CN101428814B - Synthesis of titanium-silicon molecular sieve TS-1 - Google Patents
Synthesis of titanium-silicon molecular sieve TS-1 Download PDFInfo
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- CN101428814B CN101428814B CN2007100478827A CN200710047882A CN101428814B CN 101428814 B CN101428814 B CN 101428814B CN 2007100478827 A CN2007100478827 A CN 2007100478827A CN 200710047882 A CN200710047882 A CN 200710047882A CN 101428814 B CN101428814 B CN 101428814B
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- titanium
- molecular sieve
- quaternary ammonium
- exchange resin
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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 catalysis material with good catalytic selective oxidation activity.In reactions such as benzene oxidation system phenol, oxidation of phenol preparing benzenediol, alkane oxidation system ketone and alcohol, ammoxidation of cyclohexanone preparing cyclohexanone oxime, olefin oxidation system epoxides, pure oxidation system carbonyls, HTS has excellent catalytic activity and selectivity as catalyst.U.S. Pat 4410501 reported first be the silicon source with the tetraethyl orthosilicate, butyl titanate is the titanium source, TPAOH (TPAOH) is the synthetic TS-1 HTS of template agent.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 alkali metal 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 alkali metal 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 catalyst of reduction cost, simplifies synthetic method, and synthetic titanium-silicon molecular sieve 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
-Anion 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 that 0.005～1.0 ratio is 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, make the TS-1 molecular sieve wherein through washing, drying and roasting, the silicon source is selected from tetraethyl orthosilicate or quanmethyl silicate; The titanium source is selected from titanium trichloride or titanium tribromide; Quaternary ammonium salt is selected from the tetrapropyl ammonium halide; Contain OH
-Anion exchange resin be selected from the macropore quaternary ammonium type anion exchange resin.
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.
The present invention is owing to used the macropore alkalescence anion-exchange resin to regulate pH value, avoided the existence of alkali metal 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 chloropropene, and the selectivity of epoxychloropropane has obtained better technical effect up to 94.2%.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 200.0 gram ethyl orthosilicates, titanium trichloride 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 anion exchange resin (molecular formula C
11H
12-[C
10H
11]
n-N (CH
3)
3OH) and the mixed solution 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, reactant 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 titanium trichloride addition of concentration 15 (weight) % is 24 grams, and the addition of water is 670 grams, the 4-propyl bromide addition is 7.7 grams, macroporous strong basic II type anion 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, reactant 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
| 2θ? | d(A)? | I d/I 100 |
| 7.88 8.80 11.86 13.88 14.76 15.46 15.90 19.26 20.84 23.07 23.90 24.40 | 10.4 9.32 7.46 6.38 5.96 5.73 5.57 4.61 4.26 3.58 3.45 3.38 | 0.68 0.34 0.14 0.16 0.11 0.09 0.13 0.08 0.10 1.00 0.52 0.37 |
| 25.88? | 3.44? | 0.13? |
[embodiment 3]
According to each step of [embodiment 1], crystallization temperature is constant, crystallization time 48 hours, the titanium trichloride addition of concentration 15 (weight) % is 48 grams, the addition of water is 840 grams, and the 4-propyl bromide addition is 9.0 grams, macroreticular weakly base I type anion 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, reactant 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
| 2θ? | d(A)? | I d/I 100 |
| 7.88 8.80 11.86 13.88 14.76 15.46 19.20 20.32 20.86 23.09 23.90 24.40 25.84 | 10.4 9.32 7.46 6.38 6.00 5.73 4.62 4.37 4.26 3.58 3.45 3.38 3.45 | 0.66 0.37 0.14 0.16 0.11 0.09 0.01 0.13 0.12 1 0.51 0.37 0.13 |
[embodiment 4]
According to each step of [embodiment 1], 165 ℃ of crystallization temperatures, crystallization time is constant, the titanium trichloride addition of concentration 15 (weight) % is 1.7 grams, and the addition of water is 93 grams, and the 4-propyl bromide addition is 10 grams,, macroreticular weakly base II type anion 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, reactant 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
| 2θ? | d(A)? | I d/I 100 |
| 7.98 8.89 9.04 11.86 13.16 13.88 14.76 15.46 15.9 23.09 23.90 24.42 25.84 | 10.3 9.22 9.78 7.46 6.73 6.38 6.00 5.73 5.57 3.58 3.45 3.38 3.45 | 0.78 0.35 0.20 0.14 0.08 0.16 0.11 0.09 0.13 1 0.48 0.38 0.13 |
[embodiment 5]
TS-1 HTS with [embodiment 1] preparation is made catalyst, carries out the chloro propylene epoxidation reaction.
In 500 milliliters of three mouthfuls of reactors, add 600 milligrams of catalyst, 60 ml methanol, behind 40 milliliters of chloropropenes, constant temperature to 50 ℃, under stirring condition, 50 milliliters in implantation concentration 30 (weight) % hydrogen peroxide begins reaction, 1 hour reaction time.After reaction finished, the conversion ratio that records hydrogen peroxide with iodimetric titration was 95.7%, and the selectivity of chromatography epoxychloropropane is 93.4%.
[embodiment 6]
TS-1 HTS with [embodiment 2] preparation is made catalyst, carries out the chloro propylene epoxidation reaction, and specific implementation process is with [embodiment 5].Its reaction result is: the conversion ratio of hydrogen peroxide is 93.1%, and the selectivity of epoxychloropropane is 87.6%.
[embodiment 7]
TS-1 HTS with [embodiment 3] preparation is made catalyst, carries out the chloro propylene epoxidation reaction, and specific implementation process is with [embodiment 5].Its reaction result is: the conversion ratio of hydrogen peroxide is 97.5%, and the selectivity of epoxychloropropane is 94.2%.
[embodiment 8]
TS-1 HTS with [embodiment 4] preparation is made catalyst, carries out the chloro propylene epoxidation reaction, and specific implementation process is with [embodiment 5].Its reaction result is: the conversion ratio of hydrogen peroxide is 90.1%, and the selectivity of epoxychloropropane is 93.8%.
[comparative example]
According to U.S. Pat 4410501 disclosed method synthesis of titanium silicon molecular sieve, the reactant 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 conversion ratio of hydrogen peroxide is 93%, and the selectivity of epoxychloropropane is 90%.
Claims (2)
1. the synthetic method of a titanium-silicon molecular sieve TS-1 is at first with silicon source, titanium source, quaternary ammonium salt, water with contain OH
-Anion 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 that 0.005～1.0 ratio is mixed, wherein R is a quaternary ammonium salt, is under 175～200 ℃ of conditions at crystallization temperature under agitation with this mixture, and crystallization was taken out after 60～100 hours, made the TS-1 molecular sieve through washing, drying and roasting; Wherein, the silicon source is selected from tetraethyl orthosilicate or quanmethyl silicate; The titanium source is selected from titanium trichloride or titanium tribromide; Quaternary ammonium salt is selected from the tetrapropyl ammonium halide; Contain OH
-Anion exchange resin be selected from the macropore quaternary ammonium type anion exchange resin; Wherein, described macropore quaternary ammonium type anion exchange resin is selected from C
11H
12-[C
10H
11]
n-N (CH
3)
3OH or C
11H
12-[C
10H
11]
n-N (CH
3)
2C
2H
4OHOH.
2. according to the synthetic method of the described titanium-silicon molecular sieve TS-1 of claim 1, it is characterized in that in the mixture with molar ratio computing: SiO
2/ TiO
2Be 20～80, OH
-/ SiO
2Be 0.05～0.5, H
2O/SiO
2Be 20～55, R/SiO
2Be 0.01～0.6.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102502686B (en) * | 2011-10-06 | 2013-06-19 | 大连理工大学 | Method for synthesizing titanium silicon molecular sieve |
| CN102502690A (en) | 2011-10-31 | 2012-06-20 | 大连理工大学 | Method for modifying TS (Titanium silicalite)-1 based on mixed liquor of quaternary ammonium salt and inorganic base |
| CN102627292B (en) * | 2012-04-09 | 2013-07-17 | 华东师范大学 | Preparation method of TS-1 molecular sieve |
| 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 | |
| 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 |
| 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 |
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 |
| EP0311983A2 (en) * | 1987-10-12 | 1989-04-19 | Enichem Anic S.r.l. | Method for the preparation of titanium-silicalites |
| CN1247771A (en) * | 1998-09-17 | 2000-03-22 | 中国石油化工集团公司 | Synthesis of titania-silica 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 |
-
2007
- 2007-11-07 CN CN2007100478827A patent/CN101428814B/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 |
| EP0311983A2 (en) * | 1987-10-12 | 1989-04-19 | Enichem Anic S.r.l. | Method for the preparation of titanium-silicalites |
| CN1247771A (en) * | 1998-09-17 | 2000-03-22 | 中国石油化工集团公司 | Synthesis of titania-silica 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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