CN102766534B - 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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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 cigarette mainstream flue gas, relate in particular to a kind of separation method of isolating micro-alkaline flavour ingredient from the cigarette mainstream flue gas alkaline components that contains large number of biological alkali.
Background technology
Cigarette smoke neutral and alkali composition has 1735 kinds of compounds, and wherein nitrogen heterocycles accounts for 1246 kinds.Nitrogen heterocycles in cigarette smoke contains myosmine take Nicotine as main, cotinine, nornicotine, neonicotine, neonicotine, the composition such as alkaloid and the gas phase aminated compounds such as passiflorin falls in passiflorin, 2,3-dipyridyl and a small amount of pyridine, pyrazine, pyrroles.The alkaloid majority mainly burns and sucks in process at cigarette with prototype and enters flue gas from Transformation of tobacco.An amine part is that the part aliphatic amide in tobacco directly shifts and enters flue gas and forms when being burnt and sucked by cigarette, and another part is by the generation of the composition generation cracking in tobacco.The micromolecular compound majorities such as pyridine, pyrazine, pyrroles come from the Maillard reaction.The chemical substances such as nicotine satisfy to be inhaled flavor strength and are being given and important impact is arranged aspect the tobacco physiological strength.Amine has unpleasant pungency, and the flue gas quality is had bad contribution.Research is found, pyrazine class and pyridine compounds and their are to consist of a very important class in cigarette mainstream flue gas characteristic chicken flavor compound, major part has strong burnt odor, baking is fragrant and fragrance very easy coordinate intrinsic with tobacco, the natural cigarette of the fine modification of energy and raising cigarette is fragrant, and can cover the assorted gas of part, improve pleasant impression, be widely applied in the table perfume (or spice) of cigarette.When the content of pyrazine, pyridines nitrogenous compound was high, the fragrance concentration of cigarette was higher, and fragrance is better.Acetylpyridine has the characteristic perfume of tobacco sample, 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 feature of burley tobaccos to inhale flavor and fragrance.It is fragrant that pyrazine compounds has baking more, the nut of stir-fry arranged and like cocoa aroma, be used for strengthening note, cover the assorted gas of tobacco as methylpyrazine, and dimethylpyrazine has puffed rice fragrance, is used for improving perfume quantity and enriches the aromatic degree of cigarette.Dimethylpyrazine, methylpyrazine, the aroma components such as ethyl pyrazine 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 larger, 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, such as the content of pyrazine compounds is that approximately 5-50 μ g/ props up, separate that to prepare the very little flavour ingredient of these content more difficult.Therefore, systematically dissect crucial alkaline flavour ingredient in the research main flume, remove 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 practical guided 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, described alkaline flavour ingredient is take high-quality cigarette smoke granule phase substance as raw material, and separation, vacuum distilling separation and the preparative gas chromatography separating step through extraction, alkaline components makes successively; The essential substance of described alkaline flavour ingredient comprises dimethylpyrazine or dimethylpyrazine compounds.
Further, the essential substance of described alkaline flavour ingredient is 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 comprises the following steps:
(1) extract: on the rotating disc type smoking machine, adopt the filter disc Trapping ways, collect high-quality cigarette smoke granule phase substance with cambridge filter, obtain the cambridge filter ravin; After adopting extraction solvent to extract the cambridge filter ravin that obtains, concentrating under reduced pressure obtains the concentrated solution O of Vandyke brown crude extract;
Better, described extraction solvent is ether; The concentrated solution O of described Vandyke brown crude extract is the diethyl ether solution of Vandyke brown crude extract.
Better, the method for described extraction is for soaking one or more methods in extraction, ultrasonic extraction and shaking table oscillation extraction.
Better, the vacuum tightness of described concentrating under reduced pressure is 700-1000mbar, the bath temperature that concentrating under reduced pressure adopts is 25-45 ° of C.
(2) separation of alkaline components:
(2.1) pickling: the concentrated solution 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;
Better, described acid solution is sulphuric acid soln.Further, in described sulphuric acid soln, the mass percent concentration of acid is 1-20%.Preferably, in described sulphuric acid soln, the mass percent concentration of acid is 5%.
(2.2) acquisition of alkaline components O1: after the pH value of the water-phase extract A1 that first with alkali lye, step (2.1) is obtained is adjusted to 11-12, again with organic solvent extraction repeatedly, tell organic phase and water, organic phase is carried out obtaining organic phase extract O1 after concentrating under reduced pressure, be alkaline components O1.
Better, in step (2.2), described organic solvent is ether; Described alkali lye is the aqueous solution of sodium hydroxide.Further, to select mass percent concentration be the aqueous solution of the sodium hydroxide of 10-80% to described aqueous sodium hydroxide solution.Preferably, in described sodium hydroxide solution, the mass percent concentration of alkali is 50%.
Better, in step (2.2), the vacuum tightness of described concentrating under reduced pressure is 700 – 1000mbar, the bath temperature that concentrating under reduced pressure adopts is 25-45 ° of C.
Extraction in 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 to carry out vacuum distilling to the organic phase extract O1 that step (2.2) obtains, separate obtaining 2 cut F1 and F2, then cut F2 is added the cut F2 that obtains to add solvent after the solvent constant volume.
Better, when carrying out vacuum distilling in step (3), the sequencing that adopts the liquid nitrogen condensation mode to steam by cut is collected cut F1 and cut F2 successively.In step of the present invention (3), before beginning to vacuumize, at first adopt the liquid nitrogen condensation collector to carry out condensation and collect, and till continuing to be condensed to experiment and finishing the final vacuum state and disappear, this point is very important.
Further, in step (3), the vacuum tightness of described vacuum distilling is 0.01-0.1mbar, and bath temperature is 25-45 ℃.Better, when carrying out vacuum distilling in step (3), bath temperature adopts 40 ° of C.
Better, when carrying out vacuum distilling in 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 namely organic phase extract O1 is 2.5mL; Cut F2 adds solvent can be settled to the cut F2 that obtains to add solvent after 5mL; Wherein, the solvent that adds in step (3) is selected from ether.
(4) preparative gas chromatography separates: the cut F2 that adds the solvent constant volume that step (3) is obtained adopts the preparative gas chromatography partition method to separate, collect successively by the appearance time employing liquid nitrogen condensation of material and obtain 5 cut SF1-SF5, cut SF1-SF5 respectively with the cut S F1-SF5 that obtains after the solvent constant volume with solvent cut, can be obtained alkaline flavour ingredient SF4; Wherein, the constant volume solvent that adopts is ethanol.
Above-mentioned 5 cut SF1-SF5 represent SF1, SF2, SF3, SF4 and SF5.
In step (4), described preparative gas chromatography post 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 step (4), it is 6mm that described preparative gas chromatography post 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 preparation methods as 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 step (4) preparative gas chromatography to separate, temperature programming is: first 45 ℃ kept 10 minutes, were warmed up to 80 ℃ and kept 1 minute with 5 ℃/min, then were warmed up to 240 ℃ with 20 ℃/min, kept 10 minutes, moved 36 minutes.Collecting according to appearance time the cut of collecting in cut SF1-SF5:10.67 minute to 13.06 minutes 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.
Better, in step (4) before sample introduction condensation collection tube and continue to be condensed to collect and finish at first, collect successively cut SF1-SF5.
Better, in step (4), when the preparative gas chromatography post was filled, two ends sealed filler with a small amount of silica wool.
Better, in step (4), the sample size when adopting the preparation gas phase separation can be 100 μ L, altogether sample introduction 12 pins.
In above-mentioned steps (4), described ethanol is preferably the ethanol of HPLC level.
Adopt the separation method of high-quality cigarette smoke granule phase substance neutral and alkali flavour ingredient of the present invention and adopt alkaline flavour ingredient SF14 that this separation method obtains can be widely used in preparing in cigarette shreds perfuming field.
The present invention is take high-quality cigarette smoke granule phase substance as raw material, 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 adopt preparative gas chromatography to separate to cut F2 and carry out deep separation and purification, enrichment fragrance cut combines by chemical analysis and sensory evaluating smoking, and filtering out cut SF4 is best alkaline flavour ingredient, finally determines and obtains target fraction SF4.
Outstanding advantages of the present invention is:
The present invention is take high-quality cigarette smoke granule phase substance as raw material and utilize vacuum distilling to separate with preparative gas chromatography to prepare alkaline flavour ingredient, systematically dissect and studied crucial alkaline flavour ingredient in cigarette mainstream flue gas, by removing in a large number, the cigarette flavour ingredient do not had contributive alkaline components, the flavour ingredient of gathering trace, define 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 dilutes the GC-MS total ion current figure of the alkaline components O1 of 40 times with ether;
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 Nicotine.1 represents the 2-picoline, and 2 represent the 3-vinyl pyridine.
Fig. 3 preparative gas chromatography figure;
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 2,5-dimethylpyrazine; 2 represent 2,6-dimethylpyrazine;
3 represent the 2-ethyl pyrazine; 4 represent 2,3-dimethylpyrazine.
Embodiment
Below by specific specific examples explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this specification sheets.The present invention can also be implemented or be used by other different embodiment, and the every details in this specification sheets also can be based on different viewpoints and application, carries out various modifications or change under 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 the filter disc Trapping ways, collect the sound tobacco Smoke Particulate with cambridge filter (diameter is 92mm, and every cambridge filter is collected 20 cigarette smoke granule phase substances), obtain the cambridge filter ravin; 30 cambridge filter ravin that capture high-quality cigarette smoke granule phase substances are first soaked with the 750mL ether extract, then after supersound extraction 5min, then shaking table mechanical shaking extraction 30min, place after one day, after obtaining extracting solution, then repeat to extract one time, obtain altogether the 1500mL extracting solution.The 200mL concentrated solution O of Vandyke brown crude extract, the i.e. diethyl ether solution of Vandyke brown crude extract will be obtained after the extracted twice liquid concentrating under reduced pressure that obtain; 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 concentrated solution 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 aqueous acid volume used is 250mL.Separate organic phase and water, obtain water-phase extract A1.
(2.2) acquisition of alkaline components O1: after first being adjusted to 11-12 with the pH value of the mass percent concentration water-phase extract A1 that to be 50% NaOH solution obtain step (2.1), use again extracted with diethyl ether 3 times, each ether volume is 150mL, after telling organic phase and water, after adding the 30g anhydrous sodium sulphate to spend the night in organic phase, normal pressure filters, 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 adopts is 36 ° of C.Get 10 μ L alkaline components O1, with 40 times of ether dilutions, carry out Splitless injecting samples and change 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, 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 chromatography (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: first 40 ℃ kept 1 minute, were warmed up to 200 ℃ with 3 ℃/min, then were warmed up to 230 ℃ with 10 ℃/min, 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) and can find out, the O1 component contains super amount Nicotine (climax), and peak area accounts for 95% of all the components total peak area.Obviously, need by separation and purification, the Nicotine of high-content is removed, just can carry out next step work.
(3) vacuum distilling separates:
Adopt the vacuum distilling partition method to carry out vacuum distilling to the 2.5mL organic phase extract O1 that step (2.2) obtains, separate obtaining 2 cut F1 and F2, then cut F2 is settled to solvent the cut F2 that 5mL obtains to be dissolved in solvent; Wherein, the solvent of described solvent constant volume employing is ether.When carrying out vacuum distilling, utilization EXPT Pumping Station(Britain Edwards company) vacuumize, select intelligence city HSQ-3 thermostatical water bath (Shanghai ZHICHENG Anaiytical Instrument Manufacturing Co., Ltd.) to carry out water-bath, and vacuum distillation plant (organic institute's glassware workshop, Chinese Academy of Sciences Shanghai) is collected cut F2.When carrying out vacuum distilling, only open primary pump, to keep lower vacuum tightness as 0.01-0.1mbar, 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 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 Splitless injecting samples 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 in cut F2, and high boiling composition has also been stayed in cut F2, and separation efficiency is high, good reproducibility.Preliminary GC-MS analyzes (as shown in Figure 2) and can find out, vacuum distilling cut F2 contains pyridines.Because pyrazine compounds content is very little, do not find the pyrazine class.And pyrazine class and pyridine compounds and their are to consist of a very important class in the perfume compound of cigarette mainstream flue gas feature, the fragrance very easy coordination intrinsic with tobacco that major part has strong burnt odor, baking is fragrant, the natural cigarette of the fine modification of energy and raising cigarette is fragrant, and can cover the assorted gas of part, improve pleasant impression, be widely applied in the table perfume (or spice) of cigarette.But nicotine content is still higher, and the 50%(that the Nicotine peak area accounts for total peak area is as shown in Figure 2), need further separation and purification, the Nicotine of high-content is removed.
(4) preparative gas chromatography separates:
To containing the F2 5mL of crucial alkaline flavour ingredient, use the preparative gas chromatography separation method.The cut F2 that step (3) is obtained adopts the preparative gas chromatography partition method to separate, and collects on a time period and obtains 5 cut SF1-SF5; Wherein, described collection on a time period is to cut apart according to the appearance time in gas chromatogram (Fig. 3).When being prepared the gas-chromatography separation, each sample size is 100 μ L, altogether sample introduction 12 pins, sample introduction 1200 μ L altogether.
The preparative gas chromatography separation condition: laboratory assembling preparative gas chromatograph, for Agilent G1530A gas chromatograph and adapter (Houston company) with a six-way valve assemble.The GC condition: chromatographic column is self-control preparative gas chromatography post (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: first 45 ℃ kept 10 minutes, were warmed up to 80 ℃ with 5 ℃/min and kept 1 minute, then be warmed up to 240 ℃ with 20 ℃/min, kept operation 36min 10 minutes.Other preparative gas chromatography separation conditions are: the temperature programming of adopting preparative gas chromatography to separate is: first 45 ℃ kept 10 minutes, were warmed up to 80 ℃ and kept 1 minute with 5 ℃/min, then were warmed up to 240 ℃ with 20 ℃/min, kept 10 minutes, moved 36 minutes.Each cut is collected according to the gas-chromatography 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 step (4), collect with the liquid nitrogen condensation collection tube when component begins to flow out, last, each cut is settled to 0.5mL with ethanol respectively and obtains the cut SF1-SF5 that ethanol is solvent.To carry out respectively with the cut SF1-SF5 of ethanol constant volume GC-MS detects.The same step of GC-MS condition (2.2).To advance with the cut SF4 that ethanol washes out the GC-MS instrument 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 through preparative gas chromatography, the high Nicotine of content in vacuum distilling cut F2 can be removed.Find by GC-MS detected result (as shown in Figure 4), check cut SF1-SF5 if use with the middle GC-MS condition of step (2.2), find that most of peaks can not carry out qualitative.So the heating schedule of GC-MS is adjusted into: first 40 ℃ kept 1 minute, 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, as shown in Figure 5.The peak that obtains like this can carry out qualitative analysis.Cut SF4 is the target alkalescence flavour ingredient that will obtain.
With alkaline flavour ingredient SF1-SF5 alcohol dilution, the injection of solution that is made into respectively concentration and is 3cig/mL enters in blank cigarette smokes panel test.3/milliliter alkaline flavour ingredients that refer to contain in every milliliter of ethanol 3 cigarette wherein.
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.
Be that the group of smokeing panel test that main body forms goes to carry out the fragrance comparison of smokeing panel test by the expert that smokes panel test in industry.Think through smokeing panel test and the results are shown in Table 2 with the reference cigarette blank cigarette of 10 μ L ethanol (injection) is compared.
Table 2 adds respectively the cigarette smoking result of cut SF1-SF5
Above-mentioned preparative gas chromatography 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 is analyzed and can be found out in conjunction with chemical composition SF1-SF5, and the SF4 component has perfuming effect preferably.According to table 2, we obtain conclusion, add the cut SF4(3cig/mL of appropriate amount) cigarette flavor amount, fragrance matter increase, burnt sweet sense strengthens, flue gas is finer and smoother.
Fig. 2 and Fig. 5 are compared and can find out, separate careful cutting, effectively enrichment pyrazine compounds through preparative gas chromatography.The effectively a small amount 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.
With alkaline flavour ingredient SF4 alcohol dilution, being made into respectively concentration is 6cig/mL, 3cig/mL, and the solution of 1.5cig/mL (being labeled as respectively R1, R2 and R3) injection enters in the blank coil cigarette smokes panel test.Other injecting conditions and smokeing panel test for the first time.Smoking result sees Table 5.According to table 3, we obtain conclusion, add the cut SF4(3-6cig/mL of appropriate amount) cigarette flavor amount, fragrance matter increase, burnt sweet sense strengthens, flue gas is finer and smoother.
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 in the concentrated solution O that obtains the Vandyke brown crude extract in step (1) after 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 step (2.2) after concentrating under reduced pressure is 740mbar, bath temperature is outside 33 ° of C, other separating steps are identical with embodiment 1, finally obtain target alkalescence flavour ingredient SF4.
The alkaline flavour ingredient SF4 that the present embodiment obtains detects as can be known through GC-MS, and its main fragrance matter is 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 again with ethanol, and the solution that is made into concentration and is 3cig/mL is used for smokeing panel test.
Smoke panel test: 10 μ L alkalescence flavour ingredient SF4 make an addition in blank cigarette with essence and flavoring agent injector injection, are that the group of smokeing panel test that main body forms goes to carry out the fragrance comparison of smokeing panel test by the expert that smokes panel test in industry.Think through smokeing panel test and compare with reference cigarette (adding the blank cigarette of 10 μ L ethanol), the cigarette smoke that adds this cut SF4 is softer, and 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 in the concentrated solution O that obtains the Vandyke brown crude extract in step (1) after 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 step (2.2) after concentrating under reduced pressure is 900mbar, bath temperature is outside 39 ° of C, other separating steps are identical with embodiment 1, finally obtain target alkalescence flavour ingredient SF4.
The alkaline flavour ingredient SF4 that the present embodiment obtains detects as can be known through GC-MS, and its main fragrance matter is dimethylpyrazine, and essential substance is specially 2-ethyl pyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine and 2,3-dimethylpyrazine.With alkaline flavour ingredient SF4 dissolve with ethanol, the solution that is made into concentration and is 3cig/mL is used for smokeing panel test.
Smoke panel test: 10 μ L alkalescence flavour ingredient SF4 make an addition in blank cigarette with essence and flavoring agent injector injection, are that the group of smokeing panel test that main body forms goes to carry out the fragrance comparison of smokeing panel test by the expert that smokes panel test in industry.Think through smokeing panel test and compare with reference cigarette (adding 10 μ L ethanol), the burnt fragrant and sweet sense of cigarette of adding this cut SF4 strengthens, and flue gas is softer, and fragrance matter, perfume quantity increase, and assorted gas reduces to some extent, and pungency diminishes.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not is used for restriction the present invention.Any person skilled in the art scholar all can under spirit of the present invention and category, modify or change above-described embodiment.Therefore, have in technical field under such as and know that usually the knowledgeable modifies or changes not breaking away from all equivalences of completing under disclosed spirit and technological thought, must be contained by claim of the present invention.
Claims (7)
1. the separation method of a cigarette smoke granule phase substance neutral and alkali flavour ingredient, described alkaline flavour ingredient be take the cigarette smoke granule phase substance as raw material, successively through extraction, separation, vacuum distilling separation and the preparative gas chromatography separating step of alkaline components make;
The essential substance of described alkaline flavour ingredient comprises dimethylpyrazine;
Described separation method specifically comprises the following steps:
(1) extract: on the rotating disc type smoking machine, adopt the filter disc Trapping ways, collect high-quality cigarette smoke granule phase substance with cambridge filter, obtain the cambridge filter ravin; After adopting extraction solvent to extract the cambridge filter ravin that obtains, concentrating under reduced pressure obtains the concentrated solution O of Vandyke brown crude extract;
(2) separation of alkaline components:
(2.1) pickling: the concentrated solution 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 first with alkali lye, step (2.1) is obtained is adjusted to 11-12, again with organic solvent extraction repeatedly, tell organic phase and water, organic phase is carried out obtaining organic phase extract O1 after concentrating under reduced pressure, be alkaline components O1.
(3) vacuum distilling separates: adopt the vacuum distilling partition method to carry out vacuum distilling to the organic phase extract O1 that step (2.2) obtains, separate obtaining 2 cut F1 and F2, then cut F2 is added the cut F2 that obtains to add solvent after the solvent constant volume;
(4) preparative gas chromatography separates: the cut F2 that adds the solvent constant volume that step (3) is obtained adopts the preparative gas chromatography partition method to separate, collect successively by the appearance time employing liquid nitrogen condensation of material and obtain 5 cut SF1-SF5, cut SF1-SF5 respectively with the cut SF1-SF5 that obtains after the solvent constant volume with solvent cut, can be obtained alkaline flavour ingredient SF4;
Wherein,
In step (1), described extraction solvent is ether; The concentrated solution O of described Vandyke brown crude extract is the diethyl ether solution of Vandyke brown crude extract; In step (2.2), described organic solvent is ether; In step (3), the solvent that adds is selected from ether; In step (4), the constant volume solvent that adopts is ethanol;
When adopting in step (4) preparative gas chromatography to separate, temperature programming is: first 45 ℃ kept 10 minutes, were warmed up to 80 ℃ and kept 1 minute with 5 ℃/min, then were warmed up to 240 ℃ with 20 ℃/min, kept 10 minutes, then moved 36 minutes; Collecting according to appearance time the cut of collecting in cut SF1-SF5:10.67 minute to 13.06 minutes 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.
2. the separation method of cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 1, is characterized in that, the essential substance of described alkaline flavour ingredient is 2-ethyl pyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine and 2,3-dimethylpyrazine.
3. the separation method of cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 1, it is characterized in that, in step (1) and step (2.2), the vacuum tightness of described concentrating under reduced pressure is 700 – 1000mbar, and the bath temperature that concentrating under reduced pressure adopts is 25-45 ° of C; In step (3), the vacuum tightness of described vacuum distilling is 0.01-0.1mbar, and bath temperature is 25-45 ° of C.
4. the separation method of cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 1, is characterized in that, in step (2), described acid solution is sulphuric acid soln; In described sulphuric acid soln, the mass percent concentration of acid is 1-20%; In step (2.2), described alkali lye is the aqueous solution of sodium hydroxide; In described aqueous sodium hydroxide solution, the mass percent concentration of alkali is 10-80%.
5. the separation method of cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 1, is characterized in that, in 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 step (3), before beginning to vacuumize, at first adopt the liquid nitrogen condensation collector to carry out condensation and collect, and till continuing to be condensed to experiment and finishing the final vacuum state and disappear;
In step (4), when adopting preparative chromatography to separate, condensation collection tube and continue to be condensed to fraction collection and finish at first before sample introduction is collected cut SF1-SF5 successively.
6. the separation method of cigarette smoke granule phase substance neutral and alkali flavour ingredient as claimed in claim 1, it is characterized in that, in step (4), the preparative gas chromatography post that adopts when adopting preparative gas chromatography 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 2-10%SE-30/chromsorb W-HP filler, and the order number of filler is the 60-80 order.
7. the application of the separation method that adopts the arbitrary described cigarette smoke granule phase substance neutral and alkali flavour ingredient of claim 1-6 in preparation cigarette shreds perfuming field.
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| CN103919267B (en) * | 2014-03-28 | 2016-01-20 | 广东中烟工业有限责任公司 | A kind of preparation method of novel tobacco goods |
| CN104522877B (en) * | 2014-12-06 | 2016-06-08 | 中国农业科学院烟草研究所 | A kind of method making low temperature cigarette raw material |
| CN104757703B (en) * | 2014-12-31 | 2019-04-23 | 贵州中烟工业有限责任公司 | A kind of tobacco distillate and its preparation and application |
| 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 |
| 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 |
| CN105929082B (en) * | 2016-07-14 | 2018-08-21 | 云南中烟工业有限责任公司 | A kind of method of Pyrazine and pyridine substance in separation determination 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 |
| CN114711455B (en) * | 2022-03-10 | 2022-12-23 | 浙江中烟工业有限责任公司 | Preparation method and application of alkaline flavor components with characteristics of Canadian tobacco smoke |
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| CN102326859A (en) * | 2011-06-30 | 2012-01-25 | 红云红河烟草(集团)有限责任公司 | Method for extracting tobacco essence perfume from cigarette processing waste gas |
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