CN102766534A - Method for separating alkaline scent ingredients from main stream smoke of cigarettes and application - Google Patents
Method for separating alkaline scent ingredients from main stream smoke of cigarettes and application Download PDFInfo
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- CN102766534A CN102766534A CN2012102458496A CN201210245849A CN102766534A CN 102766534 A CN102766534 A CN 102766534A CN 2012102458496 A CN2012102458496 A CN 2012102458496A CN 201210245849 A CN201210245849 A CN 201210245849A CN 102766534 A CN102766534 A CN 102766534A
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Abstract
The invention relates to a method for separating alkaline scent ingredients from the main stream smoke of cigarettes, in particular to a method for separating trace alkaline scent ingredients from alkaline ingredients containing a large amount of alkaloids such as nicotine and the like. The method comprises the following steps of: extracting collected smoke particulate matters, namely unblended cigarettes with high-quality tobacco leaves serving as raw materials, performing acid washing, concentrating, distilling under vacuum and the like to obtain a cut fraction F2 with low alkaloid content; separating the cut fraction by a gas chromatography separation method to obtain 5 cut fractions SF1 to SF5; and performing the combination of gas chromatography-mass spectrometry and sensory evaluation on SF1 to SF5, and selecting a cut fraction SF4 with an obvious sensory effect. By the method, a large number of alkaloid ingredients which do not contribute to the scent ingredients of the cigarettes are removed, and low-content active alkaline scent ingredients are enriched; and the method is applied to the field of the perfuming of cut tobaccos of the cigarettes, and has an important significance for improving the smoking quality of the cigarettes in China.
Description
Technical field
The present invention relates to the separation of crucial alkaline trace flavor component in the cigarette mainstream flue gas, relate in particular to a kind of separation method of from the cigarette mainstream flue gas alkaline components that contains large number of biological alkali, isolating micro-alkaline flavour ingredient.
Background technology
Cigarette smoke neutral and alkali composition has 1735 kinds of compounds, and wherein nitrogen heterocycles accounts for 1246 kinds.Nitrogen heterocycles in the cigarette smoke is main with Nicotine, contains myosmine, cotinine, and nornicotine, neonicotine, neonicotine, passiflorin falls in passiflorin, and 2, composition such as vegeto-alkali such as 3-dipyridyl and gas phase aminated compounds and a spot of pyridine, pyrazine, pyrroles.The vegeto-alkali majority mainly burns and sucks in the process at cigarette with prototype and transforms the entering flue gas from tobacco.An amine part is that the part aliphatic amide in the tobacco directly shifts and gets into flue gas and forms when being burnt and sucked by cigarette, and another part is by the generation of the composition generation cracking in the tobacco.Micromolecular compound majorities such as pyridine, pyrazine, pyrroles come from the Maillard reaction.Chemical substances such as nicotine then satisfy to be inhaled flavor strength and are being given and significant effects is arranged aspect the tobacco physiological strength.Amine has unpleasant pungency, and the flue gas quality is had bad contribution.Discover; Pyrazine class and pyridine compounds and their are to constitute in the cigarette mainstream flue gas characteristic perfume compound very important one type; Major part has the intensive burnt odor, baking is fragrant and be very easy to coordinate with tobacco inherent fragrance, can fine modification and to improve the natural cigarette of cigarette fragrant, and can cover the assorted gas of part; Improve pleasant impression, in the table perfume (or spice) of cigarette, be widely applied.When the content of pyrazine, pyridines nitrogenous compound was high, the fragrance concentration of cigarette was higher, and fragrance is better.Acetylpyridine, the characteristic perfume with tobacco appearance makes fume centralized, and concentration, fullness ratio strengthen, stay length, coordinate flue gas, become positive correlation with the concentration of flue gas within the specific limits.Picoline has tobacco aroma, can be used for providing the characteristic of burley tobaccos to inhale flavor and fragrance.It is fragrant that pyrazine compounds has baking more, the nut of stir-fry is arranged and like cocoa aroma, is used to strengthen note, covers the assorted gas of tobacco like methylpyrazine, and dimethylpyrazine has puffed rice fragrance, is used to improve perfume quantity and enriches the aromatic degree of cigarette.Dimethylpyrazine, methylpyrazine, aroma components such as ethyl pyrazine all have flavouring preferably and improve the effect of pleasant impression fire-cured tobacco type, blended type cigarette.
Cigarette smoke neutral and alkali composition kind is a lot of and content difference is bigger; Nicotine accounts for more than 90% of flue gas alkaline components content; But other alkaline flavour ingredient content is very low; Some content is atomic, props up for about 5-50 μ g/ such as the content of pyrazine compounds, separate and prepare relatively difficulty of the very little flavour ingredient of these content.Therefore; Systematically crucial alkaline flavour ingredient in the analysis research main flume is removed in a large number to the less composition of cigarette flavour ingredient contribution, the flavour ingredient of enrichment low levels; Define the cut that fragrance is worth, the tobacco blending is had the real directive significance of outbalance.
Summary of the invention
The object of the present invention is to provide a kind of separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient and the application in perfuming cigarette thereof.
To achieve these goals, the present invention adopts following technical scheme to realize:
The separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient of the present invention; Said alkaline flavour ingredient is a raw material with high-quality cigarette smoke granule phase substance, and separation, vacuum distilling separation and the preparation gc separating step through extraction, alkaline components makes successively; The essential substance of said alkaline flavour ingredient comprises dimethylpyrazine or dimethylpyrazine compounds.
Further, the essential substance of said alkaline flavour ingredient is a 2-ethyl pyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine and 2,3-dimethylpyrazine.
The separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient of the present invention specifically may further comprise the steps:
(1) extracts: on the rotating disc type smoking machine, adopt filter disc to capture mode, collect high-quality cigarette smoke granule phase substance, obtain the cambridge filter ravin with cambridge filter; After the cambridge filter ravin employing extraction solvent extraction that obtains, concentrating under reduced pressure obtains the liquid concentrator O of Vandyke brown crude extract;
Preferable, said extraction solvent is an ether; The liquid concentrator O of said Vandyke brown crude extract is the diethyl ether solution of Vandyke brown crude extract.
Preferable, the method for said extraction is for soaking one or more methods in extraction, ultrasonic extraction and the shaking table oscillation extraction.
Preferable, the vacuum tightness of said concentrating under reduced pressure is 700-1000mbar, the bath temperature that concentrating under reduced pressure adopted is 25-45 ° of C.
(2) separation of alkaline components:
(2.1) pickling: the liquid concentrator O of the Vandyke brown crude extract that step (1) is obtained adopts acid solution to extract, and extraction repeatedly separates organic phase and water respectively, obtains water-phase extract A1;
Preferable, said acid solution is a sulphuric acid soln.Further, the mass percent concentration of acid is 1-20% in the said sulphuric acid soln.Preferably, the mass percent concentration of acid is 5% in the said sulphuric acid soln.
(2.2) acquisition of alkaline components O1: after the pH value of the water-phase extract A1 that step (2.1) is obtained with alkali lye earlier is adjusted to 11-12; Again repeatedly with organic solvent extraction; Tell organic phase and water, organic phase is carried out obtaining organic phase extract O1 behind the concentrating under reduced pressure, be alkaline components O1.
Preferable, in the step (2.2), said organic solvent is an ether; Said alkali lye is the aqueous solution of sodium hydroxide.Further, to select mass percent concentration for use be the aqueous solution of the sodium hydroxide of 10-80% to said aqueous sodium hydroxide solution.Preferably, the mass percent concentration of alkali is 50% in the said sodium hydroxide solution.
Preferable, in the step (2.2), the vacuum tightness of said concentrating under reduced pressure is 700 – 1000mbar, the bath temperature that concentrating under reduced pressure adopted is 25-45 ° of C.
Extraction in the above-mentioned steps (2) repeatedly, as all can be 3 times.
The solution of acid of the present invention is that the solution of aqueous acid, alkali is the aqueous solution of alkali.
(3) vacuum distilling separates: adopt the vacuum distilling partition method that the organic phase extract O1 that step (2.2) obtains is carried out vacuum distilling, separate obtaining 2 cut F1 and F2, then with the cut F2 that obtains to add solvent behind the cut F2 adding solvent constant volume.
Preferable, when carrying out vacuum distilling in the step (3), the sequencing that adopts the liquid nitrogen condensation mode to steam by cut is collected cut F1 and cut F2 successively.In the step of the present invention (3), before beginning to vacuumize, at first adopt the liquid nitrogen condensation scoop to carry out condensation and collection, and till continuing to be condensed to experiment and finishing the final vacuum state and disappear, this point is very important.
Further, in the step (3), the vacuum tightness of said vacuum distilling is 0.01-0.1mbar, and bath temperature is 25-45 ℃.Preferable, when carrying out vacuum distilling in the step (3), bath temperature adopts 40 ° of C.
Preferable, when carrying out vacuum distilling in the step (3), the time that vacuumizes is 0.5-1.5 hour; More, the time that vacuumizes is 0.5 hour.
The sample size of vacuum distilling of the present invention is 2.5mL, and promptly organic phase extract O1 is 2.5mL; Cut F2 adds solvent can be settled to the cut F2 that obtains to add solvent behind the 5mL; Wherein, the solvent that is added in the step (3) is selected from ether.
(4) the preparation gc is separated: the cut F2 of the adding solvent constant volume that step (3) is obtained adopts the preparation vapour phase chromatography to separate; Adopt liquid nitrogen condensation to collect successively by the appearance time of material and obtain 5 cut SF1-SF5; Cut SF1-SF5 respectively with the cut S F1-SF5 that obtains behind the solvent constant volume with solvent cut, can be obtained alkaline flavour ingredient SF4; Wherein, the constant volume solvent that is adopted is an ethanol.
Above-mentioned 5 cut SF1-SF5 represent SF1, SF2, SF3, SF4 and SF5.
In the step (4), said preparation gas chromatographic column is the glass column packed column, and external diameter is 6-20mm, and internal diameter is 2-3.5mm, and length is 1-6m, and stationary phase is 2-10%SE-30/chromsorb W-HP (60-80mesh) filler.
Preferably, in the step (4), it is 6mm that said preparation gas chromatographic column adopts external diameter, and internal diameter is 3.5mm, and length is 3m, corresponding glass column of filling 8.5g 7% SE-30/chromsorb W-HP (60-80 mesh) filler.The preparation method of above-mentioned 7%SE-30/chromsorb W-HP (60-80mesh) is: the SE-30 solid of 3.5g adds 46.5g chromsorb W-HP (60-80mesh) with 60mL toluene heating for dissolving, and rotary evaporation makes after removing toluene; Other preparing methods like 2-10%SE-30/chromsorb W-HP (60-80mesh) are identical with the preparation method of 7% SE-30/chromsorb W-HP (60-80mesh).
Further, when adopting in the step (4) the preparation gc to separate, temperature programming is: 45 ℃ kept 10 minutes earlier, were warmed up to 80 ℃ and kept 1 minute with 5 ℃/min, were warmed up to 240 ℃ with 20 ℃/min again, kept 10 minutes, moved 36 minutes.Collecting the cut of collecting in cut SF1-SF5:10.67 minute to 13.06 minutes according to appearance time is SF1; 13.07 the cut of minute collecting by 14.22 minutes is SF2; 14.23 the cut of minute collecting by 15.85 minutes is SF3; 15.86 the cut of minute collecting by 17.96 minutes is SF4; 17.97 the cut of minute collecting by 18.62 minutes is SF5.
Preferable, in the step (4) before sample introduction condensation and collection pipe and continue to be condensed to collect and finish at first, collect cut SF1-SF5 successively.
Preferable, in the step (4), when the preparation gas chromatographic column was filled, filler was sealed with a small amount of silica wool in two ends.
Better, in the step (4), the sample size when adopting the preparation gas phase separation can be 100 μ L, altogether sample introduction 12 pins.
In the above-mentioned steps (4), said ethanol is preferably the ethanol of HPLC level.
The alkaline flavour ingredient SF14 that adopts the separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient of the present invention and adopt this separation method to obtain can be widely used in preparing in the cigarette shreds perfuming field.
The present invention is a raw material with high-quality cigarette smoke granule phase substance; Successively after extraction, pickling, alkali lye adjusting pH value, separation concentrated, vacuum distilling obtain; After the cut F1-F2 gas chromatography mass spectrometry stratographic analysis of collecting, select the cut F2 that obvious nicotine content is lower and boiling point is lower.Then cut F2 employing preparation gc is separated and carry out deep separation and purification, enrichment fragrance cut combines through chemical analysis and sensory evaluating smoking, and filtering out cut SF4 is best alkaline flavour ingredient, finally confirms and acquisition target fraction SF4.
Outstanding advantage of the present invention is:
The present invention is raw material with high-quality cigarette smoke granule phase substance and utilizes vacuum distilling to separate with preparative gas chromatography to prepare alkaline flavour ingredient; Systematically crucial alkaline flavour ingredient in the cigarette mainstream flue gas has been studied in analysis; Through removing the alkaline components that in a large number the cigarette flavour ingredient is not had contribution, the flavour ingredient of gathering trace defines the cut that fragrance is worth; The effective alkaline flavour ingredient of final acquisition, research and development are very necessary to cigarette flavors.
Description of drawings
Fig. 1 is with the GC-MS total ion current figure of the alkaline components O1 of 40 times of ether dilutions;
Wherein, maximum peak is the Nicotine peak.
The GC-MS total ion current figure of Fig. 2 vacuum distilling cut F2;
Wherein, the climax is a Nicotine.1 represents the 2-picoline, and 2 represent the 3-vinyl pyridine.
Fig. 3 prepares gas chromatogram;
A represents SF1; B represents SF2; C represents SF3; D represents SF4; E represents SF5.
Fig. 4 is the GC-MS total ion current figure of SF4 qualitatively.
Fig. 5 is the GC-MS total ion current figure of SF4 qualitatively;
1 represents 2, the 5-dimethylpyrazine; 2 represent 2, the 6-dimethylpyrazine;
3 represent the 2-ethyl pyrazine; 4 represent 2, the 3-dimethylpyrazine.
Embodiment
Below through specific specific examples embodiment of the present invention is described, those skilled in the art can understand other advantages of the present invention and effect easily by the content that this specification sheets disclosed.The present invention can also implement or use through other different embodiment, and each item details in this specification sheets also can be based on different viewpoints and application, carries out various modifications or change under the spirit of the present invention not deviating from.
The separation of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient:
(1) extract:
On RM200A rotating disc type smoking machine (Borgwaldt KC company); Adopt filter disc to capture mode; Collect sound tobacco flue gas granule phase substance with cambridge filter (diameter is 92mm, and every cambridge filter is collected 20 cigarette smoke granule phase substances), obtain the cambridge filter ravin; Earlier with 750mL ether soaking and extracting, behind the supersound extraction 5min, 30min is extracted in the shaking table vibration more then with 30 cambridge filter ravin that capture high-quality cigarette smoke granule phase substance; Place after one day; After obtaining extracting solution, repeat again to extract one time, obtain the 1500mL extracting solution altogether.With the 200mL liquid concentrator O that obtains the Vandyke brown crude extract behind the extracted twice liquid concentrating under reduced pressure that obtains, the i.e. diethyl ether solution of Vandyke brown crude extract; Wherein, the vacuum tightness of concentrating under reduced pressure is 870mbar, and bath temperature is 36 ° of C.(2) separation of alkaline components:
(2.1) pickling: the liquid concentrator O of the Vandyke brown crude extract that step (1) is obtained is transferred to separating funnel, and adopting mass percent concentration is 5% H
2SO
4Aqueous solution extraction three times, each used aqueous acid volume is 250mL.Separate organic phase and water, obtain water-phase extract A1.
(2.2) acquisition of alkaline components O1: after the pH value of the water-phase extract A1 that to use earlier mass percent concentration be 50% NaOH solution obtains step (2.1) is adjusted to 11-12; Use extracted with diethyl ether again 3 times, each ether volume is 150mL, tell organic phase and water after; Normal pressure filtered after adding 30g SODIUM SULPHATE ANHYDROUS 99PCT spent the night in organic phase; Then organic phase is carried out concentrating under reduced pressure and can obtain organic phase extract O1, be alkaline components O1, volume is 2.5mL; The vacuum tightness of wherein said concentrating under reduced pressure is 870mbar, and the bath temperature that concentrating under reduced pressure adopted is 36 ° of C.Get 10 μ L alkaline components O1,, carry out not that split stream sampling changes the gas chromatography mass spectrometry chromatographic instrument over to, obtain the GC-MS total ion current figure of the alkaline components O1 of 40 times of ether dilutions with 40 times of ether dilutions, as shown in Figure 1.
The GC-MS condition: the Agilent7890-5973MSD gas chromatograph-mass spectrometer, the GC condition: chromatographic column is 260 ° of C of Agilent DB-WAX polyoxyethylene glycol gas phase capillary column (60m x 0.32mm x 0.25 μ m); Injector temperature: 240 ℃; Carrier gas: He, 1.5mL/min; Sample size: 1.0 μ L.Temperature programming: 40 ℃ kept 1 minute earlier, were warmed up to 200 ℃ with 3 ℃/min, were warmed up to 230 ℃ with 10 ℃/min again, kept 5 minutes, moved 62.3 minutes.
The MS condition: the transmission line temperature is 240 ℃; Level Four bar temperature is 150 ℃; The EI ion source temperature is 230 ℃; Ionizing energy is 70eV; The total mass number scope is 35-300amu.
Preliminary GC-MS analyzes (Fig. 1) can find out that the O1 component contains super amount Nicotine (climax), and peak area accounts for 95% of all the components total peak area.Obviously, need to remove high-load Nicotine, just can carry out next step work through separation and purification.
(3) vacuum distilling separates:
Adopt the vacuum distilling partition method that the 2.5mL organic phase extract O1 that step (2.2) obtains is carried out vacuum distilling, separate obtaining 2 cut F1 and F2, then cut F2 is settled to the cut F2 that 5mL obtains to be dissolved in solvent with solvent; Wherein, the solvent of said solvent constant volume employing is an ether.When carrying out vacuum distilling; Utilization EXPT Pumping Station (Britain Edwards company) vacuumizes; Select for use intelligence city HSQ-3 thermostatical water bath (Shanghai ZHICHENG Anaiytical Instrument Manufacturing Co., Ltd.) to carry out water-bath, and vacuum distillation plant (the organic institute in Chinese Academy of Sciences Shanghai glassware workshop) is collected cut F2.When carrying out vacuum distilling, only driving the one-level pump, is 0.01-0.1mbar to keep lower vacuum tightness, and in the process that vacuumizes, the horizontal plane that is kept for the liquid nitrogen of condensation is not less than the height of cut F2 receiving flask.In the vacuum distillation process, the time that vacuumizes is 0.5-1.5 hour, and the temperature of water bath is 40 ° of C.With this understanding, collect cut F1 and F2.And cut F2 is settled to 5mL with ether.And cut F1, the F2 that collects carried out not split stream sampling change the gas chromatography mass spectrometry chromatographic instrument over to and carry out gas phase-mass spectrum GC-MS detailed analysis, and obtain the GC-MS total ion current figure of vacuum distilling cut F2, as shown in Figure 2.The same step of GC-MS condition (2.2).
Above-mentioned vacuum distillation method for separating can better reduce the loss of effective flavour ingredient than the normal pressure column chromatography.More Nicotine has been stayed among the cut F2, and high boiling composition has also been stayed among the cut F2, and separation efficiency is high, good reproducibility.Preliminary GC-MS analyzes (as shown in Figure 2) can find out that vacuum distilling cut F2 contains pyridines.Because pyrazine compounds content is very little, does not find the pyrazine class.And pyrazine class and pyridine compounds and their are to constitute in the perfume compound of cigarette mainstream flue gas characteristic very important one type; Major part has the intensive burnt odor, baking is fragrant is very easy to coordinate with tobacco inherent fragrance; The natural cigarette of fine modification of ability and raising cigarette is fragrant; And can cover the assorted gas of part, and improve pleasant impression, in the table perfume (or spice) of cigarette, be widely applied.But nicotine content is still than higher, and the Nicotine peak area accounts for 50% (as shown in Figure 2) of total peak area, needs further separation and purification, removes high-load Nicotine.
(4) the preparation gc is separated:
To containing the F2 5mL of crucial alkaline flavour ingredient, utilization preparation gc separation method.The cut F2 that step (3) is obtained adopts the preparation vapour phase chromatography to separate, and collects on a time period and obtains 5 cut SF1-SF5; Wherein, said collection on a time period is to cut apart according to the appearance time in the gas chromatogram (Fig. 3).When preparing the gc separation, each sample size is 100 μ L, altogether sample introduction 12 pins, sample introduction 1200 μ L altogether.
Preparation gc separation condition: laboratory assembling preparative gas chromatograph, for Agilent G1530A gas chromatograph and the adapter (Houston company) that has a six-way valve assemble.The GC condition: chromatographic column is self-control preparation gas chromatographic column (post is that external diameter is 6mm, and internal diameter is 3.5mm, and length is the glass column of 3m, 8.5g 7% SE-30/chromsorb W-HP (60-80mesh) filler).Injector temperature: 240 ℃; Carrier gas: Air, 1.5mL/min; Sample size: 100 μ L.The temperature programming condition is: 45 ℃ kept 10 minutes earlier, were warmed up to 80 ℃ with 5 ℃/min and kept 1 minute, were warmed up to 240 ℃ with 20 ℃/min again, kept operation 36min 10 minutes.Other preparation gc separation conditions are: adopt the isolating temperature programming of preparation gc to be: 45 ℃ kept 10 minutes earlier, were warmed up to 80 ℃ and kept 1 minute with 5 ℃/min, were warmed up to 240 ℃ with 20 ℃/min again, kept 10 minutes, moved 36 minutes.Each cut is collected according to the gc appearance time, and is specifically as shown in table 3: the component of collecting in 10.67 minutes to 13.06 minutes is SF1; 13.07 the component of minute collecting by 14.22 minutes is SF2; 14.23 the component of minute collecting by 15.85 minutes is SF3; 15.86 the component of minute collecting by 17.96 minutes is SF4; 17.97 the component of minute collecting by 18.62 minutes is SF5.
Each cut Fractional Collections table of table 1 preparation gas phase
| Cut | The switching valve sequence number | Collection time (minute) |
| |
1 | 10.67-13.06 |
| |
2 | 13.07-14.22 |
| |
3 | 14.23-15.85 |
| |
4 | 15.86-17.96 |
| |
5 | 17.97-18.62 |
In the step (4), when component begins to flow out, collect with the liquid nitrogen condensation collection tube, last, each cut uses ethanol to be settled to 0.5mL respectively and obtains the cut SF1-SF5 of ethanol as solvent.To carry out GC-MS with the cut SF1-SF5 of ethanol constant volume respectively detects.The same step of GC-MS condition (2.2).To advance the GC-MS instrument with the cut SF4 that ethanol washes out and detect the GC-MS total ion current figure that obtains SF4, as shown in Figure 4.Fig. 4 and Fig. 2 are compared and can find out, separate, can the high Nicotine of content among the vacuum distilling cut F2 be removed through the preparation gc.Find that through GC-MS detected result (as shown in Figure 4) if use and the middle GC-MS condition inspection of step (2.2) cut SF1-SF5, it is qualitative to find that most of peaks can not carry out.So the heating schedule of GC-MS is adjusted into: 40 ℃ kept 1 minute earlier, were warmed up to 140 ℃ with 2 ℃/min, kept operation 51min 0 minute.The same steps of other GC-MS conditions (2.2).Cut SF4 with the ethanol constant volume changes the GC-MS total ion current figure that testing conditions detects acquisition SF4, and is as shown in Figure 5.The peak that obtains like this can carry out qualitative analysis.Cut SF4 be the target alkalescence flavour ingredient that will obtain.
Alkaline flavour ingredient SF1-SF5 is used alcohol dilution, and the injection of solution that is made into concentration respectively and is 3cig/mL gets in the blank cigarette smokes panel test.Wherein 3/milliliter are meant the alkaline flavour ingredient that contains 3 cigarette in every milliliter of ethanol.
Flavour ingredient injecting condition: the solution of above-mentioned dilution is injected the not blank cigarette sample of perfuming with CIJECTOR type laboratory essence and flavoring agent injector (German BURGHART company); Every blank cigarette injection volume is 10 μ L; Start injection point (non-filter end) is 2mm, and the end injection point is 55mm.Injection speed is 10.0mm/s.The injection speed of rotation is 4.0vps.
By the expert that smokes panel test in the industry is that the group of smokeing panel test that main body is formed goes to carry out the fragrance comparison of smokeing panel test.Think that through smokeing panel test the result who compares with reference cigarette (injecting the blank cigarette of 10 μ L alcoholic acid) sees table 2.
Table 2 adds the cigarette smoking result of cut SF1-SF5 respectively
Above-mentioned preparation gc separation method can better be removed Nicotine than the normal pressure silica gel column chromatography, the better effects if of effective flavour ingredient of gathering trace, and separation efficiency is higher, and repeatability is better.Preliminary smoking result combines chemical composition SF1-SF5 to analyze can find out that the SF4 component has perfuming effect preferably.According to table 2, we obtain conclusion, and cigarette flavor amount, the fragrance matter of adding the cut SF4 (3cig/mL) of appropriate amount increase, and burnt sweet sense strengthens, and flue gas is fine and smooth more.
Fig. 2 and Fig. 5 are compared and can find out, separate careful cutting through the preparation gc, effectively the enrichment pyrazine compounds.The effectively a spot of effective flavour ingredient of enrichment of this separation method is described simultaneously, and what removal content was high contributes unconspicuous other components to fragrance, and finally obtains needed target alkalescence flavour ingredient SF4.
Alkaline flavour ingredient SF4 is used alcohol dilution, and being made into concentration respectively is 6cig/mL, 3cig/mL, and the solution of 1.5cig/mL (being labeled as R1 respectively, R2 and R3) injection gets in the blank coil cigarette smokes panel test.Other injecting conditions were smoked panel test with the first time.Smoking result is seen table 5.According to table 3, we obtain conclusion, and cigarette flavor amount, the fragrance matter of adding the cut SF4 (3-6cig/mL) of appropriate amount increase, and burnt sweet sense strengthens, and flue gas is fine and smooth more.
Table 3 adds the cigarette smoking result of the cut SF4 of different concns
The separation of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient:
The vacuum tightness of removing the concentrating under reduced pressure among the liquid concentrator O that obtains the Vandyke brown crude extract in the step (1) behind the extracting solution concentrating under reduced pressure with acquisition is 740mbar; Bath temperature is outside 33 ° of C; And the vacuum tightness that obtains the concentrating under reduced pressure of organic phase extract O1 in the step (2.2) behind the concentrating under reduced pressure is 740mbar; Bath temperature is outside 33 ° of C, and other separating steps are identical with embodiment 1, finally obtains target alkalescence flavour ingredient SF4.
The alkaline flavour ingredient SF4 that present embodiment obtains detects through GC-MS can know that its main fragrance matter is a dimethylpyrazine, and essential substance is specially 2-ethyl pyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine and 2,3-dimethylpyrazine.Alkaline flavour ingredient SF4 is dissolved with ethanol once more, and the solution that is made into concentration and is 3cig/mL is used to smoke panel test.
Smoke panel test: injecting 10 μ L alkalescence flavour ingredient SF4 with the essence and flavoring agent injector and make an addition in the blank cigarette, is that the group of smokeing panel test that main body is formed goes to carry out the fragrance comparison of smokeing panel test by the expert that smokes panel test in the industry.Think through smokeing panel test and to compare with reference cigarette (adding the blank cigarette of 10 μ L alcoholic acid) that the cigarette smoke that adds this cut SF4 is softer, burnt sweet sense strengthens, perfume quantity, and fragrance matter has lifting.
The separation of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient:
The vacuum tightness of removing the concentrating under reduced pressure among the liquid concentrator O that obtains the Vandyke brown crude extract in the step (1) behind the extracting solution concentrating under reduced pressure with acquisition is 900mbar; Bath temperature is outside 39 ° of C; And the vacuum tightness that obtains the concentrating under reduced pressure of organic phase extract O1 in the step (2.2) behind the concentrating under reduced pressure is 900mbar; Bath temperature is outside 39 ° of C, and other separating steps are identical with embodiment 1, finally obtains target alkalescence flavour ingredient SF4.
The alkaline flavour ingredient SF4 that present embodiment obtains detects through GC-MS can know that its main fragrance matter is a dimethylpyrazine, and essential substance is specially 2-ethyl pyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine and 2,3-dimethylpyrazine.Alkaline flavour ingredient SF4 is used dissolve with ethanol, and the solution that is made into concentration and is 3cig/mL is used to smoke panel test.
Smoke panel test: injecting 10 μ L alkalescence flavour ingredient SF4 with the essence and flavoring agent injector and make an addition in the blank cigarette, is that the group of smokeing panel test that main body is formed goes to carry out the fragrance comparison of smokeing panel test by the expert that smokes panel test in the industry.Think through smokeing panel test and to compare with reference cigarette (adding 10 μ L ethanol) that the burnt fragrant and sweet sense of cigarette of adding this cut SF4 strengthens, flue gas is softer, and fragrance matter, perfume quantity increase, and assorted gas reduces to some extent, and pungency diminishes.
The foregoing description is illustrative principle of the present invention and effect thereof only, but not is used to limit the present invention.Any be familiar with this technological personage all can be under spirit of the present invention and category, the foregoing description is modified or is changed.Therefore, have common knowledge the knowledgeable in the affiliated such as technical field, must contain by claim of the present invention not breaking away from all equivalence modifications of being accomplished under disclosed spirit and the technological thought or changing.
Claims (10)
1. the separation method of a cigarette smoke granule phase substance neutral and alkali flavour ingredient, said alkaline flavour ingredient is a raw material with the cigarette smoke granule phase substance, successively through extraction, the separation of alkaline components, vacuum distilling separates and preparation gc separating step makes; The essential substance of said alkaline flavour ingredient comprises dimethylpyrazine.
2. the separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 1; It is characterized in that the essential substance of said alkaline flavour ingredient is a 2-ethyl pyrazine, 2,5-dimethylpyrazine, 2; 6-dimethylpyrazine and 2, the 3-dimethylpyrazine.
3. the separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 1 is characterized in that, specifically may further comprise the steps:
(1) extracts: on the rotating disc type smoking machine, adopt filter disc to capture mode, collect high-quality cigarette smoke granule phase substance, obtain the cambridge filter ravin with cambridge filter; After the cambridge filter ravin employing extraction solvent extraction that obtains, concentrating under reduced pressure obtains the liquid concentrator O of Vandyke brown crude extract;
(2) separation of alkaline components:
(2.1) pickling: the liquid concentrator O of the Vandyke brown crude extract that step (1) is obtained adopts acid solution to extract, and extraction repeatedly separates organic phase and water respectively, obtains water-phase extract A1;
(2.2) acquisition of alkaline components O1: after the pH value of the water-phase extract A1 that step (2.1) is obtained with alkali lye earlier is adjusted to 11-12; Again repeatedly with organic solvent extraction; Tell organic phase and water, organic phase is carried out obtaining organic phase extract O1 behind the concentrating under reduced pressure, be alkaline components O1.
(3) vacuum distilling separates: adopt the vacuum distilling partition method that the organic phase extract O1 that step (2.2) obtains is carried out vacuum distilling, separate obtaining 2 cut F1 and F2, then with the cut F2 that obtains to add solvent behind the cut F2 adding solvent constant volume;
(4) the preparation gc is separated: the cut F2 of the adding solvent constant volume that step (3) is obtained adopts the preparation vapour phase chromatography to separate; Adopt liquid nitrogen condensation to collect successively by the appearance time of material and obtain 5 cut SF1-SF5; Cut SF1-SF5 respectively with the cut SF1-SF5 that obtains behind the solvent constant volume with solvent cut, can be obtained alkaline flavour ingredient SF4.
4. the separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 3 is characterized in that in the step (1), said extraction solvent is an ether; The liquid concentrator O of said Vandyke brown crude extract is the diethyl ether solution of Vandyke brown crude extract; In the step (2.2), said organic solvent is an ether; In the step (3), the solvent that is added is selected from ether; In the step (4), the constant volume solvent that is adopted is an ethanol.
5. the separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 3; It is characterized in that; In step (1) and the step (2.2), the vacuum tightness of said concentrating under reduced pressure is 700 – 1000mbar, and the bath temperature that concentrating under reduced pressure adopted is 25-45 ° of C; In the step (3), the vacuum tightness of said vacuum distilling is 0.01-0.1mbar, and bath temperature is 25-45 ° of C.
6. the separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 3 is characterized in that in the step (2), said acid solution is a sulphuric acid soln; The mass percent concentration of acid is 1-20% in the said sulphuric acid soln; In the step (2.2), said alkali lye is the aqueous solution of sodium hydroxide; The mass percent concentration of alkali is 10-80% in the said aqueous sodium hydroxide solution.
7. the separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 3; It is characterized in that; In the step (3), when carrying out vacuum distilling, the sequencing that adopts the liquid nitrogen condensation mode to steam by cut is collected cut F1 and cut F2 successively; The time that vacuumizes is 0.5-1.5 hour;
In the step (3), before beginning to vacuumize, at first adopt the liquid nitrogen condensation scoop to carry out condensation and collection, and till continuing to be condensed to experiment and finishing the final vacuum state and disappear;
In the step (4), when adopting preparative hplc to separate, condensation and collection pipe and continue to be condensed to fraction collection and finish at first before sample introduction is collected cut SF1-SF5 successively.
8. the separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 3 is characterized in that, in the step (4); The preparation gas chromatographic column that is adopted when adopting the preparation gc to separate is the glass column packed column; Its external diameter is 6-20mm, and internal diameter is 2-3.5mm, and length is 1-6m; Stationary phase is a 2-10%SE-30/chromsorb W-HP filler, and the order number of filler is the 60-80 order.
9. the separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 3; It is characterized in that when adopting the preparation gc to separate in the step (4), temperature programming is: 45 ℃ kept 10 minutes earlier; Be warmed up to 80 ℃ and kept 1 minute with 5 ℃/min; Be warmed up to 240 ℃ with 20 ℃/min again, kept 10 minutes, move 36 minutes then; Collecting the cut of collecting in cut SF1-SF5:10.67 minute to 13.06 minutes according to appearance time is SF1; 13.07 the cut of minute collecting by 14.22 minutes is SF2; 14.23 the cut of minute collecting by 15.85 minutes is SF3; 15.86 the cut of minute collecting by 17.96 minutes is SF4; 17.97 the cut of minute collecting by 18.62 minutes is SF5.
10. the separation method that adopts the arbitrary described high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient of claim 1-9 is in preparation cigarette shreds perfuming Application for Field.
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| CN103919267A (en) * | 2014-03-28 | 2014-07-16 | 广东中烟工业有限责任公司 | Novel tobacco product production method |
| CN104522877A (en) * | 2014-12-06 | 2015-04-22 | 中国农业科学院烟草研究所 | Method for manufacturing low temperature cigarette raw materials |
| CN104757703A (en) * | 2014-12-31 | 2015-07-08 | 贵州中烟工业有限责任公司 | Tobacco distillate, and preparation and application thereof |
| CN105445392A (en) * | 2015-11-13 | 2016-03-30 | 中国烟草总公司郑州烟草研究院 | Method for analyzing and detecting alkaline flavor components by using direct solvent extraction gas chromatography-mass spectrometry |
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| CN103919267A (en) * | 2014-03-28 | 2014-07-16 | 广东中烟工业有限责任公司 | Novel tobacco product production method |
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| CN104522877A (en) * | 2014-12-06 | 2015-04-22 | 中国农业科学院烟草研究所 | Method for manufacturing low temperature cigarette raw materials |
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| CN105445392A (en) * | 2015-11-13 | 2016-03-30 | 中国烟草总公司郑州烟草研究院 | Method for analyzing and detecting alkaline flavor components by using direct solvent extraction gas chromatography-mass spectrometry |
| CN105595405A (en) * | 2016-01-29 | 2016-05-25 | 广西中烟工业有限责任公司 | Method for promoting sensory quality of tobacco leaves by regulating and controlling content of alkaline flavor components |
| CN105595405B (en) * | 2016-01-29 | 2017-05-03 | 广西中烟工业有限责任公司 | Method for promoting sensory quality of tobacco leaves by regulating and controlling content of alkaline flavor components |
| CN105929082A (en) * | 2016-07-14 | 2016-09-07 | 云南中烟工业有限责任公司 | Method for separating and determining pyrazine substances and pyridine substances in saliva |
| CN109846077A (en) * | 2018-12-12 | 2019-06-07 | 云南中烟工业有限责任公司 | A kind of method and application that characteristic component is screened and prepared from tobacco |
| CN114711455A (en) * | 2022-03-10 | 2022-07-08 | 浙江中烟工业有限责任公司 | Preparation method and application of alkaline flavor component characteristic of Canadian tobacco smoke |
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