initial temperature, 7s is kept, be warming up to 300 DEG C with 40 DEG C/s, keep
20s；5th step, 300 DEG C of initial temperature, 7s is kept, be warming up to 400 DEG C with 40 DEG C/s, keep 20s；6th step, initial temperature
400 DEG C, 7s is kept, 500 DEG C is warming up to 40 DEG C/s, keeps 20s；7th step, 500 DEG C of initial temperature, 7s is kept, with 40 DEG C/s
600 DEG C are warming up to, keeps 20s；8th step, 600 DEG C of initial temperature, 7s is kept, be warming up to 700 DEG C with 40 DEG C/s, keep 20s；
9th step, 700 DEG C of initial temperature, 7s is kept, be warming up to 800 DEG C with 40 DEG C/s, keep 20s；Tenth step, 800 DEG C of initial temperature,
7s is kept, 900 DEG C is warming up to 40 DEG C/s, keeps 20s.
Crack atmosphere：Air；Cracking gas flow：20mL/min；Pyrolysis product trap conditions：Use cold-trap, mass ratio for
1:1:1 Carbotrap B, Carbotrap C, TENAX adsorbents trap jointly, -60 DEG C of condenser temperature；Thermal desorption enters batten
Part：Collecting trap temperature is risen to 280 DEG C by -60 DEG C, desorption is completed in 6min.
The chromatogram that Figure 11 is surveyed by corresponding gas chromatograph-mass spectrometer, it can be seen from fig. 11 that being cracked using multistep order
When can illustrate the tobacco leaf cracking of table mountain Baofeng well, its pyrolysis product variation with temperature behavior relation can be clearly
Find out within the temperature range of each step order cracks, cracked excluding preamble temperature outside formed product, in the step temperature
Under cracking, tobacco cracks formed product, these products can be probably to be formed by those precursors with interpretation, so as to push away
The degradation temperature and mechanism of degradation of tobacco precursor are calculated, and then speculates the change occurred during result of combustion of tobacco or mechanism again.And
Single step alternating temperature cracks or isothermal cleavage method is all difficult that the mechanism of table mountain Baofeng tobacco leaf burning is speculated.
To sum up, multistep order heating cleavage method provided by the present invention, can detect that different cracking temperatures are lower and be split
The gas phase composition that solution obtains, it can be used for studying the cracking temperature volatility discharged to tobacco additive agent or smoking material cracking
With the influence of half volatile material, so as to disclose between the material discharged when tobacco additive agent or smoking material burn and temperature
Relation, provide foundation for research tobacco additive agent or the burning behavior or combustion mechanism of smoking material.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (9)
1. cracking the method for gas phase composition under a kind of on-line checking tobacco additive agent or smoking material different temperatures, its feature exists
In comprising the following steps：
Cracking：The heating that tobacco additive agent or smoking material are carried out to multistep order cracks；
Trap sample introduction：By the tobacco additive agent of every step cracking gained or smoking material pyrolysis product after trapping, be desorbed into
Sample；
Measure：Qualitative and quantitative detection is carried out to sample introduction sample by gas chromatography-mass spectrometry.
2. according to the method for claim 1, it is characterised in that：The heating cracking of the multistep order specifically refers to：Weigh
The sample of tobacco additive agent or smoking material, sample is fixed in cracking silica tube using silica wool, places into cracking instrument,
Under atmosphere, multistep is divided to carry out platinum filament heating schedule heating, so as to heat cracking.
3. according to the method for claim 1, it is characterised in that：In the heating cracking of multistep order, after often step cracking terminates
Pyrolysis product carries out desorption sample introduction through trapping, and carries out qualitative and quantitative detection；Next step cracking is carried out after the completion of analysis again.
4. according to the method for claim 1, it is characterised in that：Cracking condition is：
Cracking gas is selected from the gaseous mixture of oxygen and nitrogen, or one or both of air, nitrogen, helium and other inert gases
Mixed gas；
Cracking gas flow is 20-100ml/min；
Crack 250-300 DEG C of instrument clack box temperature；
250-300 DEG C of transmission line temperature.
5. according to the method for claim 1, it is characterised in that：The heating schedule of multistep order is：
The first step, 100 DEG C of initial temperature, 5s-10s is kept, be warming up to 150 DEG C with 20-50 DEG C/s, keep 5s-60s；
Second step, 150 DEG C of initial temperature, 5s-10s is kept, be warming up to 200 DEG C with 20-50 DEG C/s, keep 5s-60s；
3rd step, 200 DEG C of initial temperature, 5s-10s is kept, be warming up to 250 DEG C with 20-50 DEG C/s, keep 5s-60s；
4th step, 250 DEG C of initial temperature, 5s-10s is kept, be warming up to 300 DEG C with 20-50 DEG C/s, keep 5s-60s；
5th step, 300 DEG C of initial temperature, 5s-10s is kept, be warming up to 400 DEG C with 20-50 DEG C/s, keep 5s-60s；
6th step, 400 DEG C of initial temperature, 5s-10s is kept, be warming up to 500 DEG C with 20-50 DEG C/s, keep 5s-60s；
7th step, 500 DEG C of initial temperature, 5s-10s is kept, be warming up to 600 DEG C with 20-50 DEG C/s, keep 5s-60s；
8th step, 600 DEG C of initial temperature, 5s-10s is kept, be warming up to 700 DEG C with 20-50 DEG C/s, keep 5s-60s；
9th step, 700 DEG C of initial temperature, 5s-10s is kept, be warming up to 800 DEG C with 20-50 DEG C/s, keep 5s-60s；
Tenth step, 800 DEG C of initial temperature, 5s-10s is kept, be warming up to 900 DEG C with 20-50 DEG C/s, keep 5s-60s.
6. according to the method for claim 1, it is characterised in that：Trapping ways of the pyrolysis product through trapping are in trapping sample introduction
One kind in the following manner：
(a) cold-trap and bushing pipe, adsorbent is loaded in bushing pipe；
(b) cold-trap and bushing pipe, non-adsorbed dose of filler is loaded in bushing pipe；
(c) adsorbent is filled in bushing pipe.
7. according to the method for claim 6, it is characterised in that：Also include the one or more of following characteristics：
Trapping ways (a) and condenser temperature in (b) are -196~30 DEG C；
Trapping ways (a) are Carbotrap B or Carbotrap C or TENAX with adsorbent in (c)；
Non-adsorbed dose of filler is mineral wool in Trapping ways (b).
8. according to the method for claim 1, it is characterised in that：Desorption sampling condition is in trapping sample introduction, at 200-330 DEG C
Keep 1-6min.
9. according to the method for claim 1, it is characterised in that：The qualitative detection is by spectrum data library searching, really
The constituent of gas phase composition after fixed cracking；The quantitative detection is to determine gas phase composition after cracking using peak area normalization method
Relative amount.
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| CN112899081A (en) * | 2021-01-19 | 2021-06-04 | 云南中烟工业有限责任公司 | Preparation method and application of DGP (DGP-protein) substance |
| CN113109483A (en) * | 2021-05-07 | 2021-07-13 | 上海烟草集团有限责任公司 | Analysis method for pyrolysis aroma components of potentially-fragrant raw material for cigarettes |
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| NL2036103A (en) * | 2023-05-19 | 2023-11-23 | Yunnan Tobacco Quality Supervision And Testing Station | Method for analyzing and detecting organic acid in tobacco |
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