CN100430318C - Method of synthesizing titanium containing porous material - Google Patents
Method of synthesizing titanium containing porous material Download PDFInfo
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- CN100430318C CN100430318C CNB2004100666377A CN200410066637A CN100430318C CN 100430318 C CN100430318 C CN 100430318C CN B2004100666377 A CNB2004100666377 A CN B2004100666377A CN 200410066637 A CN200410066637 A CN 200410066637A CN 100430318 C CN100430318 C CN 100430318C
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Abstract
The present invention relates to a synthetic method for porous materials containing titanium, which mainly overcomes the disadvantage of easy generation of non-skeleton titanium kinds in the synthesis of porous materials containing titanium originally. The synthetic method perfectly solves the problem by the technical scheme that a mixture comprising tetraethyl orthosilicate or silicasol used as a silicon source, tetrabutyl titanate used as a titanium source, primary amines used as templates, organic alcohol used as solvent and water is used for controlling the water content in reaction synthetic systems, and synthetic porous materials containing titanium have the characteristic of small pore diameters. The synthetic method can be used for industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of titanium containing porous material.
Background technology
Molecular sieve containing titanium is a class environment-friendly catalyst, and it successfully synthesizes is the important milestone in molecular sieve catalytic field.U.S. Pat 4410501 has been introduced the synthetic of titanium-silicon molecular sieve TS-1 first.TS-1 has MFI structure micro-pore zeolite, titanium atom has entered its skeleton structure with high dispersion state, titanium-silicon molecular sieve TS-1 has good catalytic activity to the selective oxidation of various organic reactions, selective oxidation preparing benzenediol as phenol, ammoxidation of cyclohexanone preparing cyclohexanone oxime, the epoxidation of alkene etc.Document Nature 368,321-323 (1994) has introduced the synthetic of a kind of novel molecular sieve containing titanium Ti-HMS with middle hole characteristic, this Ti-HMS is a synthetic in water and ethanol mixed solvent, and its water/pure volume ratio is near 2, and the aperture of the Ti-HMS that makes is greater than 25
In molecular sieve containing titanium synthetic, generally adopting estersil and titanium ester is starting raw material.Yet because the hydrolysis rate of estersil and titanium ester is inconsistent, in containing the system of big water gaging, the hydrolysis rate of titanium ester is too fast, causes TiO easily
2Precipitate and the outer titanium species of generation skeleton.The existence of extra-framework titanium has not only reduced the catalyst activity, also can cause H simultaneously
2O
2Decompose, reduce H
2O
2Effective rate of utilization.
Summary of the invention
The objective of the invention is in order to overcome in the past in the titanium containing porous material synthetic system water-content too high, generate the shortcoming of extra-framework titanium species easily, a kind of synthetic method of new titanium containing porous material is provided, make titanium atom high dispersing in the synthetic titanium containing porous material, promptly avoid the formation of extra-framework titanium species, and the titanium containing porous material that makes have the little characteristics in aperture.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of synthetic method of titanium containing porous material, with tetraethyl orthosilicate or silicon sol is the silicon source, tetrabutyl titanate is the titanium source, primary amine is a template, organic alcohol is solvent, with the titanium source, silicon source and alcoholic solvent are mixed and made into Sol A, and template and alcoholic solvent and water be mixed and made into sol B, again Sol A is added composition mixture in the sol B under violent stirring, wherein be with molar ratio computing: Si/Ti=5～200, primary amine/Si=0.05～0.7, water/pure volume ratio is 0.01～1, above-mentioned reaction mixture was at room temperature stirred crystallization 1～100 hour, crystallized product is through separating, washing, drying, remove template with alcohol extraction or 500～600 ℃ of roastings after, obtain titanium containing porous material.
In the technique scheme, the primary amine preferable range is that carbonatoms is 6～18 primary amine, more preferably amino dodecane or cetylamine.The crystallization time preferable range is 2～24 hours.Used organic alcohol is preferably a kind of of ethanol, Virahol or the trimethyl carbinol or its mixture.Water in the reaction mixture/pure volume ratio preferable range is 0.1～0.5.
The present invention is owing to adopt organic alcohol as reaction solvent, the water yield in the control reaction synthetic system, only added the water yield that guarantees silicon source and the hydrolysis of titanium source, stoped the generation of extra-framework titanium species effectively, and be surprised to find that the titanium containing porous material that makes has the little characteristics in aperture, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
10 gram tetrabutyl titanates are added in the 208 positive tetraethyl orthosilicates of gram and the 300 milliliters of alcoholic acid mixing solutionss, continuously stirring half hour, form uniform sol A.Again 65 gram cetylamines are dissolved in the mixing solutions of 200 milliliters of ethanol and 80 ml waters, until forming uniform sol B.Under violent stirring, Sol A is added in the sol B then, and continue to stir 2 hours.Final solid phase prod separates after filtration, behind deionized water wash, and drying at room temperature 24 hours.Wherein each component with molar ratio computing is: SiO
2/ TiO
2=34, cetylamine/SiO
2=0.27, water/pure volume ratio is 0.16.Template is removed with the alcohol extraction method.The surface characteristic of the titanium containing porous material that makes sees Table 1.
[embodiment 2]
34 gram tetrabutyl titanates are added in the mixing solutions of 210 gram tetraethyl orthosilicates and 300 milliliters of Virahols, and continuously stirring 1 hour forms uniform sol A.Again 84 gram cetylamines are dissolved in the mixing solutions of 262 milliliters of Virahols and 90 ml waters, until forming uniform sol B.Under violent stirring, Sol A is added in the sol B then, and continue to stir 3 hours.Final solid phase prod separates after filtration, behind deionized water wash, and drying at room temperature 24 hours.Wherein each component with molar ratio computing is: SiO
2/ TiO
2=10, cetylamine/SiO
2=0.35, water/pure volume ratio is 0.16.Template is removed with the alcohol extraction method.The surface characteristic of the titanium containing porous material that makes sees Table 1.
[embodiment 3]
6.8 gram tetrabutyl titanates are added 150 gram silicon sol (SiO
240 weight %) and in the mixing solutions of 300 milliliters of trimethyl carbinols, continuously stirring half hour, form uniform sol A.Again 96 gram amino dodecanes are dissolved in the mixing solutions of 600 milliliters of trimethyl carbinols and 100 ml waters, until forming uniform sol B.Under violent stirring, Sol A is added in the sol B then, and continue to stir 18 hours.Final solid phase prod separates after filtration, behind deionized water wash, and drying at room temperature 24 hours.Wherein each component with molar ratio computing is: SiO
2/ TiO
2=50, amino dodecane/SiO
2=0.52, water/pure volume ratio is 0.11.Template is removed in 530 ℃ of roastings.The surface characteristic of the titanium containing porous material that makes sees Table 1.
[embodiment 4]
3.4 gram tetrabutyl titanates are added 150 gram silicon sol (SiO
240 weight %) and in the 300ml alcoholic acid mixing solutions, continuously stirring half hour, form uniform sol A.Again 28 gram amino dodecanes are dissolved in the mixing solutions of 262 milliliters of ethanol and 90 ml waters, until forming uniform sol B.Under violent stirring, Sol A is added in the sol B then, and continue to stir 5 hours.Final solid phase prod separates after filtration, behind deionized water wash, and drying at room temperature 24 hours.Wherein each component with molar ratio computing is: SiO
2/ TiO
2=100, amino dodecane/SiO
2=0.15, water/pure volume ratio is 0.16.Template is removed in 550 ℃ of roastings.The surface characteristic of the titanium containing porous material that makes sees Table 1.
[embodiment 5]
10 gram tetrabutyl titanates are added in the mixing solutions of 210 gram tetraethyl orthosilicates and 200 milliliters of trimethyl carbinols, continuously stirring half hour, form uniform sol A.Again 169 gram cetylamines are dissolved in the mixing solutions of 500 milliliters of trimethyl carbinols and 200 ml waters, until forming uniform sol B.Under violent stirring, Sol A is added in the sol B then, and continue to stir 8 hours.Final solid phase prod separates after filtration, behind deionized water wash, and drying at room temperature 24 hours.Wherein each component with molar ratio computing is: SiO
2/ TiO
2=33, cetylamine/SiO
2=0.70, water/pure volume ratio is 0.25.Template is removed with the alcohol extraction method.The surface characteristic of the titanium containing porous material that makes sees Table 1.
[embodiment 6]
2.3 gram tetrabutyl titanates are added in the mixing solutions of 210 gram tetraethyl orthosilicates and 200 milliliters of Virahols, continuously stirring half hour, form uniform sol A.Again 24 gram cetylamines are dissolved in the mixing solutions of 550 milliliters of trimethyl carbinols and 250 ml waters, until forming uniform sol B.Under violent stirring, Sol A is added in the sol B then, and continue to stir 24 hours.Final solid phase prod separates after filtration, behind deionized water wash, and drying at room temperature 24 hours.Wherein each component with molar ratio computing is: SiO
2/ TiO
2=150, cetylamine/SiO
2=0.10, water/pure volume ratio is 0.33.Template is removed in 530 ℃ of roastings.The surface characteristic of the titanium containing porous material that makes sees Table 1.
[Comparative Examples]
2.3 gram tetrabutyl titanates are added in the mixing solutions of 208 gram tetraethyl orthosilicates and 200 milliliters of Virahols, continuously stirring half hour, form uniform sol A.Again 24 gram cetylamines are dissolved in the 360 ml water solution, until forming uniform sol B.Under violent stirring, Sol A is added in the sol B then, and continue to stir 24 hours.Final solid phase prod separates after filtration, behind deionized water wash, and drying at room temperature 24 hours.Wherein each component with molar ratio computing is: SiO
2/ TiO
2=150, cetylamine/SiO
2=0.10, water/pure volume ratio is 1.8.Template is removed in 530 ℃ of roastings.The surface characteristic of the titanium containing porous material that makes sees Table 1.
The surface characteristic of synthetic titanium containing porous material under table 1 different condition
Claims (6)
1, a kind of synthetic method of titanium containing porous material, with tetraethyl orthosilicate or silicon sol is the silicon source, tetrabutyl titanate is the titanium source, primary amine is a template, organic alcohol is solvent, with the titanium source, silicon source and alcoholic solvent are mixed and made into Sol A, and template and alcoholic solvent and water be mixed and made into sol B, again Sol A is added composition mixture in the sol B under violent stirring, wherein be: Si/Ti=5～200 with molar ratio computing, primary amine/Si=0.05～0.7, water/pure volume ratio is 0.01～1, and above-mentioned reaction mixture was at room temperature stirred crystallization 1～100 hour, and crystallized product is through separating, washing, dry, after removing template with alcohol extraction or 500～600 ℃ of roastings, obtain titanium containing porous material.
2,, it is characterized in that described primary amine is that carbonatoms is 6～18 primary amine according to the synthetic method of the described titanium containing porous material of claim 1.
3,, it is characterized in that described primary amine is amino dodecane or cetylamine according to the synthetic method of the described titanium containing porous material of claim 2.
4,, it is characterized in that crystallization time is 2～24 hours according to the synthetic method of the described titanium containing porous material of claim 1.
5,, it is characterized in that described organic alcohol is a kind of or its mixture in ethanol, Virahol or the trimethyl carbinol according to the synthetic method of the described titanium containing porous material of claim 1.
6,, it is characterized in that water in the reaction mixture/pure volume ratio is 0.1～0.5 according to the synthetic method of the described titanium containing porous material of claim 1.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327947A (en) * | 2001-06-13 | 2001-12-26 | 中国科学院兰州化学物理研究所 | Process for preparing Ti-Si molecular sieve |
| WO2002060580A1 (en) * | 2001-01-31 | 2002-08-08 | Sumitomo Chemical Company, Limited | Process for production of titanium-containing silicon oxide catalysts |
| CN1401569A (en) * | 2002-08-26 | 2003-03-12 | 大连理工大学 | Method for quick synthesis of Ti-Si nano molecular sieve catalyst and use thereof |
| CN1418813A (en) * | 2001-11-14 | 2003-05-21 | 中国石油化工股份有限公司 | Method for quick synthesis of titanium silicon molecular sieve |
| CN1488438A (en) * | 2003-07-04 | 2004-04-14 | 华东师范大学 | Method for preparing titanium-silicon molecular sieve |
| CN1513760A (en) * | 2002-12-31 | 2004-07-21 | 中国石油化工股份有限公司 | Method of synthesizing titanium silicon molecular sieve |
-
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- 2004-09-24 CN CNB2004100666377A patent/CN100430318C/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002060580A1 (en) * | 2001-01-31 | 2002-08-08 | Sumitomo Chemical Company, Limited | Process for production of titanium-containing silicon oxide catalysts |
| CN1327947A (en) * | 2001-06-13 | 2001-12-26 | 中国科学院兰州化学物理研究所 | Process for preparing Ti-Si molecular sieve |
| CN1418813A (en) * | 2001-11-14 | 2003-05-21 | 中国石油化工股份有限公司 | Method for quick synthesis of titanium silicon molecular sieve |
| CN1401569A (en) * | 2002-08-26 | 2003-03-12 | 大连理工大学 | Method for quick synthesis of Ti-Si nano molecular sieve catalyst and use thereof |
| CN1513760A (en) * | 2002-12-31 | 2004-07-21 | 中国石油化工股份有限公司 | Method of synthesizing titanium silicon molecular sieve |
| CN1488438A (en) * | 2003-07-04 | 2004-04-14 | 华东师范大学 | Method for preparing titanium-silicon molecular sieve |
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