CN101177280A - Method for quickly synthesizing nano X-type molecular sieve by low-temperature ultrasonic crystallization process - Google Patents
Method for quickly synthesizing nano X-type molecular sieve by low-temperature ultrasonic crystallization process Download PDFInfo
- Publication number
- CN101177280A CN101177280A CNA2007100312681A CN200710031268A CN101177280A CN 101177280 A CN101177280 A CN 101177280A CN A2007100312681 A CNA2007100312681 A CN A2007100312681A CN 200710031268 A CN200710031268 A CN 200710031268A CN 101177280 A CN101177280 A CN 101177280A
- Authority
- CN
- China
- Prior art keywords
- type molecular
- molecular sieve
- solution
- nano
- ultrasonic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a quick synthesis method of nanometer X type molecular sieves with low temperature ultrasonic crystallization method, in particular to quick synthesis method of nanometer X type molecular sieves by using low temperature ultrasonic wave crystallization method without template, which comprises the following steps: aluminum source is added into the NaOH solution with the pH value over 14, then the solution is stirred and dissolved into clarification to obtain solution A; silicon source is dropped into the solution A, and the solution is stirred acutely for certain hours to obtain gel solution B; the gel solution B is positioned into a water bath with 30 to 80 DEG C temperature for ultrasonic crystallization for 20 to 80 min, and the synthesized product is washed, filtered and dried, and finally the X type molecular sieves are obtained. The invention has the advantages of simple and easy operation, low synthesis temperature, short synthesis time, and uniform granules of the nanometer X type molecular sieves.
Description
Technical field
The present invention relates to a kind of method of synthesizing nano X-type molecular sieve, relate in particular to a kind of no template, the fast synthetic down evengranular nano X-type molecular sieve of cold condition.
Background technology
X type molecular sieve of many uses, as can be used as catalyzer, siccative and sorbent material, being used for gas delivery, wastewater treatments etc. cause numerous investigators' concern already.The preparation method of molecular sieve mainly contains hydrothermal method (Journal of Inorganic Materials at present, 2001,16:63～68), microwave method (petroleum journal, 1999,15:89～91), space constraint method (Chin.Chem.Lett., 2002,13:385～388) etc., but with regard to synthetic X type molecular sieve, generally all adopt hydrothermal method, but the hydrothermal method power consumption, reaction time is long, particle grain size big and distribute wide (1～10 μ m).Other reports also have Xu (Microporous and MesoporousMaterials, 2004, and Decio Coutinho (Microporous and MesoporousMaterials 75:173～181) etc., 2002,52:79～91) etc. adopt microwave-hydrothermal method and pulsed laser deposition to prepare the NaX molecular screen membrane respectively.Though the microwave method resultant velocity is fast but resultant quantity is few, industrialization remains in problem.Space constraint method energy synthesis of nano molecular sieve, but high temperature removal inert media can cause serious reunion.
Sonochemistry is meant and utilizes acoustic cavitation can quicken and control chemical reaction, improves a new cross discipline of the new chemical reaction of reaction yield and initiation.Ultrasonic wave can by liquid medium to around propagate, and in liquid medium, produce ultrasonic cavitation, the small complex in the liquid is activated under acoustic wave action, shows as a series of dynamic processes such as oscillating growth, contraction and even collapse of complex.At the utmost point of cavitation bubble collapse in the short period of time, can in little space around it, produce the high temperature of 1900～5200K and surpass the high pressure of 50MPa, the transient temperature velocity of variation is up to 10
9K/s and with intensive shockwave and momentary velocity microjet up to 400km/h.These phenomenons can increase the surface-area of inhomogeneous reaction, improve the rate of mass transfer between the interface, promote the formation of cenotype, have been widely used in the preparation of powder body material.At present, the report of ultrasonic wave synthesis of molecular sieve is few, has only with the synthetic 4A molecular sieve (SCI of ultrasonic wave; 2005; 1603～1606) and mesoporous MCM-41 (Microporous and Mesoporous Materials, 2004, (74): 37～47) 26 (9):.Shang Weiyou adopts the report of the synthetic X type molecular sieve of supersonic method to deliver.
Summary of the invention
The invention provides a kind of synthetic method of X type molecular sieve, a kind of no template especially is provided, the method for the fast synthetic uniform nano X-type molecular sieve of ultrasonic crystallization method under the cold condition.The technical process of this method is: the aluminium source is added in the NaOH solution of pH＞14, stirring and dissolving obtains solution A to clarification; The silicon source slowly is added drop-wise among the A, vigorous stirring a few hours, obtain gelating soln B, the mol ratio of material is Na
2O: SiO
2: Al
2O
3: H
2O=5～11: 3.0～4.0: 1: 100～240, it is water-bath ultrasonic crystallization 20～80min of 30～80 ℃ that B is put into temperature, and the synthetic product filters through washing, and drying obtains nano X-type molecular sieve at last.
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.
Described ultrasonic power is 120W.
Synthetic nano X-type molecular sieve uniform particles 5～40nm, this method operation is very simple, and synthesis temperature is low, and generated time is short, obtains evengranular nano X-type molecular sieve.
The invention has the beneficial effects as follows:: the invention provides and a kind ofly need not add organic template, do not need the space constraint agent, do not need ageing, under cold condition, just can synthesize the method for uniform nano X-type molecular sieve fast.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure of synthetic X type molecular sieve.
Fig. 2 is one of transmission electron microscope (TEM) photo of synthetic X type molecular sieve.
Fig. 3 be synthetic X type molecular sieve transmission electron microscope (TEM) photo two.
Embodiment
Example 1.
Weighing sodium hydroxide 19.0g, be dissolved in the 80.0g water, add the 10.0g sodium aluminate again, make it clarification, change in the there-necked flask, drip silicon sol 34.5g again, vigorous stirring 6～18h, ultrasonic crystallization 20～80min in 30～80 ℃ water-bath, the sodium hydroxide solution with 0.01mol/L washs repeatedly, filter, can obtain nano X-type molecular sieve after the drying.
Example 2
Weighing sodium hydroxide 32.0g, be dissolved in the 110.0g water, add the 10.0g sodium aluminate again, make it clarification, change in the there-necked flask, drip silicon sol 48.5g again, vigorous stirring 6～18h, ultrasonic crystallization 20～80min in 30～80 ℃ water-bath, the sodium hydroxide solution with 0.01mol/L washs repeatedly, filter, drying can obtain nano X-type molecular sieve.
Example 3
Weighing sodium hydroxide 40.5g, be dissolved in the 170.0g water, add the 16.0g sodium aluminate again, make it clarification, change in the there-necked flask, drip silicon sol 52.5g again, vigorous stirring 6～18h, ultrasonic crystallization 20～80min in 30～80 ℃ water-bath, the sodium hydroxide solution with 0.01mol/L washs repeatedly, filter, drying can obtain nano X-type molecular sieve.
Example 4
Weighing sodium hydroxide 51.6g, be dissolved in the 210.0g water, add the 19.0g sodium aluminate again, make it clarification, change in the there-necked flask, drip silicon sol 60.0g again, vigorous stirring 6～18h, ultrasonic crystallization 20～80min in 30～80 ℃ water-bath, the sodium hydroxide solution with 0.01mol/L washs repeatedly, filter, drying can obtain nano X-type molecular sieve.
Claims (6)
1. the method for a low-temperature ultrasonic crystallization method quickly synthesizing nano X-type 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=5～11: 3～4: 1: 100～240;
(d) gel that (c) obtained is ultrasonic crystallization under 30～80 ℃ the cold condition in temperature, through washing, filters, and drying obtains nano X-type 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 20～80min, and ultrasonic power is 120W.
6. synthetic method according to claim 1 is characterized in that synthetic nano X-type molecular sieve uniform particles 5～40nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100312681A CN100567151C (en) | 2007-11-06 | 2007-11-06 | The method of low-temperature ultrasonic crystallization method quickly synthesizing nano X-type molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100312681A CN100567151C (en) | 2007-11-06 | 2007-11-06 | The method of low-temperature ultrasonic crystallization method quickly synthesizing nano X-type molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101177280A true CN101177280A (en) | 2008-05-14 |
| CN100567151C CN100567151C (en) | 2009-12-09 |
Family
ID=39403732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100312681A Expired - Fee Related CN100567151C (en) | 2007-11-06 | 2007-11-06 | The method of low-temperature ultrasonic crystallization method quickly synthesizing nano X-type molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100567151C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288099A (en) * | 2013-06-05 | 2013-09-11 | 扬州大学 | Synthesis method of nano NaX molecular sieve |
| CN104030313A (en) * | 2014-05-26 | 2014-09-10 | 中国海洋石油总公司 | Method of synthesizing submicron T-type molecular sieve |
| 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 |
| CN105727853A (en) * | 2016-01-29 | 2016-07-06 | 卓达新材料科技集团有限公司 | Ambient pressure drying method of fiber needled felt/silicon-aluminium aerogel composite insulation board |
| CN106542542A (en) * | 2015-09-16 | 2017-03-29 | 神华集团有限责任公司 | A kind of 13X zeolite molecular sieves and its preparation method and application |
| CN106946271A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of X-type molecular sieve and its synthetic method |
| CN107512728A (en) * | 2017-07-03 | 2017-12-26 | 深圳大学 | The preparation method of card plugging structure multi-stage porous FAU type zeolite molecular sieves |
| CN110776042A (en) * | 2019-09-29 | 2020-02-11 | 中冶华天工程技术有限公司 | Bifunctional material for reducing and removing chromium (VI) in water and preparation method thereof |
-
2007
- 2007-11-06 CN CNB2007100312681A patent/CN100567151C/en not_active Expired - Fee Related
Cited By (13)
| 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 |
| CN103288099B (en) * | 2013-06-05 | 2016-02-10 | 扬州大学 | A kind of synthetic method of nano NaX molecular sieve |
| CN103288099A (en) * | 2013-06-05 | 2013-09-11 | 扬州大学 | Synthesis method of nano NaX molecular sieve |
| CN104030313B (en) * | 2014-05-26 | 2016-08-24 | 中国海洋石油总公司 | A kind of method of synthesizing submicron type T molecular sieve |
| CN104030313A (en) * | 2014-05-26 | 2014-09-10 | 中国海洋石油总公司 | Method of synthesizing submicron T-type molecular sieve |
| CN106542542A (en) * | 2015-09-16 | 2017-03-29 | 神华集团有限责任公司 | A kind of 13X zeolite molecular sieves and its preparation method and application |
| CN106542542B (en) * | 2015-09-16 | 2019-02-15 | 神华集团有限责任公司 | A kind of 13X zeolite molecular sieve and its preparation method and application |
| CN106946271A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of X-type molecular sieve and its synthetic method |
| CN106946271B (en) * | 2016-01-07 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of X-type molecular sieve and its synthetic method |
| CN105727853A (en) * | 2016-01-29 | 2016-07-06 | 卓达新材料科技集团有限公司 | Ambient pressure drying method of fiber needled felt/silicon-aluminium aerogel composite insulation board |
| CN107512728A (en) * | 2017-07-03 | 2017-12-26 | 深圳大学 | The preparation method of card plugging structure multi-stage porous FAU type zeolite molecular sieves |
| CN107512728B (en) * | 2017-07-03 | 2020-06-26 | 深圳大学 | Preparation method of FAU type zeolite molecular sieve with card-inserted structure and hierarchical pores |
| CN110776042A (en) * | 2019-09-29 | 2020-02-11 | 中冶华天工程技术有限公司 | Bifunctional material for reducing and removing chromium (VI) in water and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100567151C (en) | 2009-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100567151C (en) | The method of low-temperature ultrasonic crystallization method quickly synthesizing nano X-type molecular sieve | |
| Zeng et al. | Microwave synthesis of zeolites and their related applications | |
| CN107640775B (en) | Method for preparing ZSM-5 molecular sieve by using solid waste | |
| CN104098110B (en) | Preparation method and application of B-Al-ZSM-5 zeolite with controllable particle diameter | |
| CN105883849B (en) | The synthetic method of the molecular sieves of ZSM 5 of morphology controllable | |
| CN105728019A (en) | Application and preparation method of ZSM-5 molecular sieve with mesopores and micropores | |
| Essien et al. | Sol-gel-derived porous silica: Economic synthesis and characterization. | |
| KR20190020752A (en) | Continuous synthesis of zeolite-based materials | |
| CN105032478A (en) | Catalyst used for isomeric pour point depression of middle distillate in F-T synthesis and special core-shell structure composite molecular sieve of catalyst | |
| Yuan et al. | Mesoporogen-free strategy to construct hierarchical TS-1 in a highly concentrated system for gas-phase propene epoxidation with H2 and O2 | |
| CN104556094A (en) | Y/Silicalite-1 composite molecular sieve and preparation method thereof | |
| JP2000515844A (en) | Production of zeolites | |
| CN101274764B (en) | Preparation for nanometer allitic beta-zeolite | |
| CN102336425A (en) | Method for preparing aluminum hydroxide micro-powder with low oil absorption rate | |
| CN101864096A (en) | Organic/zeolite hybrid material and preparation method thereof | |
| CN101172617A (en) | Method for synthesizing nano type A molecular sieve | |
| CN102451745B (en) | Hydrocracking catalyst containing Y-type molecular sieve/amorphous silica-alumina and preparation method thereof | |
| CN107512725A (en) | With core shell structure TON MFI composite molecular screens and preparation method thereof | |
| CN110615445B (en) | Method for synthesizing ZSM-5 zeolite monobloc without template and adhesive | |
| CN102674387A (en) | Synthesis method of multi-stage nanometer crystal accumulation structure melt flow index (MFI) type molecular sieves | |
| CN103771452B (en) | A kind of square beta-molecular sieve and preparation method thereof | |
| CN103848436B (en) | A kind of method of Template-free method two-step approach Hydrothermal Synthesis ultra micro type A zeolite | |
| CN110467198A (en) | A kind of multi-stage porous ZSM-5 Micelle-like Nano-structure of Two microballoon and preparation method | |
| CN103787367B (en) | Preparation method of binder-free ZSM-5 molecular sieve forming product | |
| CN104549538B (en) | A kind of preparation method of amorphous silicon alumina supporter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091209 Termination date: 20131106 |