CN1167364C - Cigarette combustion-supporting and harm-reducing adidtive with nano pores - Google Patents
Cigarette combustion-supporting and harm-reducing adidtive with nano pores Download PDFInfo
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- CN1167364C CN1167364C CNB011340843A CN01134084A CN1167364C CN 1167364 C CN1167364 C CN 1167364C CN B011340843 A CNB011340843 A CN B011340843A CN 01134084 A CN01134084 A CN 01134084A CN 1167364 C CN1167364 C CN 1167364C
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- cigarette
- props
- content
- nitrosamines
- pipe tobacco
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Abstract
The present invention relates to cigarette additives and a purpose thereof. The cigarette additives can obviously reduce nitrosamine content in the smoke of cigarettes and/or promote the combustion of the cigarettes and are particles with porous materials, such as KA zeolize, etc. suspended in even colloid solution, particularly 3A zeolize which is the particle with porous materials with the grain diameters of 2 to 5 um m and the hole diameters of about 0.3 nanometer, which comprises potassium ions and other alkali metal ions. The cigarette additives of the present invention are sprayed on cut tobacco with the quantity of 0.5 to 10% of the weight of the cut tobacco and are dried in the air for producing cigarettes. The combustion time of the cigarettes in passive burning and inhaling burning can be respectively shortened by 5 to 12% and 20 to 26%, and nitrosamine content in the smoke is reduced by 23 to 33% and 43 to 63%, so that the pollution of smoking to environments is reduced greatly.
Description
One, technical field
The present invention relates to the tobacco shred additive and the application thereof of cigarette.Especially content of nitrosamines in the cigarette smoke be can significantly reduce and the additive and the application thereof of cigarette burning promoted
Two, background technology
Cigarette burning produces main flow and side-stream smoke.Main flume is meant that cigarette inhaled the flue gas that when combustion, the logical filter tip of smoker suck the oral cavity, and side-stream smoke is meant that cigarette props up spontaneous firing when promptly glowing, is directly released into airborne flue gas.Contained N-nitroso compound in the cigarette smoke (is representative with the nitrosamine) has strong carcinogenicity.Nitrosamine in the main flume directly endangers smoker's health, and cigarette side-stream smoke directly intersperses among among the crowd, and contaminated environment also injures involuntary smoker's health, so how cigarette falls evil and become problem demanding prompt solution in the ecological protection.
Foreign patent US19990166413P uses carbonate solution rinsing tobacco leaf, can reduce the content of nitrosamines in the blade after airing all around; This method treatment process complexity not only will expend a large amount of alkali and influence the cigarette taste, and may cause secondary pollution for environment.Patent EP0991329 uses microwave or high frequency radiation to handle tobacco leaf to reduce NNK and the NNN in the cigarette, the direct radiation treatment finished cigarettes of patent CN 1269992 usefulness microwaves, patent US2001000386 employing electrical heating contact current downflow processing sheet cigarette with heat-exchanging method in NO2 atmosphere and reduce tobacco-specific nitrosamine (TSNA).These methods may cause pipe tobacco to glow, and all exist certain risk in industrial applications.Use filter stick, comprise that the filter tip (as patent CH-A-653200, UA-A-3703901, FR-A-2165174, WO9607335 and WO9704865) of admixture zeolite all is difficult to selectively remove NOC, more can not solve the pollution problem of passive smoking.Patent JP6214772 adopts menthol, ascorbic acid, aminoacetic acid, stearic acid, lecithin and benzoic acid, 4-hydroxyl-3-methoxylbenxaldehyde etc. to make the adsorbent of tar, can reduce the content of flue gas nicotine, CO, benzo [α] pyrene and nitrosamine when being used for the fire end of cigarette.This method is the cost height not only, because it only has suction-operated, so effect is not remarkable.
Patent EP0740907 is the Y of 0.5-0.7nm with the aperture, X, ZSM-5, micro-pore zeolite such as M and β and gel (C-Gel) mix among the LC-674, be sprayed on cigarette on the pipe tobacco after forming suspension, the harmful components in combustion process in the catalytic elimination cigarette smoke comprise nitrosamine.But descend as nitrosonornicotine (NNN), nitroso anabasine (NAB) equal size in the nitrosamine, the content of dimethylnitrosamine (NDMA) but has rising.Whether the nitrosamine total amount that does not offer some clarification in this patent in cigarette master, the side-stream smoke is significantly reduced, and because the desired additives amount is excessive, causes cost to rise.Patent CN1228945 disclose a kind ofly utilize porous particulate material such as 4A zeolite to make suspension colloid solution, spray is added on the pipe tobacco new method that reduces content of nitrosamines in the cigarette, but its pore diameter range is confined to 0.4nm, and does not have combustion-supporting effect.
Three, summary of the invention
The purpose of this invention is to provide and a kind ofly have combustion-supporting simultaneously and reduce the cigarette additive of content of nitrosamines in the cigarette smoke, and the purposes of this additive, promptly contain the cigarette of this additive.
Technical scheme of the present invention is as follows: a kind of cigarette additive that reduces content of nitrosamines in the cigarette smoke, selecting its particle diameter for use is porous particulate material 3A zeolite about 4 μ m, about the 0.3nm of its aperture, contains alkali metal ions such as potassium ion.The preferential porous particulate material that uses is a potassium type A zeolite, and particle diameter is about 4 μ m.It is to suspend to use in the solution of biogum such as algin or cyclodextrin, can also be the solid mechanical mixture.The addition of porous particulate material is preferably the 1-5% of pipe tobacco weight.
The purposes of cigarette additive and method for making are among the present invention: (ratio is 1: 75-1: 400 in room temperature adding cold water with algin, the present invention adopted 1: 200), soak 0.1-1.0 hour (the present invention adopted 0.25 hour more) earlier, be heated to 30-100 ℃ (the present invention adopts 40-50 ℃) more again and keep 0.1-1.0 hour (the present invention adopted 0.25 hour) more, become transparent adhesive solution after being chilled to room temperature.Add the porous particulate material of amount of calculation, stir into uniform suspension, promptly obtain cigarette additive of the present invention.
The method for making that is used for cigarette of reduced content of nitrosamines in its flue gas of the present invention, be that amount by the cigarette additive of the algin of pipe tobacco or tobacco leaf weight 0.05-1.0% and 0.5-9.0% porous particulate material evenly is sprayed on pipe tobacco or the tobacco leaf, dry, make cigarette, promptly obtain the new cigarette of reduced content of nitrosamines in the flue gas.
Being added in the sol solution as the 3A mano-porous material of main additive component, is representative with the KA zeolite.
The A type is zeolite structured to be the three-dimensional crystalline structure that interconnects with four oxo bridges by four-membered ring with between the β cage, after being interconnected by 8 β cages, forms a α cage again in the middle of them; It is the oikocryst cave of A type zeolite, includes exchangeable cations, when cation is potassium ion K
+, then be called KA type zeolite, because its effective aperture is 3 (0.3nm), be called the 3A zeolite again again, its desirable structure cell consists of: K
96[Al
96Si
96O
384] 216H
2O or K
12[Al
12Si
12O
48] 27H
2O.Chemical formula can be written as K
2OAl
2O
32SiO
24.5H
2O, the pore passage structure of KA zeolite is the three-dimensional straight duct, and contains maximum exchangeable cations, can be carried out ion-exchange fast and in large quantities.Its specific surface is 700m
2About/g, particle diameter is about 4 μ m, general 2-5 μ m.Cation also can be to contain other alkali metal ion, as sodium, magnesium, calcium etc.
Characteristics of the present invention such as following: (1) (refers to biogum and KA zeolites such as algin or cyclodextrin at total addition level, do not comprise water) for about 3wt.%, just can obviously reduce the content of nitrosamines in the cigarette smoke and improve the cigarette burning situation, tangible combustion-supporting effect is promptly arranged.(2) to adopt the aperture be zeolite molecular sieve material about 0.3nm to the solia particle in the additive, and EP0740907 is 0.5-0.7nm for the scope of patent protection of zeolite pore, and CN1228945 is 0.4nm.What (3) measure is that cigarette is being inhaled under the combustion and the situation of glowing the apparent total amount of the nitrosamine in its flue gas respectively.
Four, the specific embodiment
Embodiment:, from cigar mill's primary processing line, take out the semi-finished product pipe tobacco for the treatment of cigarette the cut tobacco storing cabinet for detecting the removal effect of cigarette additive of the present invention for content of nitrosamines in the cigarette smoke; Spray cigarette additive of the present invention to this pipe tobacco, dry, then with obbbin cigarette again.The pipe tobacco that does not spray cigarette additive of the present invention is through handling to compare equally.
The present invention adopts Caldwell at J.Assoc.Off.Anal.Chan., and the apparatus and method of 73 (5), 783,1990 reports are collected side-stream smokes, is 150mL citric acid-disodium hydrogen phosphate buffer solution of 4.5 but change its absorption liquid into the pH value.In order to observe combustion-supporting effect more accurately, the sample cigarette keeps glowing in tapered burner, and air is in advance through super-dry in the combustion process, and flow velocity is 1L/ minute.Behind burner made mid point combustion cigarette, (four absorption tubes are adorned 15mL Na for every to absorb flue gas by absorption tube with flue gas
2HPO
4-citrate buffer solution), 4 of concurrent combustions (every burnt about 20 minutes).Add about 2 gram sodium chloride in the gained buffer solution, divide four extractions with the 240mL carrene again.Extract filters by the funnel that anhydrous sodium sulfate is housed, and the extract after the filtration is concentrated into 25mL with Rotary Evaporators (about 32 ℃ of bath temperature, vacuum is 0.03MPa).Select the rub oral examination tube of a band arm, have one on the grinding port plug of outfit and pass to the pipe wireway at the end.Put 10mL nitrosamine solution in test tube, add 0.5mL HBr/HOAc solution again, filled in grinding port plug.In reactant liquor, feed high-purity N by wireway
2, and lasting 30min, N
2Flow be 200mL/min.The NO that nitrosamine N-N bond fission produces is through N
2Blow off behind the solution, filling 10mL concentration respectively by three is that the Drexel bottle of the NaOH solution of 5mol/L purifies, and is oxidized into NO through the chromium trioxide oxidation tube again
2, be converted into NO by sulfanilamide (SN)-hydrochloride naphthodiamide absorption liquid collection
2 -And the generation chromogenic reaction, measure absorbance A then in the 540nm place.By NaNO
2Concentration～absorbance calibration curve is converted into the content of nitrosamine.
The present invention adopts Miyake at J.Chromatogr.A, and 1995, the apparatus and method of 693:376 report are collected main flume: place 150mL Na in the 1000mL separatory funnel
2HPO
4-citrate buffer solution, bleeding with pump makes separatory funnel top be evacuated to 1.3kPa, stablizes 10 minutes.Light a cigarette, the flue gas that makes cigarette inhale the combustion generation passes through Na
2HPO
4-citrate buffer solution is absorbed, 30 of cofirings.Add about 2 gram sodium chloride in the gained buffer solution, divide four extractions with the 240mL carrene again, extract filters by the funnel that anhydrous sodium sulfate is housed, and the extract after the filtration is concentrated into 25mL with Rotary Evaporators (about 32 ℃ of bath temperature, vacuum is 0.03MPa).The processing method of gained solution is the same.
Cigarette smoke is collected nitrosamine Determination on content in the liquid, and the inventor adopts the disclosed improvement AAS of CN1193741.
[example 1] (special chemical experimental factory, Tianjin produces with the 0.1051g algin, dissolve in the 20ml water down together), be heated to 40-50 ℃, dissolving, add 6.0g KA zeolite (inorganic chemical industry factory in Nanjing produces, down together) after being chilled to room temperature again, stir into pipe tobacco A (Yunnan Province's product fire-cured tobacco type that uniform suspension is sprayed on 200g, tar content is 15mg, and nicotine content in smoke is 1.2mg) on; Dry back pipe tobacco color and luster is constant.Be rolled into and light after cigarette props up, collect flue gas and analyze its content of nitrosamines.In the main flume when inhaling combustion, content of nitrosamines props up from 2.01nmol/ and is reduced to 0.67 μ g/ and props up, and reduces 54.1%; Burning time by 45 seconds/be reduced to 35 seconds/, descend about 22%.Glow content of nitrosamines in the flue gas of cigarette props up from 29.25nmol/ and is reduced to 17.98 μ g/ and props up, and reduces 27.5%; The time of glowing was reduced to 19 minutes/props up decline 5% by 20 minute/.
[example 2] dissolves in the 0.1056g algin in the 20ml water, is heated to 40-50 ℃, and dissolving is chilled to and adds the 12.0gKA zeolite after the room temperature.Stirring into uniform suspension is sprayed on the pipe tobacco A of 200g; Dry back pipe tobacco color and luster is constant.Be rolled into and light after cigarette props up, collect flue gas and analyze its content of nitrosamines.In the main flume when inhaling combustion, content of nitrosamines props up from 2.01nmol/ and is reduced to 0.61nmol/ and props up, and reduces 58.2%; Burning time by 45 seconds/foreshorten to 35 seconds/, reduce about 22%.Glow content of nitrosamines in the flue gas of cigarette props up from 29.25nmol/ and is reduced to 12.77nmol/ and props up, and reduces 29.0%.The time of glowing foreshortened to 19 minutes/props up minimizing 5% by 20 minute/.
[example 3] dissolves in the 0.3009g algin in the 60ml water, is heated to 40-50 ℃, and dissolving is chilled to and adds the 18.0gKA zeolite after the room temperature.Stirring into uniform suspension is sprayed on the pipe tobacco A of 200g; Dry back pipe tobacco color and luster is constant.Be rolled into and light after cigarette props up, collect flue gas and analyze its content of nitrosamines.In the main flume when inhaling combustion, content of nitrosamines props up from 2.01nmol/ and is reduced to 0.56nmol/ and props up, and reduces 61.6%.Burning time by 45 seconds/foreshorten to 32 seconds/, reduce about 29%.Glow content of nitrosamines in the flue gas of cigarette props up from 29.25nmol/ and is reduced to 12.5nmol/ and props up, and reduces 30.5%.The time of glowing foreshortened to 18 minutes/props up minimizing 10% by 20 minute/.When adding 2.0g K and 3.0g A zeolite respectively with above-mentioned condition, the minimizing of burning time slightly reduces by 1.
[example 4] dissolves in 1.0g β-CD (beta-cyclodextrin) in the 20ml water, is heated to 40-50 ℃, is dissolved to clarification, is chilled to add 6.0g KA zeolite after the room temperature again.Stirring into uniform suspension is sprayed on the pipe tobacco A of 200g; Dry back pipe tobacco color and luster is constant.Be rolled into and light after cigarette props up, collect flue gas and analyze its content of nitrosamines.In the main flume when inhaling combustion, content of nitrosamines props up from 2.01nmol/ and is reduced to 0.53nmol/ and props up, and reduces 63.7%.Burning time by 45 seconds/foreshorten to 35 seconds/, reduce about 22%.Glow content of nitrosamines in the flue gas of cigarette props up from 29.25nmol/ and is reduced to 12.04nmol/ and props up, and reduces 33.0%.The time of glowing foreshortened to 19 minutes/props up minimizing 5% by 20 minute/.
[example 5] on the pipe tobacco A of 100g, is rolled into 3.0g KA zeolite mechanical mixture to light after cigarette props up, and collects flue gas and analyzes its content of nitrosamines; The content of nitrosamines that glows in the flue gas props up from 29.25nmol/ and is reduced to 26.59nmol/ and props up, and has been reduced 9.1%.1.0g the similar effect that is added with 5g KA zeolite.
[example 6] dissolves in the 0.1021g algin in the 20ml water, is heated to 40-50 ℃ of dissolving, is chilled to add 12.0g KA zeolite after the room temperature again.Stirring into uniform suspension is sprayed on the pipe tobacco B (Yunnan Province produces fire-cured tobacco type, and tar content is 15mg, and nicotine content in smoke is 1.2mg) of 200g; Dry back pipe tobacco color and luster is constant.Be rolled into and light after cigarette props up, collect flue gas and analyze its content of nitrosamines.In the main flume when inhaling combustion, content of nitrosamines props up from 1.88nmol/ and is reduced to 0.83nmol/ and props up, and reduces 55.9%.Burning time by 45 seconds/foreshorten to 35 seconds/, reduce about 22%.Glow content of nitrosamines in the flue gas of cigarette props up from 22.66nmol/ and is reduced to 14.82nmol/ and props up, and reduces 32.5%.The time of glowing foreshortened to 16.5 minutes/props up minimizing 12.5% by 20 minute/.
[example 7] dissolves in the 0.046g algin in the 9.2ml water, is heated to 40-50 ℃, and dissolving is chilled to and adds the 2.76gKA zeolite after the room temperature.Stirring into uniform suspension is sprayed on the pipe tobacco C (Korea S produces, burley tobaccos) of 92g; Dry back pipe tobacco color and luster is constant.Be rolled into and light after cigarette props up, collect flue gas and analyze its content of nitrosamines; The content of nitrosamines that glows in the flue gas props up from 50.9nmol/ and is reduced to 39.1nmol/ and props up, and reduces 23.2%.
[example 8] dissolves in the 0.037g algin in the 7.4ml water, is heated to 40-50 ℃, and dissolving is chilled to the KA zeolite that adds 2.22g after the room temperature again, stirs into uniform suspension and is sprayed on 74g reconstituted tobacoo D (on (Korea S's product); Dry under the room temperature.Be rolled into and light after cigarette props up, collect flue gas and analyze its content of nitrosamines; The content of nitrosamines that glows in the flue gas props up from 25.23nmol/ and is reduced to 19.29nmol/ and props up, and reduces 23.5%.
Of the present invention combustion-supporting/remove the cigarette additive of nitrosamine in the flue gas, make simple and easy, with low cost.Adopt the made cigarette of additive of the present invention, it glows and the content of nitrosamines inhaled in the burning fume reduces 23-33% and 43-63%, burning velocity is obviously accelerated, can significantly reduce the pollution of smoking to environment, reduce the harm of cigarette for smoker and involuntary smoker's health, thereby can promote cigarette sale, for enterprise brings benefit.
Claims (4)
1, a kind of additive that can significantly reduce content of nitrosamines in the cigarette smoke and promote cigarette burning, it is characterized in that selecting for use particle diameter is the porous particulate material potassium type 3A zeolite of 2-5 μ m, about the 0.3nm of its aperture, described cigarette additive is the particulate that porous material is arranged that suspends in even colloidal solution.
2, the purposes of the described cigarette additive of a kind of claim 1 is characterized in that spraying the described additive of claim 1 on the pipe tobacco of cigarette, and the addition of porous particulate material is the 0.5-10.0% of pipe tobacco weight.
3,, it is characterized in that the addition of the porous particulate material that adds is the 0.02-1.0% of pipe tobacco weight in pipe tobacco according to the purposes of the described cigarette additive of claim 3.
4, according to the purposes of the described cigarette additive of claim 3, the addition that it is characterized in that porous particulate material is the 1-5% of pipe tobacco weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011340843A CN1167364C (en) | 2001-10-25 | 2001-10-25 | Cigarette combustion-supporting and harm-reducing adidtive with nano pores |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011340843A CN1167364C (en) | 2001-10-25 | 2001-10-25 | Cigarette combustion-supporting and harm-reducing adidtive with nano pores |
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| Publication Number | Publication Date |
|---|---|
| CN1375245A CN1375245A (en) | 2002-10-23 |
| CN1167364C true CN1167364C (en) | 2004-09-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011340843A Expired - Fee Related CN1167364C (en) | 2001-10-25 | 2001-10-25 | Cigarette combustion-supporting and harm-reducing adidtive with nano pores |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8578943B2 (en) * | 2005-12-20 | 2013-11-12 | Philip Morris Usa Inc. | Metal-containing nanowires prepared using mesoporous molecular sieves as templates, and their use in smoking articles for removing certain gas phase constituents from tobacco smoke |
| JP5339635B2 (en) * | 2007-07-23 | 2013-11-13 | アール・ジエイ・レイノルズ・タバコ・カンパニー | Smokeless tobacco composition and method of treating tobacco for using the same |
| CN101843360B (en) * | 2009-03-24 | 2012-10-10 | 湖北中烟工业有限责任公司 | Tobacco leaf laser drilling method capable of simultaneously reducing tar and CO in cigarettes |
| CN103892437B (en) * | 2014-03-28 | 2016-03-30 | 广东中烟工业有限责任公司 | A kind of production method of novel tobacco goods |
| CN104568562B (en) * | 2014-12-31 | 2017-12-29 | 中国地质大学（武汉） | The preprocess method of nitrosamine compound in a kind of water sample and its suspension |
| CN107319622A (en) * | 2017-06-29 | 2017-11-07 | 滁州卷烟材料厂 | A kind of processing and treating method of tobacco leaf |
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2001
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| CN1375245A (en) | 2002-10-23 |
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