CN1775673A - Method for preparing MCM 48 molecular sieve - Google Patents
Method for preparing MCM 48 molecular sieve Download PDFInfo
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- CN1775673A CN1775673A CN 200510111245 CN200510111245A CN1775673A CN 1775673 A CN1775673 A CN 1775673A CN 200510111245 CN200510111245 CN 200510111245 CN 200510111245 A CN200510111245 A CN 200510111245A CN 1775673 A CN1775673 A CN 1775673A
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Abstract
The invention relates to a MCM-48 molecular sieve preparing method, including the main steps of: firstly in turn placing silicon source, alkali source, template agent and water soluble fluorine salt in a vessel; then making hydrothermal crystallization reaction at 0.1MPa; and finally washing, drying and baking the resultant to obtain the target matter. As compared with existing techniques, its remarkable advantage is shortening the preparing cycle of the MCM-48 molecular sieve.
Description
Technical field
The present invention relates to a kind of preparation method of molecular sieve, the preparation method of the silica-based mesoporous molecular sieve MCM-48 of particularly a kind of high regularity.
Background technology
Mobil company had successfully developed M41S series mesopore molecular sieve in 1992.M41S series mesopore molecular sieve comprises the MCM-41 of one dimension hexagonal structure, the unsettled MCM-50 of the MCM-48 of three-dimensional cubic structure and stratiform.The pore diameter range of this molecular sieve analog is between the 2-10 nanometer, and they have following main good characteristic: 1. the duct is shaped well, the aperture homogeneous; 2. can regulate and control in the aperture size certain limit; 3. have higher specific surface area and thermostability; 4. based on the high-sequential on the micro-scale.Therefore it has a good application prospect at aspects such as catalysis, fractionation by adsorption, Subjective and Objective combinatorial chemistries.
For the MCM-48 molecular sieve, the hydrothermal stability of MCM-41 molecular sieve is high slightly, and its preparation condition ratio is easier to realize that so up to now, people mainly concentrate on sight in the preparation of MCM-41 molecular sieve.But with regard to application, a deadly defect of MCM-41 molecular sieve is that its one dimension straight hole road is very easily stopped up by foreign matter, and the MCM-48 molecular sieve is highly beneficial for macromolecular diffusion owing to having unique three-dimensional spiral duct, be difficult for causing the duct to stop up, so have more application prospect.Yet, limited the application of MCM-48 molecular sieve because the cycle of present preparation MCM-48 molecular sieve is longer.Therefore the preparation cycle that how to shorten the MCM-48 molecular sieve becomes the technical issues that need to address of the present invention.
Summary of the invention
The objective of the invention is to, the preparation method of short MCM-48 molecular sieve of a kind of preparation cycle is provided.
The preparation method of the said MCM-48 molecular sieve of the present invention, it is characterized in that, described preparation method's key step is: will comprise that at first silicon source, alkali source, template and water-soluble villiaumite place container successively, carry out the hydrothermal crystallizing reaction then, the product with the hydrothermal crystallizing reaction gets target compound behind washing, drying and roast at last;
Wherein: said silicon source is silica gel, silicon sol or tetraalkyl silicon ester; Said alkali source is alkali-metal oxyhydroxide; Said template is a cetyl trimethylammonium bromide; The mol ratio of silicon source, alkali source, template, water and water-soluble villiaumite is 1: 0.25: 0.65: 60: 0.1～0.4; 100～150 ℃ of temperature, the reaction times of hydrothermal crystallizing reaction are 10～24 hours.
In the present invention: the silicon source of recommending to use is the tetraalkyl silicon ester, preferred four C
1～C
4Alkyl silicate, the best is tetraethyl silicane acid esters [Si (OC
2H
5)
4]; The alkali source of recommending to use is potassium hydroxide or sodium hydroxide; The water-soluble villiaumite of recommending to use is Sodium Fluoride, Potassium monofluoride or Neutral ammonium fluoride.Raw material and reagent that the present invention is used are commercially available product.
Preparation method of the present invention compares with prior preparation method has following characteristics:
(1) the hydrothermal crystallizing reaction times shortens greatly behind the adding fluorion; (2) add the cycle that exists that has prolonged MCM-48 behind the fluorion, slowed down cube in opposite directions transition process of lamellar phase, reaction repeatability is good.
Description of drawings
Fig. 1 is the XRD figure spectrum of MCM-48 molecular sieve
Wherein: (a) be the XRD figure spectrum that adds the MCM-48 molecular sieve of villiaumite preparation
(b) for not adding the XRD figure spectrum of the MCM-48 molecular sieve that villiaumite prepares.
Embodiment
The preparation method of the said MCM-48 molecular sieve of the present invention comprises the steps:
(1) at first tetraethyl silicane acid esters and water are placed a container, in this container, add sodium hydroxide and cetyl trimethylammonium bromide subsequently successively, stirred 30～40 minutes, be under 30 ℃～40 ℃ the condition in temperature, in this container, add Sodium Fluoride again, stir and get reaction mixture after 1 hour; Wherein the mole proportioning of tetraethyl silicane acid esters, sodium hydroxide, cetyl trimethylammonium bromide, water and Sodium Fluoride is 1: 0.25: 0.65: 60: 0.1～0.4;
(2) will be moved in the tetrafluoroethylene cup by step (1) gained reaction mixture, 120 ℃ of hydrothermal crystallizing reactions 10～24 hours, the product that hydrothermal crystallizing is reacted washed extremely neutral, dry reaching at 450～550 ℃ of roasts and got target compound in 2～6 hours again.
The present invention is further illustrated below by embodiment, and its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention:
Embodiment 1～7
In the water with the dissolution of sodium hydroxide to 50 milliliter of 0.9 gram, the tetraethoxy that adds 10 milliliters subsequently, the cetyl trimethylammonium bromide that adds 10.6 grams after 20 minutes, add F/Si after mixing again than (F represents villiaumite, Si represents the silicon source) be 0～0.4 villiaumite, vigorous stirring changed over to after 1 hour carries out hydrothermal crystallizing at a certain temperature in the tetrafluoroethylene cup, behind the certain hour that crystallization products therefrom suction filtration, washing is extremely neutral, dry former powder, the former powder of gained can be prepared a cube mesopore MCM-48 in 6 hours at 550 ℃ of following roasts.
| Embodiment | Phase | The hydrothermal crystallizing time | Sodium Fluoride | Neutral ammonium fluoride | Potassium monofluoride |
| Embodiment 1 | Cube phase cube phase cube phase cube mutually unformed cube of phase cube phase | 40 18 14 10 10 24 24 | 0 0.1 0.2 0.3 0.4 0 0 | 0 0 0 0 0 0.1 0 | 0 0 0 0 0 0 0.1 |
Prepare a cube mesopore MCM-48 according to the foregoing description and not only shortened the reaction times greatly, and have good repeatability.The sample of synthetic gained is with XRD (X-ray diffraction) characterized by techniques, and the power at the peak of the characteristic peak that is gone out from the X-ray diffraction spectrogram is judged the structure quality of product: characteristic peak is weak more, and pore passage structure is poor more; Characteristic peak is strong more, and the duct order is good more.From accompanying drawing as can be seen, the MCM-48 XRD peak that synthesizes of fluoridize is very not weak by force, shows that the pore passage structure order is poor; The powerful big enhancing in sample XRD peak that synthesizes behind the fluoridize, eight characteristic peaks of MCM-48 are all high-visible, show that the crystal formation of gained MCM-48 is good, the duct long-range order.
Claims (7)
1, a kind of preparation method of MCM-48 molecular sieve, it is characterized in that, described preparation method's key step is: will comprise that at first silicon source, alkali source, template and water-soluble villiaumite place container successively, carry out the hydrothermal crystallizing reaction then, the product with the hydrothermal crystallizing reaction gets target compound behind washing, drying and roast at last;
Wherein: said silicon source is silica gel, silicon sol or tetraalkyl silicon ester; Said alkali source is alkali-metal oxyhydroxide; Said template is a cetyl trimethylammonium bromide; The mol ratio of silicon source, alkali source, template, water and water-soluble villiaumite is 1: 0.25: 0.65: 60: 0.1～0.4; 100～150 ℃ of temperature, the reaction times of hydrothermal crystallizing reaction are 10～24 hours.
2, preparation method as claimed in claim 1 is characterized in that, wherein said silicon source is the tetraalkyl silicon ester.
3, preparation method as claimed in claim 2 is characterized in that, wherein said silicon source is four C
1～C
4Alkyl silicate.
4, preparation method as claimed in claim 3 is characterized in that, wherein said silicon source is the tetraethyl silicane acid esters.
5, preparation method as claimed in claim 1 is characterized in that, wherein said alkali source is potassium hydroxide or sodium hydroxide.
6, preparation method as claimed in claim 1 is characterized in that, wherein said water-soluble villiaumite is Sodium Fluoride, Potassium monofluoride or Neutral ammonium fluoride.
7, as described any one preparation method of claim 1～6, it is characterized in that described preparation method comprises the steps:
(1) at first tetraethyl silicane acid esters and water are placed a container, in this container, add sodium hydroxide and cetyl trimethylammonium bromide subsequently successively, stirred 30～40 minutes, be under 30 ℃～40 ℃ the condition in temperature, in this container, add Sodium Fluoride again, stir and get reaction mixture after 1 hour; Wherein the mole proportioning of tetraethyl silicane acid esters, sodium hydroxide, cetyl trimethylammonium bromide, water and Sodium Fluoride is 1: 0.25: 0.65: 60: 0.1～0.4;
(2) will be moved in the tetrafluoroethylene cup by step (1) gained reaction mixture, 120 ℃ of hydrothermal crystallizing reactions 10～24 hours, the product that hydrothermal crystallizing is reacted washed extremely neutral, dry reaching at 450～550 ℃ of roasts and got target compound in 2～6 hours again.
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| CN 200510111245 CN1775673A (en) | 2005-12-08 | 2005-12-08 | Method for preparing MCM 48 molecular sieve |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965014A (en) * | 2014-05-15 | 2014-08-06 | 华东理工大学 | Method for preparing cyclohexanol and cyclohexanone through selective oxidation of cyclohexane |
| CN107661536A (en) * | 2017-11-16 | 2018-02-06 | 山西大学 | A kind of multi-stage porous compound hemostatic agent containing molecular sieve and its preparation method and application |
-
2005
- 2005-12-08 CN CN 200510111245 patent/CN1775673A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965014A (en) * | 2014-05-15 | 2014-08-06 | 华东理工大学 | Method for preparing cyclohexanol and cyclohexanone through selective oxidation of cyclohexane |
| CN107661536A (en) * | 2017-11-16 | 2018-02-06 | 山西大学 | A kind of multi-stage porous compound hemostatic agent containing molecular sieve and its preparation method and application |
| CN107661536B (en) * | 2017-11-16 | 2020-07-10 | 山西大学 | Hierarchical pore composite hemostatic containing molecular sieve and preparation method and application thereof |
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