CN101172617A - Method for synthesizing nano type A molecular sieve - Google Patents
Method for synthesizing nano type A molecular sieve Download PDFInfo
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- CN101172617A CN101172617A CNA2007100312677A CN200710031267A CN101172617A CN 101172617 A CN101172617 A CN 101172617A CN A2007100312677 A CNA2007100312677 A CN A2007100312677A CN 200710031267 A CN200710031267 A CN 200710031267A CN 101172617 A CN101172617 A CN 101172617A
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Abstract
The invention discloses a synthesis method of a nanometer A-type molecular sieve, in particular to a rapid synthesis method of the nanometer A-type molecular sieve using supersonic crystallization under low temperature condition, without a template agent; firstly, a solution A can be achieved by dissolving NaOH into water and adding an aluminum source, and stirring; then a silicon source can be dipped into the solution A slowly, and after stirring intensely for a plurality of hours, a solution B is obtained; and then the solution B is put into a water bath with the low temperature of 20 to 60 DEG C to be supersonic crystallized for 10 to 60min. Finally, the nanometer A-type molecular sieve is obtained after the supersonic crystallized product is washed, filtered, and dried. The method has simple and convenient operation, low synthesis temperature, short synthesis time, and even obtained particles of the nanometer A-type monocular sieve.
Description
Technical field
The present invention relates to a kind of synthetic method of A type molecular sieve, relate in particular to the synthetic fast method of ball-type nano type A molecular sieve uniformly under a kind of cold condition.
Background technology
Nano-class molecular sieve has the incomparable excellent properties of conventional molecular sieve, and is of many uses, thereby the synthetic and application of nano molecular sieve is one of focus of current research.At present, the method for preparing molecular sieve both at home and abroad mainly contains conventional hydrothermal method (no template and organic formwork) (petrochemical complex, 2005,34:1099～1102), microwave method (Catal.Today, 1998,44:301～308), space constraint method (Chemical Communication, 1999,673～674), vapor phase method (daily chemical industry, 2003,33:295～297) etc.Conventional no template hydrothermal method consumes energy, long reaction time, and also the crystal grain that obtains is not only greatly but also inhomogeneous (1～10 μ m), and this method is not suitable for preparing nano-class molecular sieve.
Microwave process for synthesizing also is the method for a kind of quick synthesis of molecular sieve of rising in recent years, and the particle diameter of its synthetic product is also smaller.SlangenPM (Microp.Mater., 1997,9:259～265) etc. have synthesized the 4A molecular sieve of hundreds of nanometer fast with microwave method under 100 ℃ after different room temperature ageings.
The space constraint method be by a kind of crystallization inert media limit crystal grain continue grow up, this method is exactly at high temperature to remove the inert media of limit grain growth (as carbon black and starch), can cause nanocrystalline reunion simultaneously.Iver Schmidt this methods of usefulness such as (Inorg.Chem.2000,39:2279～2283) has been synthesized the zeolite molecular sieve of tens nanometers.
The vapor phase method is that the presoma of preparation is made pie, is placed on a bottom and can puts in the system on the solvent and the belt supporting frame that can seal, reacts at a certain temperature.This method is synthesized when comparing consumption energy consumption, and the crystal grain of product is at several microns.Yang Xiaoyi etc. utilize this method at 100 ℃ of 4A molecular sieves that synthesize sample granularity distribution＜4 μ m.In addition at room temperature can the synthesis of nano molecular sieve, Svetlana (Science, 1999,183:958～960) etc. has synthesized the nano-scale 4 A molecular sieve, but reaction time is very long, also need add a certain amount of organic formwork agent.
Supersonic method also is a kind of quick synthesis method of rising in recent years, and it is to utilize acoustic cavitation can quicken and control chemical reaction, improves a new cross discipline of the new chemical reaction of reaction yield and initiation.Acoustic cavitation is meant that the small complex in the liquid is activated, and shows as a series of dynamic processes such as vibration, growth, contraction and even collapse of complex under acoustic wave action.At the utmost point of cavitation bubble collapse in the short period of time, can in the little space scope around it, produce the high temperature of 1900～5200 K and surpass the high pressure of 50MPa, rate of temperature change is up to 10
9K/s, and with intensive shockwave and the speed per hour jet up to 400km/h.These conditions are enough to open the strong chemical bond of bonding force (376.8～418.6kJ/mol), and promote " water burning " (aqueouscombustion) to react.Attached to microbubble or bubble on solid impurity, micronic dust or the vessel surface and in the finedraw, cause in the tiny area of strength reduction in the liquid bubbing etc. all can form this small complex because of structure is inhomogeneous.Adopt ultrasonic wave to prepare powder body material many (non-ferrous metal, 2001,53:81～83) of report both at home and abroad, report is few both at home and abroad but adopt the ultrasonic wave synthesis of molecular sieve.Stroke bright (SCI, 2005,26:1603～1606) etc. utilizes ultrasonic wave to synthesize the 4A molecular sieve of median size for 280nm fast, and particle diameter ratio hydrothermal method synthetic is much smaller, and the reaction times is 1/24 of hydrothermal method.
Existing synthesis method all has different separately shortcomings: or the temperature of reaction height, crystallization time is long, or adds organic formwork agent, or adds inert space restriction medium, or prolongs digestion time.Given this, this patent adopts ultrasonic method to synthesize nano type A molecular sieve.
Summary of the invention
The invention provides a kind of synthetic method of nano type A molecular sieve, relate in particular to a kind of no template, the method for ultrasonic crystallization method quickly synthesizing nano A type molecular sieve under the cold condition.Water-soluble with NaOH, add the aluminium source again, stirring and dissolving obtains solution A; Slowly add the silicon source then in A, vigorous stirring a few hours, obtain solution B, its mol ratio is Na
2O: SiO
2: Al
2O
3: H
2O=5～10: 2.0～3.0: 1: 90～220 are put into solution B ultrasonic crystallization 10～60min in 20～60 ℃ the low temperature water-bath, and the product of ultrasonic crystallization filters through washing, and drying obtains nano type A molecular sieve at last.
The pH of described NaOH alkaline solution＞14.Described aluminium source is Tai-Ace S 150, aluminum nitrate, aluminum isopropylate, sodium metaaluminate or sodium aluminate.Described silicon source is water glass, tetraethoxy, silicic acid, silicon-dioxide or silicon sol.Hyperacoustic power is 120W.Synthetic nano type A molecular sieve uniform particles 20～100nm.This method operation is very simple, and synthesis temperature is low, and generated time is short, the uniform particles of gained ball-type nano type A molecular sieve.
The invention has the beneficial effects as follows:: synthetic method of the present invention need not added organic formwork agent or space constraint agent, not ageing, temperature of reaction is low, and crystallization time is short, operates very simple quick.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure of A type molecular sieve.
Fig. 2 is transmission electron microscope (TEM) photo of A type molecular sieve.
Embodiment
Example 1
Weighing sodium hydroxide 21.0g, be dissolved in the 80.0g water, add the 11.0g sodium aluminate again, make it to be dissolved to clarification, drip silicon sol 30.0g again, vigorous stirring 6～18h, ultrasonic crystallization 10～60min in 20～60 ℃ of water-baths, use the sodium hydroxide solution repetitive scrubbing of 0.01mol/L at last, filter, drying can obtain nano type A molecular sieve again.
Example 2
Weighing sodium hydroxide 30.5g, be dissolved in the 200.0g water, add the 16.0g sodium aluminate again, make it to be dissolved to clarification, drip silicon sol 38.0g again, vigorous stirring 6～18h, ultrasonic crystallization 10～60min in 20～60 ℃ of water-baths, use the sodium hydroxide solution repetitive scrubbing of 0.01mol/L at last, filter, drying can obtain nano type A molecular sieve again.
Example 3
Weighing sodium hydroxide 40.0g, be dissolved in the 200.0g water, add the 18.0g sodium aluminate again, make it to be dissolved to clarification, drip silicon sol 49.0g again, vigorous stirring 6～18h, ultrasonic crystallization 10～60min in 20～60 ℃ of water-baths, use the sodium hydroxide solution repetitive scrubbing of 0.01mol/L at last, filter, drying can obtain nano type A molecular sieve again.
Example 4
Weighing sodium hydroxide 35.6g, be dissolved in the 160.0g water, add the 14.0g sodium aluminate again, make it to be dissolved to clarification, drip silicon sol 31.5g again, vigorous stirring 6～18h, ultrasonic crystallization 10～60min in 20～60 ℃ of water-baths, use the sodium hydroxide solution repetitive scrubbing of 0.01mol/L at last, filter, drying can obtain nano type A molecular sieve again.
Claims (6)
1. the method for a synthesizing nano type A molecular sieve, its step comprises:
(a) it is soluble in water to get NaOH, makes its clarification;
(b) add the aluminium source in the solution of (a) preparation, stir and make its clarification;
(c) drip the silicon source again in the solution of (b) preparation, stir 6～18h, form white gels, its mol ratio is Na
2O: SiO
2: Al
2O
3: H
2O=5～10: 2～3: 1: 90～220;
(d) gel that (c) obtained is ultrasonic crystallization under 20～60 ℃ the cold condition in temperature, through washing, filters, and drying obtains nano type A molecular sieve.
2. synthetic method according to claim 1 is characterized in that pH＞14 of alkaline solution in described (a).
3. synthetic method according to claim 1 is characterized in that the aluminium source is Tai-Ace S 150, aluminum nitrate, aluminum isopropylate, sodium metaaluminate or sodium aluminate in described (b).
4. synthetic method according to claim 1 is characterized in that the silicon source is water glass, tetraethoxy, silicic acid, silicon-dioxide or silicon sol in described (c).
5. synthetic method according to claim 1 is characterized in that the ultrasonic crystallization time in the step (d) is 10～60min, and hyperacoustic power is 120W.
6. synthetic method according to claim 1 is characterized in that synthetic nano type A molecular sieve uniform particles 20～100nm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894121A (en) * | 2014-03-12 | 2014-07-02 | 上海交通大学 | Preparation and application of nano zeolite reinforced xanthan gum composite hydrogel functional microspheres |
| CN104045095A (en) * | 2014-01-16 | 2014-09-17 | 常州大学 | Preparation method of porous 5A molecular sieve for straight-chain alkane adsorption |
| CN104071816A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院过程工程研究所 | Method for improving crystallization of sodium aluminate by ultrasonic field |
| CN107961759A (en) * | 2016-10-19 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of 5A adsorbent of molecular sieve and its preparation method and application |
| CN110467196A (en) * | 2019-09-20 | 2019-11-19 | 苏州立昂新材料有限公司 | The preparation method of the A type molecular sieve of Template-free method |
-
2007
- 2007-11-06 CN CNA2007100312677A patent/CN101172617A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104071816A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院过程工程研究所 | Method for improving crystallization of sodium aluminate by ultrasonic field |
| CN104045095A (en) * | 2014-01-16 | 2014-09-17 | 常州大学 | Preparation method of porous 5A molecular sieve for straight-chain alkane adsorption |
| CN103894121A (en) * | 2014-03-12 | 2014-07-02 | 上海交通大学 | Preparation and application of nano zeolite reinforced xanthan gum composite hydrogel functional microspheres |
| CN103894121B (en) * | 2014-03-12 | 2016-02-10 | 上海交通大学 | The preparations and applicatio of nano zeolite strengthening xanthans composite aquogel functional microsphere |
| CN107961759A (en) * | 2016-10-19 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of 5A adsorbent of molecular sieve and its preparation method and application |
| CN107961759B (en) * | 2016-10-19 | 2020-08-11 | 中国石油化工股份有限公司 | 5A molecular sieve adsorbent and preparation method and application thereof |
| CN110467196A (en) * | 2019-09-20 | 2019-11-19 | 苏州立昂新材料有限公司 | The preparation method of the A type molecular sieve of Template-free method |
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