CN106376970A - Additive for reducing harmful substances in mainstream smoke of cigarette as well as preparation method and application thereof - Google Patents
Additive for reducing harmful substances in mainstream smoke of cigarette as well as preparation method and application thereof Download PDFInfo
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- CN106376970A CN106376970A CN201610920400.3A CN201610920400A CN106376970A CN 106376970 A CN106376970 A CN 106376970A CN 201610920400 A CN201610920400 A CN 201610920400A CN 106376970 A CN106376970 A CN 106376970A
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- acid
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- flue gas
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/287—Treatment of tobacco products or tobacco substitutes by chemical substances by inorganic substances only
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention provides an additive for reducing harmful substances in the mainstream smoke of cigarette as well as a preparation method and application thereof. According to the invention, titanate is added into tobacco as an additive; and the structural formula of titanate is MxTiOLy.nH2O, wherein M is lithium, sodium, potassium, magnesium, calcium, aluminum, zinc or mixed component; L is citric acid, carbonic acid, malic acid, oxalic acid, formic acid, acetic acid, malonic acid, succinic acid, adipic acid, butenedioic acid or corresponding mixed component; x and y are 1-4; and n is 2-10. The additive provided by the invention is water soluble and has the functions of combustion adjustment and oxidation catalysis and can effectively reduce the release of hydrogen cyanide, NH3 and crotonaldehyde in smoke so as to reduce the harm to a human body caused by harmful components in the smoke.
Description
Technical field
The invention belongs to Tar field, specifically, it is related to a kind of titanate and preparation method and purposes, lead to
Cross the difunctional of the combustionregulator that this titanate has and catalyst, reduce harmful components burst size in cigarette mainstream flue gas.
Background technology
With the pay attention to day by day to " smoking and health " problem, the harmful components reducing in cigarette mainstream flue gas have become phase
One of pass industry focus of attention.
For in 7 kinds of main flumes such as carbon monoxide, hydrocyanic acid, nitrosamine, ammonia, benzopyrene, phenol and crotonic aldehyde
Main harmful components, employ in industry and add additivated method in Nicotiana tabacum L., by chemistry such as absorption, combustion-supporting and catalysis
Tar reduction acts on, and reduces the content of above-mentioned harmful components.But being subtracted using generally existing of the combustionregulator such as traditional potassium acetate
Evil effect undesirable it is impossible to meet the requirement of the Harm reduction techniques tar reduction of increasingly stringent, simultaneously too much using additive to affect
The aesthetic quality of Medicated cigarette.
The new material that predecessors such as the titanate of titanium dioxide and correlation etc. have catalysis oxidation function can be effectively
The smoke components such as oxidizing carbon monoxide, nitrosamine, phenol, crotonic aldehyde, therefore to study it as additive and to subtract in tar reduction
The effect of evil aspect also becomes study hotspot.CN204519347U discloses one kind and receives in acetate fiber section interpolation solid-state titanate
Rice noodle, thus the method that forms binary compound filter candle, significantly reduces the content of nitrosamine.CN104805730A discloses one
Plant method solid titania being added in cigarette paper, by catalytic action, when sucking Medicated cigarette, effectively reduce an oxygen
Change the content of carbon.But these materials are solid it is impossible to be dissolved in water so that it is added directly to cigarette as additive due to it
The weakness such as there is easy blocking pipeline during leaf, cannot uniformly spray.Therefore, find the soluble additive containing titanium to realize dropping
Burnt harm reduction is the problem of common concern in current industry.
The carboxylic acid titanate of the metals such as potassium, sodium, because it has two kinds of metals and two kinds of ions simultaneously, is subject to more and more
To concern.This kind of material has the component similar to the metal carboxylate combustionregulator such as potassium acetate in itself, and have can be in Medicated cigarette again
The titanate component of the titanium dioxide with catalysis activity is generated in combustion process.Various metals cation and acid anion
Coexist and ensure that material has higher catalytic performance, also ensure that high-dissolvability in water for the additive.Add with respect to other
Plus agent, these carboxylic acid titanates just have very high active component ratio it is ensured that less additive addition.Therefore, non-
Often it is necessary this application in terms of Tar for class material systematically to be studied and inquires into.
Content of the invention
The invention provides a kind of additive reducing cigarette mainstream flue gas harmful substance and its preparation method and application.
The additive of the reduction cigarette mainstream flue gas harmful substance that the present invention provides is using titanate as tobacco additive agent,
During cigarette smoking, can optionally reduce the burst size of harmful constituents in cigarette flue gas, thus reducing harmful in flue gas
The harm to human body for the composition.
The additive of the reduction cigarette mainstream flue gas harmful substance that the present invention provides, is to be added using titanate as additive
In Nicotiana tabacum L., selected titanate structural formula is defined as MxTiOLy.nH2O.Described M be preferably lithium, sodium, potassium, magnesium, calcium,
Aluminum, zinc or mixed composition；L be preferably citric acid, carbonic acid, malic acid, oxalic acid, formic acid, acetic acid, malonic acid, succinic acid, oneself two
Acid, butene dioic acid or corresponding mixed composition.The value of x, y is preferably 1-4, and most preferably 2.N value is preferably 2-10, more preferably
4-8.
Described titanate is preferably based on the titanate K of potassium and oxalic acidxTiO(OOC-COO)y.nH2O.The value of x, y is preferably
1-4, most preferably 2.N value is preferably 2-10, more preferably 4-8.
The preparation method optimal technical scheme of additive of the present invention includes：The titanium hydroxide solid of brand-new is added to dissolved with grass
In the hot solution of acid, the hot solution mesoxalic acid percentage by weight of the oxalic acid being used is 5-10%, and guarantees the hydroxide added
Titanium percentage by weight in the solution is 5-8%；It is heated to reflux and stirs, form the solution of clarification；State then up in solution
Add potassium oxalate saturated aqueous solution it is ensured that this solution mesoxalic acid potassium is 0.5-2 with the mass ratio of the titanium hydroxide being initially added:1,
After solution is sufficiently mixed, sucking filtration concentrates, and so that crystal is separated out, obtains potassium titanyl oxalate crystal.
Described titanate is dissolved or dispersed in water or alcohol solvent as additive and passes through with spray, dipping or note
The method penetrated adds in Nicotiana tabacum L..Wherein titanate mass content in the solution is 0.1%～15%.
Metatitanic acid salt additives together can be added with other humectation type additives and flavored type additive.
In every Medicated cigarette, contained titanate accounts for Medicated cigarette percentage by weight is 0.01%～1%.
As described above, the present invention uses a kind of titanate to be used as tobacco additive agent, after being added into Nicotiana tabacum L., can effectively drop
The burst size of hydrocyanic acid, ammonia, crotonic aldehyde etc. in low main flume, reaches as high as 12%, and the different amount added is to being harmful to into
Divide reduction rate also different.The cigaret additive safety non-toxic of the present invention, low cost, preparation method is simple and yield is high, suitable work
Industry metaplasia is produced.
Brief description
Fig. 1 is the x-ray diffractogram of powder of titanate.
Fig. 2 is the thermogravimetric curve figure of titanate.
Fig. 3 is the scanning electron microscope (SEM) photograph of the tobacco sample local that with the addition of titanate.
Specific embodiment
The present invention will be further described with embodiment as follows, but the scope of the invention be certainly not limited to these enforcement
Example.Following examples use following reagent and equipment
1st, reagent
Titanium hydroxide, oxalic acid, potassium oxalate, deionized water, dehydrated alcohol
2nd, equipment
(U.S. TA is public for D8ADVANCE type X-ray diffractometer (German Bruker company), SDT-Q600 thermogravimetric analyzer
Department), fly to receive Prox desk-top ESEM (Phenom company)
Embodiment one
Preparation method based on potassium and the titanate of oxalic acid is as follows：The titanium hydroxide solid of brand-new is added to dissolved with oxalic acid
In hot solution, the hot solution mesoxalic acid percentage by weight of the oxalic acid being used is 5%, and guarantees the titanium hydroxide adding in solution
In percentage by weight be 6.8%；It is heated to reflux and stirs, form the solution of clarification；State addition oxalic acid in solution then up
Potassium saturated aqueous solution is it is ensured that this solution mesoxalic acid potassium is 1.4 with the mass ratio of the titanium hydroxide being initially added:1, solution is abundant
After mixing, sucking filtration concentrates, and so that crystal is separated out, obtains potassium titanyl oxalate crystal.
Measure the crystalline phase of the potassium titanyl oxalate obtaining in embodiment one using X-ray diffractometer, specific measurement result is shown in
Fig. 1.Spectrogram display diffraction peak shape is sharp, and diffracted intensity is also very high, and synthesized sample crystallization is fine.
Above-mentioned potassium titanyl oxalate sample is heated in air atmosphere, by SDT-Q600 thermogravimetric analyzer record not
Synthermal corresponding sample weight loss curve.See Fig. 2.
The thermogravimetric curve of potassium titanyl oxalate presents typical two step pyrolysis.First step weightlessness is made by losing of water of crystallization
Become, it starts second step weightlessness at 350 degree about, ultimately produces potassium oxide and titanium dioxide.Illustrate at a temperature of cigarette burning,
Unharmful substance produces, and above-mentioned product nor affects on the sense organ of Medicated cigarette.
Embodiment two
Preparation method based on sodium and the titanate of oxalic acid is as follows：The titanium hydroxide of brand-new is added to the thermosol dissolved with oxalic acid
In liquid (percentage by weight in this solution for the oxalic acid is 5%, and the percentage by weight of titanium hydroxide is 6.8%), it is heated to reflux simultaneously
Stirring, forms the solution of clarification.State then up and add the saturated hot-water solution of Disodium oxalate. in solution it is ensured that solution mesoxalic acid sodium
Mass ratio with the titanium hydroxide being initially added is 1.13:1.After being sufficiently mixed, it is kept stirring for 30 minutes.By above-mentioned solution sucking filtration
After concentrate.Gained crystal obtains the titanate Na based on sodium and oxalic acid after drying2TiO(OOC-COO)2.2H2O.
Embodiment three
Preparation method based on potassium and the titanate of malonic acid is as follows：The titanium hydroxide (IV) of brand-new is added to dissolved with the third two
The hot solution (percentage by weight in this solution for the malonic acid is 5.8%, and the percentage by weight of titanium hydroxide is 6.8%) of acid
In, it is heated to reflux and stirs, form the solution of clarification.State the saturated aqueous solution adding malonic acid potassium in solution then up, really
Protecting malonic acid potassium and the mass ratio of the titanium hydroxide being initially added in solution is 1.52:1.After being sufficiently mixed, it is kept stirring for 30 points
Clock.By evaporation and concentration after above-mentioned solution sucking filtration.So that crystal is separated out after adding ethanol, after filtration, use washing with alcohol crystal, after being dried
Obtain the titanate K based on potassium and malonic acid2TiO(OOCCH2COO)2.4H2O.
The titanate sample containing potassium and oxalic acid synthesized by Example one, with spray, impregnates Nicotiana tabacum L. or directly toward volume
The method of cigarette injection adds the aqueous solution of potassium titanyl oxalate on tobacco sample.In the aqueous solution being used, the content of titanate is
2-15g every 100g water.The percentage by weight that the potassium titanyl oxalate being added accounts for Nicotiana tabacum L. is 0.01%～1%.
Example IV
By deposition conditions on Nicotiana tabacum L. for the scanning electron microscopic observation potassium titanyl oxalate.Scanning electron microscope used is
PhenomProx desk-top ESEM, by untreated for tobacco sample direct observation.Specific electromicroscopic photograph is shown in Fig. 3.
It can be seen that titanate is successfully attached on Nicotiana tabacum L. under scanning electron microscope.When concentration is higher, the shape of attachment sample
Looks are essentially corynebacterium, simultaneously the also bigger granule with the presence of Part-spherical.When concentration is relatively low, it is possible to achieve titanate exists
It is evenly distributed in Nicotiana tabacum L..
The photo of scanning electron microscope also illustrates to regulate and control titanate sample by adjusting the concentration adding titanate sample
The mass percent of deposition in Nicotiana tabacum L..
Further look at the size learning metatitanic acid salt particle in 1-5 microns, do not observe the sign of concentration of local.
The Medicated cigarette propping up for potassium titanyl oxalate 1mg/, flue gas inspection the results are shown in Table 1.
The testing result of 1 seven kinds of index smoke components of table.
Above testing result it can be seen that：
1st, hydrogenation cyanogen, NH3, crotonaldehyde release amount reduce
Compared with comparison Nicotiana tabacum L., the hydrogenation cyanogen burst size in test Nicotiana tabacum L. flue gas reduces by 11.6%, NH3Burst size reduces
12.4%, crotonaldehyde release amount reduces by 11.2%.
2nd, harm sex index reduces
Compared with comparison Nicotiana tabacum L., the overall harm sex index of test Nicotiana tabacum L. flue gas reduces by 7.6%.
Result of the test shows, the titanate such as potassium titanyl oxalate is harmful to during reducing cigarette smoking as Nicotiana tabacum L. additive
The burst size of composition.This kind of material has the difunctional of combustionregulator and oxidation catalyst, and is easy in process of production
Add in form of an aqueous solutions.
The foregoing is only the exemplary embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, the modification made, replacement, improvement etc., should be included in protection scope of the present invention.
Claims (10)
1. a kind of additive reducing harmful substance in cigarette mainstream flue gas is it is characterised in that described additive is metal metatitanic acid
Salt, structural formula is defined as MxTiOLy·nH2O.
2. as claimed in claim 1 a kind of additive reducing harmful substance in cigarette mainstream flue gas it is characterised in that described
M be lithium, sodium, potassium, magnesium, calcium, aluminum, zinc or mixed composition；L is citric acid, carbonic acid, malic acid, oxalic acid, formic acid, acetic acid, the third two
Acid, succinic acid, adipic acid, butene dioic acid or corresponding mixed composition；The value of x, y is 1-4, and n value is 2-10.
3. as claimed in claim 2 a kind of additive reducing harmful substance in cigarette mainstream flue gas it is characterised in that described
X, y value is 4-8 for 2, n value.
4. as claimed in claim 1 a kind of additive reducing cigarette mainstream flue gas harmful substance it is characterised in that described gold
Genus titanate is KxTiO(OOC-COO)y·nH2The value of O, x, y is 1-4,.It is preferably 2.N value is 2-10, more preferably 4-8.
5. as claimed in claim 4 a kind of additive reducing cigarette mainstream flue gas harmful substance it is characterised in that described x,
The value of y is 4-8 for 2, n value.
6. as a kind of preparation method of described reduction cigarette mainstream flue gas harmful substance additive arbitrary in claim 1-5,
It comprises the steps：The titanium hydroxide solid of brand-new is added to the thermosol dissolved with the oxalic acid in the hot solution of oxalic acid, being used
Liquid mesoxalic acid percentage by weight is 5-10%, and guarantees that the titanium hydroxide adding percentage by weight in the solution is 5-8%；Plus
Hot reflux is simultaneously stirred, and forms the solution of clarification；State then up and add potassium oxalate saturated aqueous solution in solution it is ensured that in this solution
Potassium oxalate is 0.5-2 with the mass ratio of the titanium hydroxide being initially added:1, after solution is sufficiently mixed, sucking filtration concentrates, and makes crystal
Separate out, obtain potassium titanyl oxalate crystal.
7. as a kind of preparation method of described reduction cigarette mainstream flue gas harmful substance additive arbitrary in claim 1-5,
It comprises the steps：The titanium hydroxide solid of brand-new is added to the thermosol dissolved with the oxalic acid in the hot solution of oxalic acid, being used
Liquid mesoxalic acid percentage by weight is 5%, and guarantees that the titanium hydroxide adding percentage by weight in the solution is 6.8%；Heating
Flow back and stir, form the solution of clarification；State then up and add potassium oxalate saturated aqueous solution in solution it is ensured that this solution medium-height grass
Sour potassium is 1.4 with the mass ratio of the titanium hydroxide being initially added:1, after solution is sufficiently mixed, sucking filtration concentrates, and so that crystal is separated out,
Obtain potassium titanyl oxalate crystal.
8. the application process of the additive preparing as described preparation method arbitrary in claim 1-7 it is characterised in that
Titanate is dissolved in water or ethanol solution, by being added in Nicotiana tabacum L. with the method for spray, dipping or injection.
9. application process as described in claim 8 is it is characterised in that wherein titanate mass percent in the solution contains
Measure as 0.1%～15%.
10. application process as claimed in claim 8 or 9 it is characterised in that in every Medicated cigarette this additive contained account for Medicated cigarette weight
Amount percentage ratio is 0.01%～1%.
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| CN201610920400.3A CN106376970A (en) | 2016-10-21 | 2016-10-21 | Additive for reducing harmful substances in mainstream smoke of cigarette as well as preparation method and application thereof |
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| CN201610920400.3A CN106376970A (en) | 2016-10-21 | 2016-10-21 | Additive for reducing harmful substances in mainstream smoke of cigarette as well as preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109171001A (en) * | 2018-09-14 | 2019-01-11 | 上海烟草集团有限责任公司 | Application of the sodium oxalate in reducing cigarette smoke in TSNAs burst size |
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