CN1500721A - Process for preparing pure silicon MCM-41 molecular sieves - Google Patents
Process for preparing pure silicon MCM-41 molecular sieves Download PDFInfo
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- CN1500721A CN1500721A CNA021452407A CN02145240A CN1500721A CN 1500721 A CN1500721 A CN 1500721A CN A021452407 A CNA021452407 A CN A021452407A CN 02145240 A CN02145240 A CN 02145240A CN 1500721 A CN1500721 A CN 1500721A
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Abstract
The present invention relates to the preparation process of pure silicon MCM-41 molecular sieve and solves the problems in the preparation process, including excessive high crystallization reaction temperature, excessive high crystallization reaction pressure, excessive long crystallization reaction period and strong corrosion of the crystallization liquid. The technological scheme of the present invention is that fluoride salt is added into the reaction system comprising quaternary ammonium base, silicon source and surfactant. The present invention may be used in industrial preparation of pure silicon MCM-41 molecular sieve.
Description
Technical field
The present invention relates to a kind of method for preparing pure silicon MCM-41 molecular sieve.
Background technology
The medium pore crystals material is at first synthetic by Mobil company.Its hole size can be controlled in the scope of 20～100A, and the pore distribution homogeneous, is named as MCM-41.U.S. Pat 5108725, US5102643, US5098684 and US5057296 have described building-up process, and reaction reagent is formed physics and structural performance.
In above-mentioned patent, adopt quaternary ammonium hydroxide, silicon source (the perhaps silicate of quaternary ammonium hydroxide) and tensio-active agent (cetyl trimethylammonium bromide or its oxyhydroxide) in autoclave, 100～150 ℃ of crystallization 2～7 days.
The principle of crystallization is that silicon oxide or silica-alumina mixed oxide attract micellar surface (micella is by the water-soluble generation of tensio-active agent), roasting can make between Siliciumatom or silicon, aluminium atom between form cross connection, thereby constitute molecular sieve structure.Crystallization process needs a large amount of quaternary ammonium salts, and needs to react under High Temperature High Pressure 2～7 days.
U.S. Pat 6096287 has been introduced a kind of method of synthetic mesoporous molecular sieve, use hydrofluoric acid solution dissolved oxygen silicon after, short period of time crystallization and getting at room temperature.This method is applicable to various silicon oxide.After adopting hydrofluoric acid, can make to be reflected under 25～80 ℃ and finish, but hydrofluoric acid has very strong corrodibility and toxicity, has so just limited the scope of application of this method.
Summary of the invention
Technical problem to be solved by this invention is to have crystallization temperature height in the conventional art, crystallization pressure height, and the long or strong problem of crystallization liquid corrodibility of crystallization time provides a kind of new method for preparing pure silicon MCM-41 molecular sieve.This method has that crystallization temperature is low, and crystallization pressure is low, and crystallization time is short, and the MCM-41 molecular sieve pore distribution that makes is narrow, the characteristics that specific surface area is big.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing pure silicon MCM-41 molecular sieve, with tetraethyl orthosilicate, silicon sol or silicon gel is the silicon source, the salt of cetyltrimethyl ammonium or alkali are that salt or the alkali of CTMA is tensio-active agent, quaternary ammonium hydroxide is or/and organic amine is template RN, and fluoride salt and water composition mixture, wherein be: CTMA/SiO with molar ratio computing
2=0.1～0.6, H
2O/SiO
2=60～100, RN/SiO
2=0.2～0.5, F
-/ SiO
2=0.02～0.2, be under 0～80 ℃ of condition with above-mentioned reaction mixture at crystallization temperature, crystallization time is 2～20 hours, and crystallized product is through separation, washing, drying, and calcination gets pure silicon MCM-41 molecular sieve in air.
The tensio-active agent preferred version is for being selected from cetyl trimethylammonium bromide in the technique scheme; The quaternary ammonium hydroxide preferred version is selected from TPAOH, TBAH, tetraethyl ammonium hydroxide or Tetramethylammonium hydroxide; Organic amine preferred version select oneself diamines, diethylamine, quadrol, triethylamine or n-Butyl Amine 99.The fluoride salt preferred version is selected from least a in Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride or the cesium fluoride.The crystallization temperature preferable range is 0～40 ℃, and the crystallization time preferable range is 3～8 hours.
The present invention, owing in reaction system, added fluoride salt, crystallization can be carried out under normal pressure, lower temperature, crystallization time also shortens greatly, only is 2～20 hours, and the pure silicon MCM-41 molecular sieve that is obtained to have a pore distribution narrow, the characteristics that specific surface area is big, in addition because fluoride salt does not have severe corrosive, so reaction mass can not constitute trouble to reaction vessel, obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
The mixing solutions that cetyl trimethylammonium bromide (CTMABr), tetraethyl ammonium hydroxide (TEAOH), the water of requirement are formed is added in the container of band whipping appts.At room temperature after the stirring and dissolving, add the positive tetraethyl orthosilicate of 50 grams, add a certain amount of Neutral ammonium fluoride.At crystallization temperature is 40 ℃, and under the normal pressure, crystallization is 3 hours under the whipped state.The relative molar content of each component wherein:
CTMABr/SiO
2＝0.2，TEAOH/SiO
2＝0.35，H
2O/SiO
2＝45，NH
4F/SiO
2＝0.02
Crystallization is isolated crystallized product after finishing, and after 120 ℃ of dryings, 550 ℃ of calcinations 6 hours, gets mesopore pure silicon molecular sieve.Be determined as the MCM-41 molecular sieve through the XRD diffraction, its physical adsorption data see Table 1.
[embodiment 2]
With embodiment 1 operation.Just changing template is TPAOH (TPAOH), and crystallization temperature is 25 ℃, and crystallization time is 8 hours, and the mole relative content of component is in the raw material:
CTMABr/SiO
2＝0.2，TPAOH/SiO
2＝0.35，H
2O/SiO
2＝45，NH
4F/SiO
2＝0.05
The molecular sieve that obtains is determined as the MCM-41 molecular sieve through the XRD diffraction, and its physical adsorption data see Table 1.
[embodiment 3]
With embodiment 1 operation.But template is TPAOH (TPAOH), and crystallization temperature is 10 ℃, and crystallization time is 18 hours, and the relative molar content of component is in the raw material:
CTMABr/SiO
2＝0.2，TPAOH/SiO
2＝0.35，H
2O/SiO
2＝45，NH
4F/SiO
2＝0.1
The molecular sieve that obtains is determined as the MCM-41 molecular sieve through the XRD diffraction, and its physical adsorption data see Table 1.
[comparative example 1]
With embodiment 1 operation.But do not add Neutral ammonium fluoride in the raw material.
CTMABr/SiO
2＝0.2，TPAOH/SiO
2＝0.35，H
2O/SiO
2＝45
The molecular sieve that obtains is determined as the MCM-41 molecular sieve through the XRD diffraction, and its physical adsorption data see Table 1.
Table 1 physical adsorption data
Embodiment S
BET, centimetre
2/ gram pore volume, centimetre
3/ gram mean pore size, nanometer
Embodiment 1 751.84 0.73 3.22
Embodiment 2 917.66 0.89 3.87
Embodiment 3 792.97 0.61 3.72
Comparative example 1 523.27 0.84 6.39
Claims (7)
1, a kind of method for preparing pure silicon MCM-41 molecular sieve, with tetraethyl orthosilicate, silicon sol or silicon gel is the silicon source, the salt of cetyltrimethyl ammonium or alkali are that salt or the alkali of CTMA is tensio-active agent, quaternary ammonium hydroxide is or/and organic amine is template RN, and fluoride salt and water composition mixture, wherein be: CTMA/SiO with molar ratio computing
2=0.1～0.6, H
2O/SiO
2=60～100, RN/SiO
2=0.2～0.5, F
-/ SiO
2=0.02～0.2, be under 0～80 ℃ of condition with above-mentioned reaction mixture at crystallization temperature, crystallization time is 2～20 hours, and crystallized product is through separation, washing, drying, and calcination gets pure silicon MCM-41 molecular sieve in air.
2,, it is characterized in that tensio-active agent is a cetyl trimethylammonium bromide according to the described method for preparing pure silicon MCM-41 molecular sieve of claim 1.
3, according to the described method for preparing pure silicon MCM-41 molecular sieve of claim 1, it is characterized in that quaternary ammonium hydroxide is selected from TPAOH, TBAH, tetraethyl ammonium hydroxide or Tetramethylammonium hydroxide.
4,, it is characterized in that organic amine select oneself diamines, diethylamine, quadrol, triethylamine or n-Butyl Amine 99 according to the described method for preparing pure silicon MCM-41 molecular sieve of claim 1.
5,, it is characterized in that fluoride salt is selected from least a in Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride or the cesium fluoride according to the described method for preparing pure silicon MCM-41 molecular sieve of claim 1.
6,, it is characterized in that crystallization temperature is 0～40 ℃ according to the described method for preparing pure silicon MCM-41 molecular sieve of claim 1.
7,, it is characterized in that crystallization time is 3～8 hours according to the described method for preparing pure silicon MCM-41 molecular sieve of claim 1.
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| CN 02145240 CN1208246C (en) | 2002-11-13 | 2002-11-13 | Process for preparing pure silicon MCM-41 molecular sieves |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302990C (en) * | 2005-04-13 | 2007-03-07 | 华东理工大学 | Process for preparing and controlling ordered pore structure of mesicpore molecular sieve |
| CN100364888C (en) * | 2005-12-08 | 2008-01-30 | 华东理工大学 | Method for preparing mesoporous molecular sieve |
| CN107840346A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of application of the preparation method of silica zeolite, processing method and silica zeolite, catalyst and catalyst |
| CN107840345A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of application of the preparation method of silica zeolite, processing method and silica zeolite, catalyst and catalyst |
| CN109987613A (en) * | 2019-04-25 | 2019-07-09 | 中触媒新材料股份有限公司 | A kind of method of rapid synthesis pure silicon MCM-41 molecular sieves |
-
2002
- 2002-11-13 CN CN 02145240 patent/CN1208246C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302990C (en) * | 2005-04-13 | 2007-03-07 | 华东理工大学 | Process for preparing and controlling ordered pore structure of mesicpore molecular sieve |
| CN100364888C (en) * | 2005-12-08 | 2008-01-30 | 华东理工大学 | Method for preparing mesoporous molecular sieve |
| CN107840346A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of application of the preparation method of silica zeolite, processing method and silica zeolite, catalyst and catalyst |
| CN107840345A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of application of the preparation method of silica zeolite, processing method and silica zeolite, catalyst and catalyst |
| CN107840345B (en) * | 2016-09-21 | 2019-07-19 | 中国石油化工股份有限公司 | A kind of application of the preparation method of silica zeolite, processing method and silica zeolite, catalyst and catalyst |
| CN109987613A (en) * | 2019-04-25 | 2019-07-09 | 中触媒新材料股份有限公司 | A kind of method of rapid synthesis pure silicon MCM-41 molecular sieves |
| CN109987613B (en) * | 2019-04-25 | 2020-11-24 | 中触媒新材料股份有限公司 | Method for rapidly synthesizing pure silicon MCM-41 molecular sieve |
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|---|---|
| CN1208246C (en) | 2005-06-29 |
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