CN101012063A - Method for preparing titanium-containing molecular sieve - Google Patents
Method for preparing titanium-containing molecular sieve Download PDFInfo
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- CN101012063A CN101012063A CN 200710061509 CN200710061509A CN101012063A CN 101012063 A CN101012063 A CN 101012063A CN 200710061509 CN200710061509 CN 200710061509 CN 200710061509 A CN200710061509 A CN 200710061509A CN 101012063 A CN101012063 A CN 101012063A
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- molecular sieve
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Abstract
The invention discloses a making method of dielectric hole molecular sieve with titanium, which comprises the following steps: dissolving surface activator in the deionized water; forming even solution with density at 0.1-10%; dripping titanium source, silicon source and alcohol solutin; stirring; aging; filtering; washing through deionized water until the pH value is 6-8; drying; sintering; obtaining the product with visible catalytic activity.
Description
Technical field
The invention belongs to a kind of method for preparing titanium-containing meso-porous molecular sieve, specifically a kind of synthetic method with titanium-containing meso-porous molecular sieve of daylight photocatalytic activity.
Background technology
Since Corma in 1994 etc. had synthesized the Ti-MCM-41 molecular sieve first, the unique texture of Ti-MCM-41 molecular sieve and catalytic oxidation performance thereof had caused academia's extensive concern.At present synthetic Ti-MCM-41 molecular sieve generally adopts hydrothermal crystallization method in the alkaline medium or the ELECTROSTATIC S in the strong acid media
+X
-I
+" the assembling approach.The former easily causes the formation of extra-framework titanium, and the existence of extra-framework titanium can make the decomposing hydrogen dioxide solution as oxygenant, thereby the catalytic activity of Ti-MCM-41 molecular sieve is reduced greatly; Then there is the problem that the molecular sieve granularity is big, the catalyst surface utilization ratio is low in the latter.And with this kind method synthetic mesopore molecular sieve, the content of titanium is lower, and titanium silicon ratio is generally about 1: 100 (mol ratio), as photocatalyst material, is not too desirable.
Summary of the invention
The present invention provides the method for the mesopore molecular sieve of preparation high titanium content in a kind of room temperature following table surfactant system.
The present invention is achieved in that under the room temperature in the certain density surfactant soln, slowly add titanium, silicon and alcoholic acid mixing solutions, stir and make its formation gel, ageing under the room temperature, wash then, filter, dry, roasting, obtain having the titanium-containing meso-porous molecular sieve of photocatalytic activity.
Preparation method of the present invention comprises the steps:
(1), tensio-active agent is dissolved in the deionized water, make it form homogeneous solution, the mass concentration of solution is 0.1%～10%;
(2), be 1～5: 0～9 by the molar ratio of titanium, silicon and dehydrated alcohol: 1～5, titanium source and silicon source be dissolved in be made into mixing solutions in the dehydrated alcohol;
(3), be 1～10: 0.1～1 by the mol ratio of titanium and tensio-active agent, the mixing solutions of the titanium, silicon and the dehydrated alcohol that prepare is added drop-wise in the surfactant soln, fully stirred room temperature ageing 1～2 day 10 hours～24 hours;
(4), filter, and with deionized water wash to pH6～8, drying 450 ℃～600 ℃ roastings 3～8 hours, obtains titanium-containing meso-porous molecular sieve.
Used tensio-active agent is cats product, anion surfactant and nonionogenic tenside.Wherein cats product comprises cetyl trimethylammonium bromide (CTAB), cetyltriethylammonium bromide (CTEAB), distearyl dimethyl ammonium chloride (D1821), dodecyl benzyl dimethyl ammonium chloride (1227) etc.; Anion surfactant comprises sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkenyl sulphonate, alcohol ether carboxylate etc.; Ionic surfactant pack is drawn together Soxylat A 25-7 (AEO) series of surfactants.
Described Soxylat A 25-7 (AEO) series of surfactants is C
10～12H
22～26(EO)
9H, C
8～10H
18～22(EO)
9H, C
12～14H
22～26(EO)
7H etc.
Used silicon source is: tetraethoxy, water glass, white carbon black, water glass, silicon sol or solid silicone bead, tetramethoxy-silicane etc.
Used titanium source is: tetra-n-butyl titanate, metatitanic acid four inclined to one side propyl ester, titanium tetrachloride, titanium tetrafluoride, titanium sulfate, titanyl sulfate etc.
The present invention compared with prior art has following advantage:
Compare with general synthetic method, the present invention utilizes the formed special supramolecular structure of tensio-active agent amphiphile, amphiphilic molecule, has at room temperature directly synthesized the titanium-containing meso-porous molecular sieve with daylight photocatalytic activity, and synthesis technique is simple, the reaction conditions gentleness is suitable for suitability for industrialized production.Compare with the technology of existing suitability for industrialized production, desired equipment is also simple relatively.
Embodiment
Embodiment 1
Under the room temperature, distearyl dimethyl ammonium chloride (D1821) cats product is dissolved in to be mixed with mass percent concentration in the deionized water be 0.5% homogeneous solution 100ml, the mixing solutions 30ml of butyl (tetra) titanate, tetraethoxy and dehydrated alcohol (mol ratio is 2: 8: 5) is slowly added, fully stirred 24 hours, room temperature ageing 2 days, filter, deionized water wash is to pH6, drying at room temperature, roasting is 8 hours in 450 ℃ of retort furnaces, obtains titanium-containing meso-porous molecular sieve (titanium silicon mol ratio 2: 8) product.
Embodiment 2
Under the room temperature, the alcohol ether carboxylate salt anionic surfactant is dissolved in to be mixed with mass percent concentration in the deionized water be 3% homogeneous solution 100ml, the mixing solutions 30ml of butyl (tetra) titanate, silicon sol and dehydrated alcohol (mol ratio is 2: 8: 5) is slowly added, fully stirred 10 hours, room temperature ageing 2 days is filtered, deionized water wash is to pH7, drying at room temperature, roasting is 5 hours in 550 ℃ of retort furnaces, obtains titanium-containing meso-porous molecular sieve (titanium silicon mol ratio 2: 8) product.
Embodiment 3
Under the room temperature, nonionogenic tenside fatty acid methyl ester ethoxylate (FMEE) is dissolved in that to be mixed with mass percent concentration in the deionized water be 10% homogeneous solution 200ml, the mixing solutions 30ml of titanyl sulfate, tetraethoxy and dehydrated alcohol (mol ratio is 5: 5: 5) is slowly added, fully stirred 16 hours, room temperature ageing 2 days, filter, deionized water wash is to pH6, drying at room temperature, roasting is 6 hours in 500 ℃ of retort furnaces, obtains molecular sieve containing titanium (titanium silicon mol ratio 5: 5) product.
Embodiment 4
Under the room temperature, cats product distearyl dimethyl ammonium chloride (D1821) is dissolved in that to be mixed with mass percent concentration in the deionized water be 3% homogeneous solution 100ml, mixing solutions 40ml with butyl (tetra) titanate, white carbon black and dehydrated alcohol (mol ratio is 1: 9: 3) slowly adds then, fully stirred 24 hours, room temperature ageing 2 days, filter, deionized water wash is to pH7, drying at room temperature, roasting is 5 hours in 550 ℃ of retort furnaces, obtains titanium-containing meso-porous molecular sieve (titanium silicon mol ratio 1: 9) product.
Embodiment 5
Under the room temperature, the anion surfactant alcohol ether carboxylate is dissolved in that to be mixed with mass percent concentration in the deionized water be 6% homogeneous solution 100ml, mixing solutions 25ml with titanium tetrachloride, tetraethoxy and dehydrated alcohol (mol ratio is 3: 7: 1) slowly adds then, fully stirred 20 hours, room temperature ageing 2 days is filtered, deionized water wash is to pH8, drying at room temperature, roasting is 3 hours in 600 ℃ of retort furnaces, obtains titanium-containing meso-porous molecular sieve (titanium silicon mol ratio 3: 7) product.
Embodiment 6
Under the room temperature, the anion surfactant alcohol ether carboxylate is dissolved in that to be mixed with mass percent concentration in the deionized water be 3% homogeneous solution 100ml, the mixing solutions 30ml of metatitanic acid four inclined to one side propyl ester, tetramethylsilane and dehydrated alcohol (mol ratio is 2: 8: 5) is slowly added, fully stirred 10 hours, room temperature ageing 2 days is filtered, deionized water wash is to pH6, drying at room temperature, roasting is 4 hours in 580 ℃ of retort furnaces, obtains titanium-containing meso-porous molecular sieve (titanium silicon mol ratio 2: 8) product.
Embodiment 7
Under the room temperature, cats product distearyl dimethyl ammonium chloride (D1821) is dissolved in that to be mixed with mass percent concentration in the deionized water be 3% homogeneous solution 100ml, mixing solutions 50ml with butyl (tetra) titanate, water glass and dehydrated alcohol (mol ratio is 1: 6: 3) slowly adds then, fully stirred 24 hours, room temperature ageing 2 days, filter, deionized water wash is to pH8, drying at room temperature, roasting is 5 hours in 530 ℃ of retort furnaces, obtains titanium-containing meso-porous molecular sieve (titanium silicon mol ratio 1: 6) product.
Embodiment 8
Under the room temperature, cats product distearyl dimethyl ammonium chloride (D1821) is dissolved in that to be mixed with mass percent concentration in the deionized water be 5% homogeneous solution 100ml, the mixing solutions 30ml of metatitanic acid four inclined to one side propyl ester, water glass and dehydrated alcohol (mol ratio is 2: 8: 5) is slowly added, fully stirred 24 hours, room temperature ageing 2 days, filter, deionized water wash is to pH6, drying at room temperature, roasting is 5 hours in 550 ℃ of retort furnaces, obtains titanium-containing meso-porous molecular sieve (titanium silicon mol ratio 2: 8) product.
Embodiment 9
Under the room temperature, nonionogenic tenside C
10～12H
22～26(EO)
9H is dissolved in that to be mixed with mass percent concentration in the deionized water be 01% homogeneous solution 100ml, the mixing solutions 50ml of titanium sulfate, tetraethoxy and dehydrated alcohol (mol ratio is 1: 0: 5) is slowly added, fully stirred 12 hours, room temperature ageing 2 days, filter, deionized water wash is to pH7, drying at room temperature, roasting is 3 hours in 600 ℃ of retort furnaces, obtains pure titanium mesopore molecular sieve product.
Claims (8)
1, a kind of method for preparing titanium-containing meso-porous molecular sieve is characterized in that comprising the steps:
(1), tensio-active agent is dissolved in the deionized water, make it form homogeneous solution, the mass concentration of solution is 0.1%～10%;
(2), be 1～5: 0～9 by the molar ratio of titanium, silicon and dehydrated alcohol: 1～5, titanium source and silicon source be dissolved in be made into mixing solutions in the dehydrated alcohol;
(3), be 1～10: 0.1～1 by the mol ratio of titanium and tensio-active agent, the mixing solutions of the titanium, silicon and the dehydrated alcohol that prepare is added drop-wise in the surfactant soln, fully stirred room temperature ageing 1～2 day 10 hours～24 hours;
(4), filter, and with deionized water wash to pH6～8, drying 450 ℃～600 ℃ roastings 3～8 hours, obtains titanium-containing meso-porous molecular sieve.
2, a kind of method for preparing titanium-containing meso-porous molecular sieve as claimed in claim 1 is characterized in that described tensio-active agent is cats product, anion surfactant or nonionogenic tenside.
3, a kind of method for preparing titanium-containing meso-porous molecular sieve as claimed in claim 2 is characterized in that described cats product is cetyl trimethylammonium bromide, cetyltriethylammonium bromide, distearyl dimethyl ammonium chloride or dodecyl benzyl dimethyl ammonium chloride.
4, a kind of method for preparing titanium-containing meso-porous molecular sieve as claimed in claim 2 is characterized in that described anion surfactant is sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkenyl sulphonate or alcohol ether carboxylate.
5, a kind of method for preparing titanium-containing meso-porous molecular sieve as claimed in claim 2 is characterized in that described nonionogenic tenside is the Soxylat A 25-7 series of surfactants.
6, a kind of method for preparing titanium-containing meso-porous molecular sieve as claimed in claim 5 is characterized in that described Soxylat A 25-7 series of surfactants is C
10～12H
22～26(EO)
9H, C
8～10H
18～22(EO)
9H, C
12～14H
22～26(EO)
7H etc.
7, a kind of method for preparing titanium-containing meso-porous molecular sieve as claimed in claim 1 is characterized in that described silicon source is tetraethoxy, water glass, white carbon black, water glass, silicon sol, solid silicone bead or tetramethoxy-silicane.
8, a kind of method for preparing titanium-containing meso-porous molecular sieve as claimed in claim 1 is characterized in that described titanium source is tetra-n-butyl titanate, metatitanic acid four inclined to one side propyl ester, titanium tetrachloride, titanium tetrafluoride, titanium sulfate or titanyl sulfate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497450B (en) * | 2008-01-31 | 2011-11-02 | 中国石油化工股份有限公司 | Method for preparing titanium-containing mesoporous material |
| CN102344150A (en) * | 2010-07-29 | 2012-02-08 | 中国石油化工股份有限公司 | Synthetic method for mesopore titanium-silicon molecular sieve |
| CN102372283A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve and its preparation method |
| CN105498832A (en) * | 2014-10-20 | 2016-04-20 | 中国石油化工股份有限公司 | Preparation method for catalyst used for preparing 1,2-epoxybutane through epoxidation of 1-butene |
| CN110482566A (en) * | 2019-09-02 | 2019-11-22 | 杭州电子科技大学 | A kind of meso titanium silica compound and its application in nucleic acid molecules detection |
-
2007
- 2007-02-07 CN CNB2007100615097A patent/CN100554157C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497450B (en) * | 2008-01-31 | 2011-11-02 | 中国石油化工股份有限公司 | Method for preparing titanium-containing mesoporous material |
| CN102344150A (en) * | 2010-07-29 | 2012-02-08 | 中国石油化工股份有限公司 | Synthetic method for mesopore titanium-silicon molecular sieve |
| CN102372283A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve and its preparation method |
| CN105498832A (en) * | 2014-10-20 | 2016-04-20 | 中国石油化工股份有限公司 | Preparation method for catalyst used for preparing 1,2-epoxybutane through epoxidation of 1-butene |
| CN105498832B (en) * | 2014-10-20 | 2018-12-28 | 中国石油化工股份有限公司 | The preparation method of the catalyst of 1,2- epoxy butane is prepared for 1- butylene epoxidation |
| CN110482566A (en) * | 2019-09-02 | 2019-11-22 | 杭州电子科技大学 | A kind of meso titanium silica compound and its application in nucleic acid molecules detection |
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| CN100554157C (en) | 2009-10-28 |
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