CN100384733C - Method for preparing sieve of containing titanium MCM-41 - Google Patents
Method for preparing sieve of containing titanium MCM-41 Download PDFInfo
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- CN100384733C CN100384733C CNB2005100287854A CN200510028785A CN100384733C CN 100384733 C CN100384733 C CN 100384733C CN B2005100287854 A CNB2005100287854 A CN B2005100287854A CN 200510028785 A CN200510028785 A CN 200510028785A CN 100384733 C CN100384733 C CN 100384733C
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- molecular sieve
- mcm
- sio
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- titaniferous mcm
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Abstract
This invention relates to a method for preparing Ti-containing MCM-41 molecular sieve. The method comprises: adding polyethylene glycol into the reaction system containing TiCl3, Si source, quaternary ammonium base and templating agent, and reacting to obtain Ti-containing MCM-41 molecular sieve. The method does not add low molecular alcohol in the reaction system, thus has easy operation without the need for removing it by evaporating before crystallization. The method can be used in industrial manufacture of Ti-containing MCM-41 molecular sieve.
Description
Technical field
The present invention relates to a kind of preparation method of titaniferous MCM-41 molecular sieve.
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.Wherein, the HTS with central hole structure makes the gating catalytic oxidation of the bigger organic molecule of volume become possibility.U.S. Pat 5108725, US5102643, US5098684 and US5057296 have described building-up process, and reaction reagent is formed physics and structural performance.
In the preparation of Ti-MCM-41, employed titanium source is organic titanium, and employed silicon source is organosilicon mostly, and is synthetic with hydrothermal method under autogenous pressure.Because the hydrolysis rate of estersil and titanium ester is inconsistent, the too fast TiO that causes of the hydrolysis rate of titanium ester
2Precipitate and the outer titanium species of generation skeleton.When catalyzer was applied to catalyzed reaction, the existence of the outer titanium species of skeleton can cause H
2O
2Be decomposed into H
2And O
2, reduce H
2O
2Effective rate of utilization.Therefore, people propose two kinds of methods and reduce the hydrolysis rate in titanium source to avoid the generation of titanium species outside the skeleton in joining the process of glue.A kind of method is to stir fast when the preparation glue, and before adding quaternary ammonium alkali solution positive tetraethyl orthosilicate/tetraethyl titanate mixture is cooled to-10 ℃; Another kind method is earlier the titanium source to be dissolved in the alcohol, and then adds the silicon source, but before crystallization, the alcohol of adding must evaporate, otherwise can reduce the degree of crystallinity of molecular sieve and the order of structure.Though these two kinds of methods can both reduce the hydrolysis rate in titanium source, thereby avoid TiO
2Sedimentary generation, but building-up process is numerous and diverse and wayward.
Summary of the invention
Technical problem to be solved by this invention is to overcome when having synthesizing titanium-containing MCM-41 molecular sieve in the above-mentioned document owing to add alcohol, it must be evaporated before the crystallization, and the problem of troublesome poeration provides a kind of new method for preparing titaniferous MCM-41 molecular sieve.It is low that this method has a crystallization temperature, and building-up process is simplified and manageable characteristics relatively.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of titaniferous MCM-41 molecular sieve is the silicon source with tetraethyl orthosilicate, silicon sol or silicon gel, is the titanium source with the titanous chloride, alkyl trimethyl ammonium halogenide C
mH
2m+1(CH
3)
3NX is a template, and quaternary ammonium hydroxide RN and molecular weight are 1000～20000 polyoxyethylene glycol PG and water composition mixture, wherein with molar ratio computing are: Si/Ti=20～200, C
mH
2m+1(CH
3)
3NX/SiO
2=0.05～0.7, H
2O/SiO
2=40～200, RN/SiO
2=0.1～0.45, PG/C
mH
2m+1(CH
3)
3NX=0.02～0.2, m=12～18, X is a halogen; Above-mentioned reaction mixture was at room temperature stirred crystallization 18～96 hours, and crystallized product gets titaniferous MCM-41 molecular sieve through separation, washing, drying, roasting.
In the technique scheme, template alkyl trimethyl ammonium halogenide C
mH
2m+1(CH
3)
3The NX preferred version is a cetyl trimethylammonium bromide; The quaternary ammonium hydroxide preferred version is for being selected from TPAOH, TBAH, tetraethyl ammonium hydroxide or Tetramethylammonium hydroxide; The crystallization time preferable range is 48～70 hours; The molecular weight polyethylene glycol preferable range is 2000～20000.
The present invention is the titanium source owing to adopting titanous chloride, and has added polyoxyethylene glycol in reaction system, and crystallization can be carried out under lower temperature, and the synthetic molecular sieve containing titanium has typical MCM-41 XRD diffracting spectrum.Simultaneously building-up process simplify relatively, easy to control, obtained better technical effect.
Description of drawings
Fig. 1 is the XRD diffractogram of synthetic titaniferous MCM-41 molecular sieve of the present invention.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
The mixing solutions that titanium trichloride aqueous solution (17 weight % concentration), 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 50 positive tetraethyl orthosilicate of gram and a certain amount of polyoxyethylene glycol (molecular weight 6000), violent stirring is 48 hours again.The relative molar content of each component wherein:
SiO
2/TiO
2＝40，CTMABr/SiO
2＝0.2，TEAOH/SiO
2＝0.35，H
2O/SiO
2＝45，
PG/CTMABr＝0.08
After crystallization finishes, isolate crystallized product, after 80 ℃ of dryings, work in-process are roasting 5～8 hours in roasting 1 hour, the air in 550 ℃ of stream of nitrogen gas, then the Ti-MCM41 mesoporous molecular sieve, have typical MCM-41 XRD diffractive features peak.
[embodiment 2]
The mixing solutions that titanium trichloride aqueous solution (17 weight % concentration), cetyl trimethylammonium bromide (CTMABr), Tetramethylammonium hydroxide (TMAOH), 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 50 positive tetraethyl orthosilicate of gram and a certain amount of polyoxyethylene glycol (molecular weight 20000), violent stirring is 48 hours again.The relative molar content of each component wherein:
SiO
2/TiO
2＝30，CTMABr/SiO
2＝0.2，TMAOH/SiO
2＝0.26，H
2O/SiO
2＝40，
PG/CTMABr＝0.02
After crystallization finishes, isolate crystallized product, after 80 ℃ of dryings, work in-process are roasting 5～8 hours in roasting 1 hour, the air in 550 ℃ of stream of nitrogen gas, then the Ti-MCM-41 mesoporous molecular sieve, have typical MCM-41 XRD diffractive features peak.
[embodiment 3]
The mixing solutions that titanium trichloride aqueous solution (17 weight % concentration), palmityl trimethyl ammonium chloride (CTMACl), 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 50 gram 40% silicon sol and a certain amount of polyoxyethylene glycol (molecular weight 6000), violent stirring is 48 hours again.The relative molar content of each component wherein:
SiO
2/TiO
2＝85，CTMACl/SiO
2＝0.25，TEAOH/SiO
2＝0.3，H
2O/SiO
2＝60，
PG/CTMACl＝0.05
After crystallization finishes, isolate crystallized product, after 80 ℃ of dryings, work in-process are roasting 5～8 hours in roasting 1 hour, the air in 550 ℃ of stream of nitrogen gas, then the Ti-MCM-41 mesoporous molecular sieve, have typical MCM-41 XRD diffractive features peak.
[embodiment 4]
The mixing solutions that titanium trichloride aqueous solution (17 weight % concentration), palmityl trimethyl ammonium chloride (CTMACl), TBAH (TBAOH), the water of requirement are formed is added in the container of band whipping appts.At room temperature after the stirring and dissolving, add 50 gram 40% silicon sol and a certain amount of polyoxyethylene glycol (molecular weight 4000), violent stirring is 48 hours again.The relative molar content of each component wherein:
SiO
2/TiO
2＝150，CTMACl/SiO
2＝0.5，TBAOH/SiO
2＝0.15，H
2O/SiO
2＝60，
PG/CTMACl＝0.15
After crystallization finishes, isolate crystallized product, after 80 ℃ of dryings, work in-process are roasting 5～8 hours in roasting 1 hour, the air in 550 ℃ of stream of nitrogen gas, then the Ti-MCM-41 mesoporous molecular sieve, have typical MCM-41 XRD diffractive features peak.
Claims (5)
1. the preparation method of a titaniferous MCM-41 molecular sieve is the silicon source with tetraethyl orthosilicate, silicon sol or silicon gel, is the titanium source with the titanous chloride, alkyl trimethyl ammonium halogenide C
mH
2m+1(CH
3)
3NX is a template, and quaternary ammonium hydroxide RN and molecular weight are 1000～20000 polyoxyethylene glycol PG and water composition mixture, wherein with molar ratio computing are: Si/Ti=20～200, C
mH
2m+1(CH
3)
3NX/SiO
2=0.05～0.7, H
2O/SiO
2=40～200, RN/SiO
2=0.1～0.45, PG/C
mH
2m+1(CH
3)
3NX=0.02～0.2, m=12～18, X is a halogen; Above-mentioned reaction mixture was at room temperature stirred crystallization 18～96 hours, and crystallized product gets titaniferous MCM-41 molecular sieve through separation, washing, drying, roasting.
2. according to the preparation method of the described titaniferous MCM-41 of claim 1 molecular sieve, it is characterized in that alkyl trimethyl ammonium halogenide is cetyl trimethylammonium bromide.
3. according to the preparation method of the described titaniferous MCM-41 of claim 1 molecular sieve, it is characterized in that quaternary ammonium hydroxide is selected from TPAOH, TBAH, tetraethyl ammonium hydroxide or Tetramethylammonium hydroxide.
4. according to the preparation method of the described titaniferous MCM-41 of claim 1 molecular sieve, it is characterized in that crystallization time is 48～70 hours.
5. according to the preparation method of the described titaniferous MCM-41 of claim 1 molecular sieve, it is characterized in that molecular weight polyethylene glycol is 2000～20000.
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|---|---|---|---|
| CNB2005100287854A CN100384733C (en) | 2005-08-15 | 2005-08-15 | Method for preparing sieve of containing titanium MCM-41 |
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| CN100384733C true CN100384733C (en) | 2008-04-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502429B (en) * | 2015-12-30 | 2017-06-30 | 山西大同大学 | A kind of preparation method of mesopore molecular sieve |
| CN111905798B (en) * | 2019-05-09 | 2023-04-07 | 中国科学院大连化学物理研究所 | Preparation method and application of titanium-containing mesoporous material MCM-41 |
| CN110813373A (en) * | 2019-11-27 | 2020-02-21 | 吉林大学 | Titanium-silicon molecular sieve catalyst, preparation method and application thereof in olefin epoxidation reaction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| US5783167A (en) * | 1993-06-15 | 1998-07-21 | Consejo Superior Investigaciones Cientificas | Structure material of the zeolite type with ultralarge pores and a lattice comprised of silicone and titanium oxides: its synthesis and utilization for the selective oxidation of organic products |
| CN1239016A (en) * | 1998-06-12 | 1999-12-22 | 中国石油化工总公司 | Process for preparing Ti-Si molecular sieve |
| CN1475442A (en) * | 2002-08-15 | 2004-02-18 | 中国石油化工股份有限公司 | Preparation method of titanium silicon moleculor sieve |
-
2005
- 2005-08-15 CN CNB2005100287854A patent/CN100384733C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| US5783167A (en) * | 1993-06-15 | 1998-07-21 | Consejo Superior Investigaciones Cientificas | Structure material of the zeolite type with ultralarge pores and a lattice comprised of silicone and titanium oxides: its synthesis and utilization for the selective oxidation of organic products |
| CN1239016A (en) * | 1998-06-12 | 1999-12-22 | 中国石油化工总公司 | Process for preparing Ti-Si molecular sieve |
| CN1475442A (en) * | 2002-08-15 | 2004-02-18 | 中国石油化工股份有限公司 | Preparation method of titanium silicon moleculor sieve |
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| CN1915818A (en) | 2007-02-21 |
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