CN101774605A - Preparation method for mesoporous molecular sieve MCM-48 - Google Patents
Preparation method for mesoporous molecular sieve MCM-48 Download PDFInfo
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- CN101774605A CN101774605A CN201010107602A CN201010107602A CN101774605A CN 101774605 A CN101774605 A CN 101774605A CN 201010107602 A CN201010107602 A CN 201010107602A CN 201010107602 A CN201010107602 A CN 201010107602A CN 101774605 A CN101774605 A CN 101774605A
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Abstract
The invention provides a preparation method for synthesizing a mesoporous molecular sieve MCM-48 of high regularity, which comprises the following steps: (1) heating up a mixture composed of tetraethyl orthosilicate, cetyl trimithyl ammonium bromide, sodium hydroxide, non-water-soluble additive and water to 40-60 DEG C and mixing to react for 2 hours, and adjusting the pH value to 10-12 with hydrochloric acid and transferring into a reaction kettle; (2) performing hydro-thermal crystallization with the temperature of 80-150 DEG C for 8-24 hours, and obtaining the pure silicon MCM-48 molecular sieve of high regularity with the crystallized product being separated, washed, dried and burned in the air for six hours. The invention has the advantages that the fluoride bearing additive used, i.e. the sodium fluosilicate, has low toxicity, the storage is stable, and the prepared pure silicon molecular sieve MCM-48 has the advantages of high crystallinity, high polymerization degree of skeleton, uniform and regular pore diameter, good experimental reproducibility and the like, and thereby facilitating the realization of industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of mesopore molecular sieve, be specifically related to reduce the preparation method of the mesopore molecular sieve MCM-48 of objectionable constituent in the cigarette smoke.
Background technology
U.S. Mobil company had reported M41S series mesopore molecular sieve first in 1992.This class material has the adjustable aperture of homogeneous, big specific surface and higher advantages such as thermostability, in fields such as catalysis, absorption, parting materials good prospects for application is arranged.Cube MCM-48 is a member of M41S series, contains two and has 2 to 7nm separate 3 D pore canal network structure and mirror symmetry (spacer is Ia3d), and this structure more helps reactive material to be transmitted therein, and stops up insensitive to the duct.And some macromolecular reaction is selected the shape effect, more help guest molecule conveying, therefore have good long-range order and higher thermostability, in selectivity catalysis, absorption, still the aspects such as assembling of nanocluster all have more tempting application prospect.But about the research report of aspects such as synthetic, the sign of mesoporous MCM-48 and application will be less than MCM-41 far away.At on January 11st, 2006 bulletin, Granted publication number is CN03116140.5, name is called in " ternary mixed-cation; nonionic and anion surfactant are that template prepares MCM-48 mesoporous molecular sieve method " Chinese patent, a kind of MCM-48 mesoporous molecular sieve preparation method is disclosed, it is relatively harsher that but this patent and prior art are used to prepare the condition of MCM-48, the template large usage quantity, crystallization temperature is higher and the cycle is longer, and the little quantitative response in laboratory adopts the static crystallization process mostly, make crystallization inhomogeneous in case amplify phenomenons such as reacting easy generation caking, the material degree of crystallinity and the degree of order that obtain are relatively poor, reaction is difficult for repeating, and is difficult to realize suitability for industrialized production.
Summary of the invention
Therefore the problem to be solved in the present invention is to seek a kind ofly can synthesize regularity height, better crystallinity degree in short period, and be convenient to the method for multiple pure silicon MCM-48 molecular sieve, make it be more suitable for suitability for industrialized production, and this material is applied in the cigarette filter tip its reduction effect of preliminary assessment to main objectionable constituent in the cigarette smoke.
Technical scheme of the present invention is: the mixture heating up to 40 that positive tetraethyl orthosilicate, cetyl trimethylammonium bromide, sodium hydroxide, water-insoluble additive and water are formed was to 60 ℃ of stirring reactions 2 hours, with hydrochloric acid its pH value being adjusted to 10 transfers in the reactor after 12,80 to 150 ℃ of hydrothermal crystallizings 8 to 24 hours, crystallized product through separate, in the washing, dry, air calcination 6 hours high regularity pure silicon MCM-48 molecular sieve; Wherein the mol ratio between each material is: cetyl trimethylammonium bromide/positive tetraethyl orthosilicate=0.15 to 0.4, sodium hydroxide/positive tetraethyl orthosilicate=0.56 to 0.76, H
2The positive tetraethyl orthosilicate of O/=65 to 100, water-insoluble additive/positive tetraethyl orthosilicate=0.02 to 0.07.
Wherein, water-insoluble additive is a Sodium Silicofluoride.
The invention provides the method for synthesising mesoporous molecular sieve MCM-48 in a kind of short period, this method is added a kind of water-insoluble fluorochemicals Sodium Silicofluoride in synthesis technique, and this additive normal temperature, normal pressure are stablized down; Meet heat and oxidation, reducing substances and can not burn, explode, water insoluble, generate F with the alkali effect in the reaction
-And silicate, to compare with general water-soluble fluorochemical additive, this additive toxicity is less, and security is higher, and the silicate that generates with the alkali effect also can be used as the silicon source, will reduce raw materials cost.This method can be prepared the pure silicon mesopore molecular sieve MCM-48 of regularity height, better crystallinity degree in short period, compare with traditional synthetic method, can save time largely, cut down the consumption of energy and cost, more help realizing the suitability for industrialized production of pure silicon mesopore molecular sieve MCM-48.This molecular sieve is used for reducing the main objectionable constituent of cigarette smoke, has obtained effect preferably.
Characteristics of the present invention are that employed fluorochemical additive Sodium Silicofluoride toxicity is less, store more stablely, place reaction and alkali effect just to discharge effective constituent F
-, shortened reaction time.Pure silicon molecular sieve MCM-48 better crystallinity degree, skeleton polymerization degree height, thermostability and good hydrothermal stability that this method is prepared, repeatable high, the silicate that discharges with the alkali effect helps pure silicon molecular sieve MCM-48 and realizes suitability for industrialized production as the silicon source cost that can economize in raw materials.
Description of drawings
Fig. 1 is the small angle X-ray diffraction spectrogram of the embodiment of the invention one product;
Fig. 2,3 is the high-resolution-ration transmission electric-lens spectrogram of the embodiment of the invention one product;
Fig. 4 is the high-resolution-ration transmission electric-lens spectrogram of the product of embodiment one, Comparative Examples 1, Comparative Examples 2;
Wherein, A is the high-resolution-ration transmission electric-lens spectrogram of embodiment one among Fig. 4, and B is the high-resolution-ration transmission electric-lens spectrogram of Comparative Examples one; C is the high-resolution-ration transmission electric-lens spectrogram of Comparative Examples two.
Embodiment
Embodiment one
Earlier cetyl trimethylammonium bromide is added in the entry, stirring makes its dissolving, add sodium hydroxide, Sodium Silicofluoride and positive tetraethyl orthosilicate then successively, above-mentioned reaction mixture was heated to 50 ℃ of stirring reactions 2 hours, transfer in the reactor after being adjusted to the pH value of mixed solution between the 11-12 with hydrochloric acid then, 110 ℃ of hydrothermal crystallizings 16 hours, crystallized product through separate, in the washing, dry, air calcination 6 hours the orderly pure silicon MCM-48 of high regularity molecular sieve.
Wherein the mol ratio between each material is: cetyl trimethylammonium bromide/positive tetraethyl orthosilicate=0.25, sodium hydroxide/positive tetraethyl orthosilicate=0.60, H
2The positive tetraethyl orthosilicate of O/=80, Na
2SiF
6/ positive tetraethyl orthosilicate=0.03.
As shown in Figure 1, from the small angle X-ray diffraction spectrogram, possesses the characteristic peak of MCM-48 as additive synthetic material with Sodium Silicofluoride; Shown in accompanying drawing 2,3, from the high-resolution-ration transmission electric-lens spectrogram, this material aperture homogeneous is about about 3nm, and has very high regularity.
Comparative Examples one
Synthesize the MCM-48 molecular sieve with Sodium Fluoride as additive:
Remove with Sodium Fluoride replacement fluorine water glass, F
-/ Si is than outside constant, and other synthesis conditions are identical with embodiment 1.
Comparative Examples two
The MCM-48 molecular sieve is synthesized in not doping:
Except that without any additives, other synthesis conditions are identical with embodiment 1.
As shown in Figure 4, the product with embodiment one, Comparative Examples one, Comparative Examples two are produced carries out the small angle X-ray diffraction spectrum analysis, and the strong more pore passage structure of characteristic peak is good more, and the degree of order is high more.The power of the characteristic peak from the figure adopts the product of the embodiment of the invention one preparation as can be seen, and structure is better, the degree of order is higher, and second Comparative Examples one and Comparative Examples do not have notable difference.Can find out also that from accompanying drawing 4 be both hydrothermal crystallizing reaction 16 hours, the reaction of adding Sodium Silicofluoride has generated orderly MCM-48, and interpolation Sodium Fluoride and non-additive reaction also form orderly MCM-48 in a large number.
Embodiment two
The mesoporous material 5mg that gets embodiment one preparation makes an addition to and makes composite filter tip in the cigarette filter tip, be used for reducing the main objectionable constituent of cigarette smoke, obtained effect preferably, wherein benzo (a) pyrene can reduce by 15%, crotonic aldehyde can reduce by 16%, and tobacco-specific nitrosamine (NNK) can reduce by 18%.
Claims (5)
1. the preparation method of a mesopore molecular sieve MCM-48 is characterized in that comprising the steps:
(1) mixture heating up to 40 that positive tetraethyl orthosilicate, cetyl trimethylammonium bromide, sodium hydroxide, water-insoluble additive and water are formed is adjusted to 10 with hydrochloric acid with its pH value and transfers in the reactor after 12 to 60 ℃ of stirring reactions 2 hours;
(2) 80 to 150 ℃ of hydrothermal crystallizings 8 to 24 hours, crystallized product through separate, in the washing, dry, air calcination 6 hours high regularity pure silicon MCM-48 molecular sieve; Wherein the mol ratio between each material is: cetyl trimethylammonium bromide/positive tetraethyl orthosilicate=0.15 to 0.4, sodium hydroxide/positive tetraethyl orthosilicate=0.56 to 0.76, H
2The positive tetraethyl orthosilicate of O/=65 to 100, water-insoluble additive/positive tetraethyl orthosilicate=0.02 to 0.07.
2. the preparation method of mesopore molecular sieve MCM-48 according to claim 1 is characterized in that: described water-insoluble additive is a Sodium Silicofluoride.
3. the preparation method of mesopore molecular sieve MCM-48 according to claim 1 is characterized in that: described pH value is 11.5.
4. the preparation method of mesopore molecular sieve MCM-48 according to claim 1 is characterized in that: described hydrothermal crystallizing stirs in reactor and carries out.
5. the preparation method of mesopore molecular sieve MCM-48 according to claim 1 is characterized in that: described crystallization time is 16 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259886A (en) * | 2011-06-01 | 2011-11-30 | 华东师范大学 | Preparation method of MCM-48 mesoporous molecular sieve |
| CN103172080A (en) * | 2013-03-27 | 2013-06-26 | 南京理工大学 | Method for preparing mesoporous molecular sieve |
| WO2014000247A1 (en) * | 2012-06-29 | 2014-01-03 | 海洋王照明科技股份有限公司 | Method for preparing polyacrylonitrile-methyl methacrylate gel electrolyte film, corresponding electrolyte and preparation method thereof |
| CN103855427A (en) * | 2012-12-07 | 2014-06-11 | 海洋王照明科技股份有限公司 | Modified polymethyl methacrylate electrolyte as well as preparation method, lithium ion battery and application thereof |
| CN103855424A (en) * | 2012-12-07 | 2014-06-11 | 海洋王照明科技股份有限公司 | Modified polyvinyl chloride electrolyte as well as preparation method thereof, lithium ion battery and application lithium ion battery |
| CN104803827A (en) * | 2015-03-17 | 2015-07-29 | 南京钟腾化工有限公司 | Method for preparing 2,6-dichlorotoluene by catalyzing o-chlorotoluene with ionic liquid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594085A (en) * | 2004-07-05 | 2005-03-16 | 华东理工大学 | Synthesis method of molecular sieve |
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2010
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259886A (en) * | 2011-06-01 | 2011-11-30 | 华东师范大学 | Preparation method of MCM-48 mesoporous molecular sieve |
| WO2014000247A1 (en) * | 2012-06-29 | 2014-01-03 | 海洋王照明科技股份有限公司 | Method for preparing polyacrylonitrile-methyl methacrylate gel electrolyte film, corresponding electrolyte and preparation method thereof |
| CN104271648A (en) * | 2012-06-29 | 2015-01-07 | 海洋王照明科技股份有限公司 | Method for preparing polyacrylonitrile-methyl methacrylate gel electrolyte film, corresponding electrolyte and preparation method thereof |
| CN103855427A (en) * | 2012-12-07 | 2014-06-11 | 海洋王照明科技股份有限公司 | Modified polymethyl methacrylate electrolyte as well as preparation method, lithium ion battery and application thereof |
| CN103855424A (en) * | 2012-12-07 | 2014-06-11 | 海洋王照明科技股份有限公司 | Modified polyvinyl chloride electrolyte as well as preparation method thereof, lithium ion battery and application lithium ion battery |
| CN103172080A (en) * | 2013-03-27 | 2013-06-26 | 南京理工大学 | Method for preparing mesoporous molecular sieve |
| CN104803827A (en) * | 2015-03-17 | 2015-07-29 | 南京钟腾化工有限公司 | Method for preparing 2,6-dichlorotoluene by catalyzing o-chlorotoluene with ionic liquid |
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