CN101428814A - Synthesis of titanium-silicon molecular sieve TS-1 - Google Patents
Synthesis of titanium-silicon molecular sieve TS-1 Download PDFInfo
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- CN101428814A CN101428814A CNA2007100478827A CN200710047882A CN101428814A CN 101428814 A CN101428814 A CN 101428814A CN A2007100478827 A CNA2007100478827 A CN A2007100478827A CN 200710047882 A CN200710047882 A CN 200710047882A CN 101428814 A CN101428814 A CN 101428814A
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- molecular sieve
- titanium
- silicon molecular
- quaternary ammonium
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Abstract
The invention relates to a method for synthesizing titanium silicon molecular sieve TS-1, which aims to solve the problems in the prior art that the existence of alkali metal ions in TPAOH causes the synthesized TS-1 catalytic activity reduction, even complete inactivation, TPAOH without metal ions is difficult to obtain, and the price is high. The invention adopts and mixes silicon source, titanium source, quaternary ammonium salt, water and anion exchange resin containing OH<-> according to the following mol ratio: SiO2/TiO2 10-200, OH<->/SiO2 0.03-1.0, H2O/SiO2 20-60, and R/SiO2 0.005-1.0, wherein, R refers to quaternary ammonium salt; and the mixer is stirred at the crystallization temperature being 120-200 DEG C, then taken out after crystallization for 5-100 hours, washed, dried and baked to obtain the TS-1 molecular sieve. The problems are well solved and the invention can be used in manufacturing production of synthesizing titanium silicon molecular sieves.
Description
Technical field
The present invention relates to the synthetic method of titanium-silicon molecular sieve TS-1.
Background technology
HTS is a kind of active catalytic material of good catalytic selective oxidation that has.In reactions such as benzene oxidation system phenol, oxidation of phenol preparing benzenediol, oxidation of alkanes system ketone and alcohol, ammoxidation of cyclohexanone preparing cyclohexanone oxime, olefin oxidation system epoxide, pure oxidation system carbonyl compound, HTS has excellent catalytic activity and selectivity as catalyzer.U.S. Pat 4410501 reported first be the silicon source with the tetraethyl orthosilicate, tetrabutyl titanate is the titanium source, TPAOH (TPAOH) is the synthetic TS-1 HTS of template.European patent EP 0311983 is open with SiO
2-TiO
2Coprecipitate is a raw material, with TPAOH (TPAOH) solution impregnation SiO
2-TiO
2Coprecipitate comes the method for synthesizing titanium-silicon molecular sieve TS-1.Shortcoming with the synthetic TS-1 of TPAOH is: often have alkalimetal ion in the TPAOH and the catalytic activity of synthetic TS-1 is reduced, even make its whole inactivations; And the TPAOH of metal ion is not difficult to obtain, and costs an arm and a leg.
Summary of the invention
Technical problem to be solved by this invention is to exist the existence owing to alkalimetal ion in the TPAOH that synthetic TS-1 catalytic activity is reduced in order to overcome in the past in the document, even whole inactivations, and the TPAOH of metal ion is not difficult to obtain, expensive problem provides a kind of synthetic method of new titanium-silicon molecular sieve TS-1.This method has the catalyzer of reduction cost, simplify synthetic method, and synthetic HTS TS-1 has the higher degree of crystallinity and the characteristics of catalytic activity.
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-silicon molecular sieve TS-1, and at first with silicon source, titanium source, quaternary ammonium salt, water with contain OH
-Anionite-exchange resin count in molar ratio: SiO
2/ TiO
2Be 10～200, OH
-/ SiO
2Be 0.03～1.0, H
2O/SiO
2Be 20～60, R/SiO
2Be 0.005～1.0 mixed, wherein R is a quaternary ammonium salt, is under 120～200 ℃ of conditions at crystallization temperature under agitation with this mixture, and crystallization was taken out after 5～100 hours, made the TS-1 molecular sieve through washing, drying and roasting.
In the technique scheme, in the mixture with molar ratio computing preferable range: SiO
2/ Al
2O
3Be 20～80, OH
-/ SiO
2Be 0.05～0.5, H
2O/SiO
2Be 10～55, R/SiO
2Be 0.01～0.6.Silicon source preferred version is for being selected from tetraethyl orthosilicate or quanmethyl silicate; Titanium source preferred version is for being selected from titanous chloride or titanium tribromide; The quaternary ammonium salt preferred version is for being selected from the tetrapropyl ammonium halide; Contain OH
-The anionite-exchange resin preferred version for being selected from the macropore quaternary ammonium type anion exchange resin.
The present invention is owing to used the macropore basic anion exchange resin to regulate pH value, avoided the existence of alkalimetal ion, improved the catalytic activity of the molecular sieve of preparation widely, reduced production cost, preparation process is also simple greatly simultaneously, synthesized the titanium silicon TS-1 molecular sieve with MFI structure, its degree of crystallinity is up to 99%.The HTS that makes is used for the epoxidation reaction of propenyl chloride, and the selectivity of epoxy chloropropane has obtained better technical effect up to 94.2%.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
With 200.0 gram tetraethoxys, titanous chloride 20 grams of concentration 15 (weight) %, 100 gram water are put into 1000 milliliters of reactors, stir 0.5 hour.Then, adding contains 6.4 gram 4-propyl bromides, 38 milliliters of macroporous strong basic I type anionite-exchange resin (molecular formula C
11H
12-[C
10H
11]
n-N (CH
3)
3OH) and the mixing solutions of 48 gram water, stirred 2 hours, change in 1000 milliliters of stainless steel autoclaves that are lined with PTFE 175 ℃ of crystallization temperatures, crystallization time 72 hours over to.After crystallization finishes, filter, the wash crystallization product, 120 ℃ of dryings after 12 hours, 550 ℃ of roastings 5 hours.It is the titanium-silicon molecular sieve TS-1 with MFI structure that X-ray diffractometer records the gained crystal, and the XRD data see Table 1, and its degree of crystallinity is 98%.Wherein, reaction mixture is with molar ratio computing SiO
2/ TiO
2=50, OH
-/ iO
2=0.07, H
2O/SiO
2=33, R/SiO
2=0.025.
Table 1
[embodiment 2]
Each step according to [embodiment 1], crystallization temperature and crystallization time are constant, and just the titanous chloride add-on of concentration 15 (weight) % is 24 grams, and the add-on of water is 670 grams, the 4-propyl bromide add-on is 7.7 grams, macroporous strong basic II type anionite-exchange resin (molecular formula C
11H
12-[C
10H
11]
n-N (CH
3)
2C
2H
4OHOH) be 26 milliliters.It is the titanium-silicon molecular sieve TS-1 with MFI structure that X-ray diffractometer records the gained crystal, and the XRD data see Table 2, and its degree of crystallinity is 99%.Wherein, reaction mixture is with molar ratio computing SiO
2/ TiO
2=41, OH
-/ SiO
2=0.1, H
2O/SiO
2=38, R/SiO
2=0.03.
Table 2
[embodiment 3]
According to each step of [embodiment 1], crystallization temperature is constant, crystallization time 48 hours, the titanous chloride add-on of concentration 15 (weight) % is 48 grams, the add-on of water is 840 grams, and the 4-propyl bromide add-on is 9.0 grams, macroreticular weakly base I type anionite-exchange resin (molecular formula C
11H
12-[C
10H
11]
n-N (CH
3)
3OH) be 66 milliliters.It is the titanium-silicon molecular sieve TS-1 with MFI structure that X-ray diffractometer records the gained crystal, and the XRD data see Table 3, and its degree of crystallinity is 96%.Wherein, reaction mixture is with molar ratio computing SiO
2/ TiO
2=20, OH
-/ SiO
2=0.08, H
2O/SiO
2=49, R/SiO
2=0.035.
Table 3
[embodiment 4]
According to each step of [embodiment 1], 165 ℃ of crystallization temperatures, crystallization time is constant, the titanous chloride add-on of concentration 15 (weight) % is 1.7 grams, and the add-on of water is 93 grams, and the 4-propyl bromide add-on is 10 grams,, macroreticular weakly base II type anionite-exchange resin (molecular formula C
11H
12-[C
10H
11]
n-N (CH
3)
2C
2H
4OHOH) be 56 milliliters.It is the titanium-silicon molecular sieve TS-1 with MFI structure that X-ray diffractometer records the gained crystal, and the XRD data see Table 4, and its degree of crystallinity is 98%.Wherein, reaction mixture is with molar ratio computing SiO
2/ TiO
2=60, OH/SiO
2=0.08, H
2O/SiO
2=54, R/SiO
2=0.040.
Table 4
[embodiment 5]
TS-1 HTS with [embodiment 1] preparation is made catalyzer, carries out the chloro propylene epoxidation reaction.
In 500 milliliters of three mouthfuls of reactors, add 600 milligrams of catalyzer, 60 ml methanol, behind 40 milliliters of propenyl chlorides, constant temperature to 50 ℃, under agitation condition, 50 milliliters in implantation concentration 30 (weight) % hydrogen peroxide begins reaction, 1 hour reaction times.After reaction finished, the transformation efficiency that records hydrogen peroxide with iodimetry,iodometry was 95.7%, and the selectivity of stratographic analysis epoxy chloropropane is 93.4%.
[embodiment 6]
TS-1 HTS with [embodiment 2] preparation is made catalyzer, carries out the chloro propylene epoxidation reaction, and specific implementation process is with [embodiment 5].Its reaction result is: the transformation efficiency of hydrogen peroxide is 93.1%, and the selectivity of epoxy chloropropane is 87.6%.
[embodiment 7]
TS-1 HTS with [embodiment 3] preparation is made catalyzer, carries out the chloro propylene epoxidation reaction, and specific implementation process is with [embodiment 5].Its reaction result is: the transformation efficiency of hydrogen peroxide is 97.5%, and the selectivity of epoxy chloropropane is 94.2%.
[embodiment 8]
TS-1 HTS with [embodiment 4] preparation is made catalyzer, carries out the chloro propylene epoxidation reaction, and specific implementation process is with [embodiment 5].Its reaction result is: the transformation efficiency of hydrogen peroxide is 90.1%, and the selectivity of epoxy chloropropane is 93.8%.
[comparative example]
According to U.S. Pat 4410501 disclosed method synthesis of titanium silicon molecular sieve, the reaction mixture mol ratio is: SiO
2/ TiO
2=50, OH
-/ iO
2=0.4, H
2O/SiO
2=80, R/SiO
2=0.6.React according to embodiment 5, reaction result is as follows: the transformation efficiency of hydrogen peroxide is 93%, and the selectivity of epoxy chloropropane is 90%.
Claims (5)
1, a kind of synthetic method of titanium-silicon molecular sieve TS-1 is at first with silicon source, titanium source, quaternary ammonium salt, water with contain OH
-Anionite-exchange resin count in molar ratio: SiO
2/ TiO
2Be 10～200, OH
-/ SiO
2Be 0.03～1.0, H
2O/SiO
2Be 20～60, R/SiO
2Be 0.005～1.0 mixed, wherein R is a quaternary ammonium salt, is under 120～200 ℃ of conditions at crystallization temperature under agitation with this mixture, and crystallization was taken out after 5～100 hours, made the TS-1 molecular sieve through washing, drying and roasting.
2,, it is characterized in that in the mixture with molar ratio computing: SiO according to the synthetic method of the described titanium-silicon molecular sieve TS-1 of claim 1
2/ TiO
2Be 20～80, OH
-/ SiO
2Be 0.05～0.5, H
2O/SiO
2Be 10～55, R/SiO
2Be 0.01～0.6.
3,, it is characterized in that the silicon source is selected from tetraethyl orthosilicate or quanmethyl silicate according to the synthetic method of the described titanium-silicon molecular sieve TS-1 of claim 1; The titanium source is selected from titanous chloride or titanium tribromide; Quaternary ammonium salt is selected from the tetrapropyl ammonium halide; Contain OH
-Anionite-exchange resin be selected from the macropore quaternary ammonium type anion exchange resin.
4,, it is characterized in that crystallization temperature is 150～175 ℃ according to the synthetic method of the described titanium-silicon molecular sieve TS-1 of claim 1.
5,, it is characterized in that crystallization time is 20～60 hours according to the synthetic method of the described titanium-silicon molecular sieve TS-1 of claim 1.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266794A (en) * | 2011-07-07 | 2011-12-07 | 中北大学 | Method for producing magnetic-loaded titanium silicon molecular sieve catalyst and specialized colliding ultrasonic micro hybrid reactor |
| CN102502686A (en) * | 2011-10-06 | 2012-06-20 | 大连理工大学 | Method for synthesizing titanium silicon molecular sieve |
| CN102627292A (en) * | 2012-04-09 | 2012-08-08 | 华东师范大学 | Preparation method of TS-1 molecular sieve |
| CN103657715A (en) * | 2013-12-04 | 2014-03-26 | 中国科学院山西煤炭化学研究所 | Catalyst for methanol or dimethyl ether carbonylation synthesis of methyl acetate, preparation method and application thereof |
| US9486790B2 (en) | 2011-10-31 | 2016-11-08 | Dalian University Of Technology | Modification method of titanium-silicalite zeolite based on the mixture of quaternary ammonium salt and inorganic alkali |
| TWI594951B (en) * | 2016-06-14 | 2017-08-11 | Preparation and Application of Titanium Oxide - containing Materials | |
| CN108821304A (en) * | 2018-07-03 | 2018-11-16 | 西北大学 | High activity multi-stage porous Titanium Sieve Molecular Sieve and its preparation method and application |
| CN112744837A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, preparation method thereof and method for producing epoxy compound by oxidation reaction of macromolecular olefin |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1127311B (en) * | 1979-12-21 | 1986-05-21 | Anic Spa | SYNTHETIC, CRYSTALLINE, POROUS MATERIAL CONSTITUTED BY SILICON AND TITANIUM OXIDES, METHOD FOR ITS PREPARATION AND ITS USES |
| IT1222868B (en) * | 1987-10-12 | 1990-09-12 | Montedipe Spa | METHOD FOR THE PREPARATION OF TITANIUM SILICALITES |
| CN1089279C (en) * | 1998-09-17 | 2002-08-21 | 中国石油化工集团公司 | Synthesis of titania-silica molecular sieve |
| CN1212892C (en) * | 2002-12-31 | 2005-08-03 | 中国石油化工股份有限公司 | Method of synthesizing titanium silicon molecular sieve |
-
2007
- 2007-11-07 CN CN2007100478827A patent/CN101428814B/en active Active
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| CN102266794A (en) * | 2011-07-07 | 2011-12-07 | 中北大学 | Method for producing magnetic-loaded titanium silicon molecular sieve catalyst and specialized colliding ultrasonic micro hybrid reactor |
| CN102266794B (en) * | 2011-07-07 | 2012-10-24 | 中北大学 | Method for producing magnetic-loaded titanium silicon molecular sieve catalyst and specialized colliding ultrasonic micro hybrid reactor |
| CN102502686A (en) * | 2011-10-06 | 2012-06-20 | 大连理工大学 | Method for synthesizing titanium silicon molecular sieve |
| US9486790B2 (en) | 2011-10-31 | 2016-11-08 | Dalian University Of Technology | Modification method of titanium-silicalite zeolite based on the mixture of quaternary ammonium salt and inorganic alkali |
| CN102627292A (en) * | 2012-04-09 | 2012-08-08 | 华东师范大学 | Preparation method of TS-1 molecular sieve |
| CN103657715A (en) * | 2013-12-04 | 2014-03-26 | 中国科学院山西煤炭化学研究所 | Catalyst for methanol or dimethyl ether carbonylation synthesis of methyl acetate, preparation method and application thereof |
| CN103657715B (en) * | 2013-12-04 | 2015-08-19 | 中国科学院山西煤炭化学研究所 | The catalyst of methyl alcohol or the acetic acid synthesized methyl esters of Dimethyl ether carbonylation and method for making and application |
| TWI594951B (en) * | 2016-06-14 | 2017-08-11 | Preparation and Application of Titanium Oxide - containing Materials | |
| CN108821304A (en) * | 2018-07-03 | 2018-11-16 | 西北大学 | High activity multi-stage porous Titanium Sieve Molecular Sieve and its preparation method and application |
| CN108821304B (en) * | 2018-07-03 | 2020-02-14 | 西北大学 | High-activity hierarchical pore titanium silicalite molecular sieve and preparation method and application thereof |
| CN112744837A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, preparation method thereof and method for producing epoxy compound by oxidation reaction of macromolecular olefin |
| CN112744837B (en) * | 2019-10-31 | 2022-06-28 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, preparation method thereof and method for producing epoxy compound through oxidation reaction of macromolecular olefin |
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