CN101698483A - Lanthanum-doped mesoporous silica, preparation method and application thereof as additives of filter tip - Google Patents
Lanthanum-doped mesoporous silica, preparation method and application thereof as additives of filter tip Download PDFInfo
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- CN101698483A CN101698483A CN200910193518A CN200910193518A CN101698483A CN 101698483 A CN101698483 A CN 101698483A CN 200910193518 A CN200910193518 A CN 200910193518A CN 200910193518 A CN200910193518 A CN 200910193518A CN 101698483 A CN101698483 A CN 101698483A
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Abstract
The invention discloses lanthanum-doped (La-doped) mesoporous silica, a preparation method and an application thereof as the additives of a filter tip. The method for preparing the La-doped mesoporous silica comprises the following steps: (1) mixing laurylamine, ethanol and distilled water according to the mole ratio of 1:25-35:45-50 to obtain a solution A; (2) mixing La(NO3)3.6H2O, tetraethoxysilane (TEOS) and distilled water according to the mole ratio of 1:50-60:600-700 to obtain a solution B; (3) mixing and stirring the solution A and the solution B to obtain a mixed solution; and (4) sequentially subjecting the mixed solution obtained in step (3) to ageing treatment, washing treatment by distilled water, ethanol extraction and filtration, collecting and drying the precipitate, and calcining the dried sample to obtain the La-doped mesoporous silica. The method of the invention has the advantages of simple process and widely-obtainable and low-cost synthetic materials, and achieves good effect of removing the absorption of small-molecular substances of aldehydes and ketones in the smoke of cigarettes.
Description
Technical field
The invention belongs to cigarette holder additive technology field, be specifically related to reduce in the cigarette smoke technology of harmful small molecules aldoketones substances content, relate in particular to a kind of lanthanum-doped mesoporous silica and preparation method thereof and as the application in the additives of filter tip.
Background technology
Small molecules aldehyde ketone compound is one of principal pollutant in the atmosphere, studies show that both at home and abroad aldehyde compound has genetoxic, active aldehyde radical makes them to form adducts with the DNA covalent attachment, cause DNA interchain linkage, DNA splitting of chain etc., in addition, it still is the main component of photo-chemical smog.Therefore small molecules aldehyde ketone compound is listed in one of various countries' priority pollutant, and it is subjected to extensive concern to health effects always.
Contain group compounds of aldehydes and ketones in the cigarette smoke, mainly comprise 8 kinds low molecule aldehyde ketones of formaldehyde, acetaldehyde, acetone, propenal, propionic aldehyde, crotonic aldehyde (crotonaldehyde), 2-butanone and butyraldehyde etc., these all are objectionable impuritiess.
China is production of cigarettes and consumption big country, and the objectionable constituent content that reduces cigarette smoke is significant in the core competitiveness in World tobacco market to harm and raising China tobacco industry of numerous smokers' health for reducing smoking.
Filter tip is as the bridge between smoker and the main flume, and the part objectionable constituent in the energy filtering flue gas reduce tar content, reduce the harm of flue gas to HUMAN HEALTH and environment.But the effect of common filter tip reduction objectionable constituent is unsatisfactory.
At present a lot of to the research of cigarette filter material, mainly divide two aspects:
Be to adopt novel filter tip material on the one hand, make filter tip with conjugated fibre, porous mineral and natural phant etc.Though the type material filter tip can reduce the objectionable impurities in the cigarette, but water-soluble, biodegradable, can reduce pollution, but toxic substance content is gone back wide apart from alleviating smoking effectively to the harm of human body in the flue gas of processing back, also needs further development to environment.
Be that traditional filter tip material is improved on the other hand, mainly contain four direction: add absorbent charcoal material, add biological active materials (as oxyphorase etc.), add catalyzer (as precious metal etc.) and nanotechnology.Also there are relative merits separately in these four kinds of methods: the gac additive is more common, low price, but it is undesirable to fall burnt effect; Biological filter tip falls burnt effective, but less stable, and the cost height; It is more obvious that burnt effect falls in catalyzer, but cost an arm and a leg, and precious metal etc. has potential safety hazard to human body; The nano grain surface avtive spot is many, the chemical reaction contact surface is big, and have higher catalytic efficiency, but complex process, cost are higher, and during the suction, whether the nano material in the filter tip comes off and enters in the main flume still unknownly, so its use has limitation.
Meso pore silicon oxide material is the brand-new material system of rising in recent years, have that pore passage structure is regular, the aperture is adjustable continuously, specific surface area and characteristics such as pore volume is big, thermostability and chemical stability are good, thereby absorption with separate, field such as bulky molecular catalysis has a wide range of applications.Meso pore silicon oxide material has a variety of, as MCM-41, MCM-48, HMS, MSU and SBA etc.
Have not yet to see meso pore silicon oxide material is used for additives of filter tip, carry out the relevant report that toxic substance is removed in the cigarette smoke, also not seeing has the relevant report that meso pore silicon oxide material is used for the removal of aldoketones material.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of preparation method simple, easy to operate, can reduce the tar content in the cigarette smoke, especially the lanthanum-doped mesoporous silica of content of group compounds of aldehydes and ketones.
Another object of the present invention provides the preparation method of above-mentioned lanthanum-doped mesoporous silica.
Another object of the present invention provides the application of above-mentioned lanthanum-doped mesoporous silica as additives of filter tip.
Above-mentioned purpose of the present invention is achieved by following scheme:
A kind of lanthanum-doped mesoporous silica is the adulterated HMS of lanthanum (La-HMS).
HMS is the SiO 2 molecular sieve of hexagonal structure, synthetic by neutral surface active agent and neutral inorganics by hydrogen bond self-assembly approach, have bigger specific surface area, bigger pore volume and equal first-class characteristics of pore size, therefore the inventor selects HMS to be used for the present invention from multiple meso pore silicon oxide material, and discovery obtains good test effect, can significantly reduce the content of the aldoketones material in the cigarette smoke.
Lanthanum-doped mesoporous silica of the present invention is to prepare by the following method and get, and its concrete preparation process is as follows:
(1) with amino dodecane (DDA), ethanol and distilled water by 1: (25～35): be mixed with solution A after the mixed in molar ratio of (45～50);
(2) with La (NO
3)
36H
2O, tetraethoxy (TEOS) and distilled water are by 1: (50～60): be mixed with solution B after the mixed in molar ratio of (600～700);
(3) will obtain mixed solution after solution A and the solution B mixing stirring;
(4) ageing of step (3) gained mixed solution elder generation is handled, then distilled water wash, then use the alcohol extraction after-filtration, collecting precipitation carries out drying treatment, obtains lanthanum-doped mesoporous silica of the present invention (containing lanthanum hexagonal nano mesopore silicon oxide) after the dry gained sample calcining.
In the above-mentioned steps (3), the mixing churning time of solution A and solution B was at least 8 hours.
In the above-mentioned steps (4), the time that ageing is handled was at least 10 minutes.
In the above-mentioned steps (4), the time of alcohol extraction is for being at least 2 hours.
In the above-mentioned steps (4), collect alcohol extraction liquid and carry out drying treatment, drying temperature is 50～90 ℃, at least 2 hours time of drying.
In the above-mentioned steps (4), the temperature of calcination processing is 500～800 ℃, and calcination time was at least 2 hours.
Among the above-mentioned preparation method, the churning time of step (3), the ageing treatment time of step (4), alcohol extraction time, time of drying and calcination time, all adopt the describing mode of " at least " to provide minimum suitable time, then effect is bad to be lower than this minimum suitable time, just can realize the present invention as long as be higher than this minimum suitable time.Can consider that the time of selecting to be not less than minimum suitable time gets final product in conjunction with the time of concrete running cost and whole process of preparation in the time of practical application.
Among the above-mentioned preparation method, the mol ratio of amino dodecane and tetraethoxy is 1: (3～4).
The inventor with method for preparing gained lanthanum-doped mesoporous silica as additive, add in the cigarette filter, test its adsorption effect then to 8 kinds of common aldoketones substances content in the cigarette mainstream flue gas, simultaneously in contrast with the cigarette with filter tip that do not add lanthanum-doped mesoporous silica, found that in the cigarette smoke that is added with lanthanum-doped mesoporous silica of the present invention, the content of 8 kinds of common aldoketones materials all is starkly lower than and does not add lanthanum-doped mesoporous silica, illustrate that thus the inventive method prepares the gained lanthanum-doped mesoporous silica and has good tar adsorption effect, especially adsorb the effect of the harmful aldoketones material of small molecules.
The present invention compared with prior art has following characteristics:
1. mesoporous material has the duct of arranging long-range order, big specific surface, high porosity and narrowly distributing and continuously adjustable within the specific limits aperture, mesoporous aperture shows the performance of good material of main part to the bigger guest molecule of volume, mixes lanthanum and have higher catalytic efficiency later in the duct; The present invention utilizes these structural advantages of mesopore silicon oxide, and mesopore silicon oxide is used for the removal of cigarette smoke objectionable impurities, removes in particular for the absorption of small molecules aldoketones material, obtains good absorption removal effect;
2. preparation method of the present invention, its technology is simple, only need simply stir, washs and calcine;
3. preparation method of the present invention, its synthesis material (as ethanol and tetraethoxy etc.) source is abundant, low price, cost is low.
Description of drawings
Fig. 1 is the transmission electron microscope picture of embodiment 1 preparation gained lanthanum-doped mesoporous silica;
Fig. 2 is the graph of pore diameter distribution of embodiment 2 preparation gained lanthanum-doped mesoporous silicas;
Fig. 3 is the XRD figure of embodiment 3 preparation gained lanthanum-doped mesoporous silicas;
Fig. 4 is the nitrogen adsorption-desorption isotherm of embodiment 4 preparation gained lanthanum-doped mesoporous silicas.
Embodiment
Below in conjunction with specific embodiment the present invention is done description further, but specific embodiment is not done any qualification to the present invention.
Embodiment 1
Its preparation process of the lanthanum-doped mesoporous silica of present embodiment is as follows:
(1) is mixed with solution A with stirring after 10g amino dodecane, 90ml ethanol and the mixing of 50ml distilled water;
(2) with 1.5gLa (NO
3)
36H
2Stir after O, 44.6ml tetraethoxy (TEOS) and 40ml distilled water mix and be mixed with solution B;
(3) solution A and solution B mixing stirring were obtained mixed solution after 24 hours;
(4) ageing of step (3) gained mixed solution elder generation was handled 30 minutes, then use the 800ml distilled water wash, then use 600ml alcohol extraction 4 hours, it is following dry 4 hours to collect 80 ℃ of alcohol extraction liquids, at last the good sample of drying was calcined 4 hours under 640 ℃ in air, obtained lanthanum-doped mesoporous silica.
The transmission electron microscope picture that present embodiment prepares the gained lanthanum-doped mesoporous silica as shown in Figure 1, as can be seen from the figure, this lanthanum-doped mesoporous silica presents honeycomb or spongy, diameter is about 40～50nm, does not have tangible agglomerating particles.
Embodiment 2
Its preparation process of the lanthanum-doped mesoporous silica of present embodiment is as follows:
(1) is mixed with solution A with stirring after 8g amino dodecane, 90ml ethanol and the mixing of 50ml distilled water;
(2) with 1gLa (NO
3)
36H
2Stir after O, 44.6ml tetraethoxy (TEOS) and 40ml distilled water mix and be mixed with solution B;
(3) solution A and solution B mixing stirring were obtained mixed solution after 24 hours;
(4) ageing of step (3) gained mixed solution elder generation was handled 30 minutes, then use the 800ml distilled water wash, then use 600ml alcohol extraction 4 hours, it is following dry 4 hours to collect 80 ℃ of alcohol extraction liquids, at last the good sample of drying was calcined 6 hours under 640 ℃ in air, obtained lanthanum-doped mesoporous silica.
The graph of pore diameter distribution that present embodiment prepares the gained lanthanum-doped mesoporous silica as shown in Figure 2, as can be seen from the figure, the aperture of this lanthanum-doped mesoporous silica is about 2～4nm.
Its preparation process of the lanthanum-doped mesoporous silica of present embodiment is as follows:
(1) is mixed with solution A with stirring after 12g amino dodecane, 90ml ethanol and the mixing of 50ml distilled water;
(2) with 2gLa (NO
3)
36H
2Stir after O, 44.6ml tetraethoxy (TEOS) and 40ml distilled water mix and be mixed with solution B;
(3) solution A and solution B mixing stirring were obtained mixed solution after 24 hours;
(4) ageing of step (3) gained mixed solution elder generation was handled 30 minutes, then use the 800ml distilled water wash, then use 600ml alcohol extraction 4 hours, it is following dry 4 hours to collect 80 ℃ of alcohol extraction liquids, at last the good sample of drying was calcined 4 hours under 640 ℃ in air, obtained lanthanum-doped mesoporous silica.
The aperture that present embodiment prepares the gained lanthanum-doped mesoporous silica is about 2～4nm, the about 1000m of specific surface area
2g
-1
There is unique strong charateristic avsorption band in the XRD figure that present embodiment prepares the gained lanthanum-doped mesoporous silica when as can be seen from the figure interfacial angle is in 2=2.4 ° as shown in Figure 3, shows that this is a kind of typical mesoporous material.
Embodiment 4
Its preparation process of the lanthanum-doped mesoporous silica of present embodiment is as follows:
(1) is mixed with solution A with stirring after 10g amino dodecane, 90ml ethanol and the mixing of 50ml distilled water;
(2) with 1.52gLa (NO
3)
36H
2Stir after O, 44.6ml tetraethoxy (TEOS) and 40ml distilled water mix and be mixed with solution B;
(3) solution A and solution B mixing stirring were obtained mixed solution after 12 hours;
(4) ageing of step (3) gained mixed solution elder generation was handled 30 minutes, then use the 800ml distilled water wash, then use 600ml alcohol extraction 4 hours, it is following dry 4 hours to collect 80 ℃ of alcohol extraction liquids, at last the good sample of drying was calcined 4 hours under 460 ℃ in air, obtained lanthanum-doped mesoporous silica.
Nitrogen adsorption-desorption isotherm that present embodiment prepares the gained lanthanum-doped mesoporous silica as shown in Figure 4, this is a kind of typical VI type isothermal curve, and has H1 type hysteresis loop, its isothermal absorption branch is at relative pressure P/P
0Two flex points are successively arranged in=0.7-0.97 the scope, are rapid capillary condensation in the middle of the flex point.This is the capillary adsorption phenomena that typically has the mesopore molecular sieve of homogeneous duct distribution.
The absorption of aldoketones material test in embodiment 5 cigarette smokes
Present embodiment is selected embodiment 4 preparation gained lanthanum-doped mesoporous silicas, it is added in the cigarette filter as sorbent material, detect then by in the filter-tip cigarette smoke, the content of formaldehyde, acetaldehyde, acetone, propenal, propionic aldehyde, crotonic aldehyde (crotonaldehyde), 2-butanone and these 8 kinds of aldoketones materials of butyraldehyde, the result is as shown in table 1.
Simultaneously, present embodiment is got the cigarette that does not add lanthanum-doped mesoporous silica in the filter tip and is organized in contrast, also detect by in the filter-tip cigarette smoke, and the content of above-mentioned 8 kinds of aldoketones materials, the result is as shown in table 1.
Aldehyde ketone content in table 1 cigarette smoke (μ g/ props up)
As can be seen from Table 1, be added with the cigarette of lanthanum-doped mesoporous silica of the present invention in the filter tip, the content of 8 kinds of aldoketones materials is all less than not adding lanthanum-doped mesoporous silica in the filter tip in its flue gas content, the lanthanum-doped mesoporous silica that the inventive method preparation is described thus has the removal effect of aldoketones material absorption preferably, can be used as the additive of cigarette filter.
Claims (8)
1. the preparation method of a lanthanum-doped mesoporous silica, this method comprises the steps:
(1) amino dodecane, ethanol and distilled water are mixed with solution A after by 1: 25～35: 45～50 mixed in molar ratio;
(2) with La (NO
3)
36H
2O, tetraethoxy and distilled water are mixed with solution B after by 1: 50～60: 600～700 mixed in molar ratio;
(3) will obtain mixed solution after solution A and the solution B mixing stirring;
(4) ageing of step (3) gained mixed solution elder generation is handled, distilled water wash is then used the alcohol extraction after-filtration then, and the collecting precipitation thing carries out drying treatment, after dry gained sample is calcined, obtains lanthanum-doped mesoporous silica of the present invention.
2. according to the described preparation method of claim 1, the mol ratio that it is characterized in that described amino dodecane and tetraethoxy is 1: 3～4.
3. according to the described preparation method of claim 1, it is characterized in that in the described step (3), the mixing churning time of solution A and solution B was at least 8 hours.
4. according to the described preparation method of claim 1, it is characterized in that in the described step (4) that the time that ageing is handled was at least 10 minutes.
5. according to the described preparation method of claim 1, it is characterized in that in the described step (4), the time of alcohol extraction was at least 2 hours.
6. according to the described preparation method of claim 1, it is characterized in that in the described step (4) that collect alcohol extraction liquid and carry out drying treatment, drying temperature is 50～90 ℃, at least 2 hours time of drying.
7. according to the described preparation method of claim 1, it is characterized in that in the described step (4), the temperature of calcination processing is 500～800 ℃, calcination time was at least 2 hours.
8. the lanthanum-doped mesoporous silica of the described method of claim 1 preparation is as the application in the additive for filter tip of cigarette.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857235A (en) * | 2010-06-11 | 2010-10-13 | 济南大学 | Method for preparing mesoporous silicon dioxide microspheres by using laurylamine as template |
| CN101862037A (en) * | 2010-05-28 | 2010-10-20 | 华南理工大学 | Preparation method and application of hexagonal mesoporous monox coated nano-TiO2 composite material |
| KR101733850B1 (en) * | 2013-11-26 | 2017-05-08 | 차이나 토바코 추안우 인더스트리얼 컴퍼니 리미티드 | Micro-mesoporous core shell composite molecular sieve for reducing the harmful composition contained in a cigarette and a producing method thereof |
| CN107934983A (en) * | 2017-12-13 | 2018-04-20 | 重庆中烟工业有限责任公司 | Micro- mesoporous yolk shell composite molecular sieve of a kind of carried metal and preparation method thereof and a kind of cigarette |
| CN113618079A (en) * | 2021-08-12 | 2021-11-09 | 长春工业大学 | Method for synthesizing gold oligomer nanoparticles in mesoporous lanthanum-doped calcium silicate pore channel |
-
2009
- 2009-10-30 CN CN200910193518A patent/CN101698483A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862037A (en) * | 2010-05-28 | 2010-10-20 | 华南理工大学 | Preparation method and application of hexagonal mesoporous monox coated nano-TiO2 composite material |
| CN101862037B (en) * | 2010-05-28 | 2012-05-09 | 华南理工大学 | Preparation method and application of hexagonal mesoporous monox coated nano-TiO2 composite material |
| CN101857235A (en) * | 2010-06-11 | 2010-10-13 | 济南大学 | Method for preparing mesoporous silicon dioxide microspheres by using laurylamine as template |
| CN101857235B (en) * | 2010-06-11 | 2012-01-11 | 济南大学 | Method for preparing mesoporous silicon dioxide microspheres by using laurylamine as template |
| KR101733850B1 (en) * | 2013-11-26 | 2017-05-08 | 차이나 토바코 추안우 인더스트리얼 컴퍼니 리미티드 | Micro-mesoporous core shell composite molecular sieve for reducing the harmful composition contained in a cigarette and a producing method thereof |
| CN107934983A (en) * | 2017-12-13 | 2018-04-20 | 重庆中烟工业有限责任公司 | Micro- mesoporous yolk shell composite molecular sieve of a kind of carried metal and preparation method thereof and a kind of cigarette |
| CN113618079A (en) * | 2021-08-12 | 2021-11-09 | 长春工业大学 | Method for synthesizing gold oligomer nanoparticles in mesoporous lanthanum-doped calcium silicate pore channel |
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Open date: 20100428 |