CN102910643A - Preparation method of mesoporous-microporous titanium silicalite molecular sieves - Google Patents
Preparation method of mesoporous-microporous titanium silicalite molecular sieves Download PDFInfo
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- CN102910643A CN102910643A CN 201210422108 CN201210422108A CN102910643A CN 102910643 A CN102910643 A CN 102910643A CN 201210422108 CN201210422108 CN 201210422108 CN 201210422108 A CN201210422108 A CN 201210422108A CN 102910643 A CN102910643 A CN 102910643A
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Abstract
The invention relates to a preparation method of molecular sieves, in particular to a preparation method of mesoporous-microporous titanium silicalite molecular sieves. The method includes: uniformly mixing tetrapropylammonium hydroxide, tetrabutyl titanate, tetraethyl orthosilicate and deionized water in the mass ratio of 1:20-90:8:1500, reacting at the constant temperature of 35 DEG C prior to mixing with polymethyl vinyl fluoride, and crystallizing for 1 hour at the temperature of 140 DEG C to obtain nano-clusters; and mixing hexadecyl trimethyl ammonium bromide, the deionized water, ammonia water 25% in concentration and the polymethyl vinyl fluoride, crystallizing for 72 hours at the temperature of 120 DEG C to obtain a product, and subjecting the product to suction filtration, washing, drying at the room temperature and roasting for 4 hours at the temperature of 500 DEG C so that the mesoporous-microporous titanium silicalite molecular sieves are obtained. Experimental results show that the mesoporous-microporous titanium silicalite molecular sieves prepared by the method are large in specific surface area, and micropores are reserved in pore walls of mesopores; primary and secondary building units of TS-1 molecular sieves are successfully introduced into the pore walls of the mesoporous molecular sieves; and the mesoporous-microporous titanium silicalite molecular sieves prepared by the method has good selectivity on generation of styrene oxide in epoxidation reaction of styrene.
Description
Technical field
The present invention relates to a kind of preparation method of molecular sieve.
Background technology
In the fine chemistry industry process, for example in the green catalysis oxidizing reaction, traditional catalyzer is the TS-1 molecular sieve, and nineteen eighty-three is synthetic first by people such as Taramasso, and its unique catalytic oxidation performance has caused widely to be paid close attention to.Catalytic oxidation process take the TS-1 molecular sieve as catalyzer is pollution-free, and reaction conditions is gentle, has overcome shortcoming seriously polluted in the traditional technology, the tediously long complexity of reaction process.As far back as 1987, the device that the phenol hydroxylation of annual output 1 Mt take TS-1 as catalyzer is produced diphenol was constructed and put into operation in Italy.But because its duct is between 0.5～0.6 nm, present application is confined to catalyzing expoxidation of olefines, phenol hydroxylation, ammoxidation of cyclohexanone etc.Because the effect of TS-1 molecular sieve is very little in macromolecular catalytic oxidation process, this has just limited its application in fine chemistry industry and pharmaceutical industry.
The Ti-MCM-41 that emerges in recent years, Ti-SBA-15, the mesoporous titanium-silicon molecular screens such as Ti-HMS, for macromolecular catalyzed oxidation provides good chance, this in some pharmaceutical industry asks particularly that for the production of fine chemicals the production of body is very important.Yet the catalytic oxidation activity of order mesoporous titanium silicalite material is compared greatly inferior with hydrothermal stability with the micropore titanium silicon molecular sieve of routine.
Micro porous molecular sieve has good catalytic oxidation activity and hydrothermal stability with respect to mesopore molecular sieve, and this crystal formation that comes from its hole wall is regularly arranged, and amorphism therefore how to improve the mesopore molecular sieve hole wall is the target that many investigators pursue.2003, Xiao Fengshou etc. successfully synthesize mesoporous titanium-silicon molecular screen MTS-9 with triblock copolymer high polymer templates P123, the nano-cluster that will contain microporous titanium silicon fluorite primary and secondary structural unit is incorporated in the hole wall of molecular sieve, no matter be 500 ℃ of roastings or the boiling water thermal treatment of 120 h.The feature meso-hole structure of MTS-9 is all very stable, shows that it has had higher hydrothermal stability.2005, Wang Runwei etc. are take cetyl trimethylammonium bromide (CTAB) as template, mesoporous titanium-silicon molecular screen JQW-3 and JQW-4 in colorant, have been synthesized respectively, compare with traditional mesoporous titanium-silicon molecular screen Ti-MCM-41, the hydrothermal stability of the two improves greatly, phenol, vinylbenzene, 2,3, the test of the catalytic oxidation of 6 one pseudocuminols shows, the catalytic activity of JQW-3 and JQW-4 is similar to TS-1 and be higher than Ti-MCM-41.
Summary of the invention
The present invention aim to provide a kind of specific surface area larger mesoporous-preparation method of micropore titanium silicon molecular sieve.
Of the present invention mesoporous-preparation method of micropore titanium silicon molecular sieve, comprise.
(1) with TPAOH, positive four butyl esters of metatitanic acid, tetraethoxy and deionized water mix by the mass ratio of 1:20-90:8:1500, mix with poly-first vinyl fluoride after 35 ℃ of isothermal reactions, and 140 ℃ of lower crystallization 1 hour obtain nano-cluster.
(2) cetyl trimethylammonium bromide, deionized water, 25% ammoniacal liquor are mixed with poly-first vinyl fluoride, crystallization 72h in 120 ℃, products therefrom gets final product through suction filtration, washing, drying at room temperature, 500 ℃ of roasting 4h.
Preferably, crystallization is to carry out in having the teflon-lined still.
More preferably, TPAOH, the mass ratio of positive four butyl esters of metatitanic acid, tetraethoxy and deionized water is 1:20:8:1500.
Perhaps more preferably, TPAOH, the mass ratio of positive four butyl esters of metatitanic acid, tetraethoxy and deionized water is 1:30:8:1500.
Perhaps more preferably, TPAOH, the mass ratio of positive four butyl esters of metatitanic acid, tetraethoxy and deionized water is 1:60:8:1500.
Perhaps more preferably, TPAOH, the mass ratio of positive four butyl esters of metatitanic acid, tetraethoxy and deionized water is 1:90:8:1500.
Through experiment showed, that the present invention makes mesoporous-micropore titanium silicon molecular sieve has large specific surface area, and has micropore to exist in the mesoporous wall; It successfully has been incorporated into the primary and secondary structural unit of TS-1 molecular sieve in the hole wall of mesopore molecular sieve; The present invention makes in cinnamic epoxidation reaction, and mesoporous-micropore titanium silicon molecular sieve has preferably selectivity to the generation of Styryl oxide.
Embodiment
Embodiment one.
With TPAOH, positive four butyl esters of metatitanic acid, tetraethoxy and deionized water mix by the mass ratio of 1:20:8:1500, pack into behind the reaction certain hour in 35 ℃ of water bath with thermostatic control cups and have in the still of poly-first vinyl fluoride liner, in 140 ℃ of lower crystallization 1 hour, obtain the settled solution of directed agents.
Cetyl trimethylammonium bromide, deionized water, 25% ammoniacal liquor and nano-cluster are mixed by a certain percentage, and packing into behind the reaction 5h in 30 ℃ of water bath with thermostatic control cups has in the teflon-lined still.Crystallization 72h in 120 ℃ of baking ovens, products therefrom gets final product through suction filtration, washing, drying at room temperature, 500 ℃ of roasting 4h.
Embodiment two.
With TPAOH, positive four butyl esters of metatitanic acid, tetraethoxy and deionized water mix by the mass ratio of 1:90:8:1500, pack into behind the reaction certain hour in 35 ℃ of water bath with thermostatic control cups and have in the still of poly-first vinyl fluoride liner, in 140 ℃ of lower crystallization 1 hour, obtain the settled solution of directed agents.
Cetyl trimethylammonium bromide, deionized water, 25% ammoniacal liquor and nano-cluster are mixed by a certain percentage, and packing into behind the reaction 5h in 30 ℃ of water bath with thermostatic control cups has in the teflon-lined still.Crystallization 72h in 120 ℃ of baking ovens, products therefrom gets final product through suction filtration, washing, drying at room temperature, 500 ℃ of roasting 4h.
Embodiment three.
With TPAOH, positive four butyl esters of metatitanic acid, tetraethoxy and deionized water mix by the mass ratio of 1:30:8:1500, pack into behind the reaction certain hour in 35 ℃ of water bath with thermostatic control cups and have in the still of poly-first vinyl fluoride liner, in 140 ℃ of lower crystallization 1 hour, obtain the settled solution of directed agents.
Cetyl trimethylammonium bromide, deionized water, 25% ammoniacal liquor and nano-cluster are mixed by a certain percentage, and packing into behind the reaction 5h in 30 ℃ of water bath with thermostatic control cups has in the teflon-lined still.Crystallization 72h in 120 ℃ of baking ovens, products therefrom gets final product through suction filtration, washing, drying at room temperature, 500 ℃ of roasting 4h.
Embodiment four.
With TPAOH, positive four butyl esters of metatitanic acid, tetraethoxy and deionized water mix by the mass ratio of 1:60:8:1500, pack into behind the reaction certain hour in 35 ℃ of water bath with thermostatic control cups and have in the still of poly-first vinyl fluoride liner, in 140 ℃ of lower crystallization 1 hour, obtain the settled solution of directed agents.
Cetyl trimethylammonium bromide, deionized water, 25% ammoniacal liquor and nano-cluster are mixed by a certain percentage, and packing into behind the reaction 5h in 30 ℃ of water bath with thermostatic control cups has in the teflon-lined still.Crystallization 72h in 120 ℃ of baking ovens, products therefrom gets final product through suction filtration, washing, drying at room temperature, 500 ℃ of roasting 4h.
Embodiment five.
With vinylbenzene respectively with implement one to four the product mass ratio with 0.05 and mix, again with H
2O
2Mix vinylbenzene and H
2O
2Mol ratio be 3, then add solvent acetone, react 6h under 60 ℃ of water-baths.Analyze the product of gained with gas chromatograph.
Experiment showed, that the HTS that the present invention makes has preferably selectivity to styrene catalyzed epoxidation reaction generation Styryl oxide.
Claims (6)
1. the preparation method of mesoporous-micropore titanium silicon molecular sieve is characterized in that comprising:
(1) with TPAOH, positive four butyl esters of metatitanic acid, tetraethoxy and deionized water mix by the mass ratio of 1:20-90:8:1500, mix with poly-first vinyl fluoride after 35 ℃ of isothermal reactions, and 140 ℃ of lower crystallization 1 hour obtain nano-cluster;
(2) cetyl trimethylammonium bromide, deionized water, 25% ammoniacal liquor are mixed with poly-first vinyl fluoride, crystallization 72h in 120 ℃, products therefrom gets final product through suction filtration, washing, drying at room temperature, 500 ℃ of roasting 4h.
As claimed in claim 1 mesoporous-preparation method of micropore titanium silicon molecular sieve, it is characterized in that crystallization is to carry out in having the teflon-lined still.
As claimed in claim 1 or 2 mesoporous-preparation method of micropore titanium silicon molecular sieve, it is characterized in that TPAOH, the mass ratio of positive four butyl esters of metatitanic acid, tetraethoxy and deionized water is 1:20:8:1500.
As claimed in claim 1 or 2 mesoporous-preparation method of micropore titanium silicon molecular sieve, it is characterized in that TPAOH, the mass ratio of positive four butyl esters of metatitanic acid, tetraethoxy and deionized water is 1:30:8:1500.
As claimed in claim 1 or 2 mesoporous-preparation method of micropore titanium silicon molecular sieve, it is characterized in that TPAOH, the mass ratio of positive four butyl esters of metatitanic acid, tetraethoxy and deionized water is 1:60:8:1500.
As claimed in claim 1 or 2 mesoporous-preparation method of micropore titanium silicon molecular sieve, it is characterized in that TPAOH, the mass ratio of positive four butyl esters of metatitanic acid, tetraethoxy and deionized water is 1:90:8:1500.
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| CN104556112A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Titanium-silicon micro-mesoporous molecular sieve composite material and synthetic method thereof |
| CN105355464A (en) * | 2015-11-10 | 2016-02-24 | 西安科技大学 | Mesopore-micropore carbon micro sphere of high specific surface area for super capacitor and preparation method of carbon micro sphere |
| CN107308983A (en) * | 2017-06-30 | 2017-11-03 | 科比环保科技（天津自贸试验区）有限公司 | Room temperature is except interior VOC catalyst and preparation method thereof |
| CN107694600A (en) * | 2016-10-24 | 2018-02-16 | 晋中市智诚科技服务中心 | A kind of microporous mesoporous composite molecular sieve film of support type and preparation method thereof |
| CN110330025A (en) * | 2019-06-15 | 2019-10-15 | 武汉理工大学 | Silicon titanium is than the adjustable TS-1 zeolite single crystal and preparation method thereof with orderly multi-stage porous |
| WO2020097878A1 (en) | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparation of hierarchical ts-1 molecular sieve |
| WO2020097877A1 (en) | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing hierarchical porous titanosilicate ts-1 molecular sieve |
| WO2020097876A1 (en) | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing ts-1 molecular sieve with hierarchical pores |
| CN113492017A (en) * | 2020-04-08 | 2021-10-12 | 中国石油天然气股份有限公司 | Supported catalyst for preparing acrylic acid by catalytic oxidation of propane, and preparation method and application thereof |
| CN114768748A (en) * | 2022-04-22 | 2022-07-22 | 山东亮剑环保新材料有限公司 | Preparation method of all-silicon micro-mesoporous composite molecular sieve VOCs adsorbent |
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| CN104556112B (en) * | 2013-10-29 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of micro- mesoporous molecular sieve composite material of titanium silicon and its synthetic method |
| CN104556112A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Titanium-silicon micro-mesoporous molecular sieve composite material and synthetic method thereof |
| CN105355464A (en) * | 2015-11-10 | 2016-02-24 | 西安科技大学 | Mesopore-micropore carbon micro sphere of high specific surface area for super capacitor and preparation method of carbon micro sphere |
| CN105355464B (en) * | 2015-11-10 | 2017-10-17 | 西安科技大学 | A kind of ultracapacitor high specific surface area and mesoporous micropore carbon microspheres and preparation method thereof |
| CN107694600A (en) * | 2016-10-24 | 2018-02-16 | 晋中市智诚科技服务中心 | A kind of microporous mesoporous composite molecular sieve film of support type and preparation method thereof |
| CN107308983B (en) * | 2017-06-30 | 2019-09-20 | 科比环保科技（天津自贸试验区）有限公司 | Room temperature removes the catalyst and preparation method thereof of interior VOC |
| CN107308983A (en) * | 2017-06-30 | 2017-11-03 | 科比环保科技（天津自贸试验区）有限公司 | Room temperature is except interior VOC catalyst and preparation method thereof |
| WO2020097878A1 (en) | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparation of hierarchical ts-1 molecular sieve |
| WO2020097877A1 (en) | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing hierarchical porous titanosilicate ts-1 molecular sieve |
| WO2020097876A1 (en) | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing ts-1 molecular sieve with hierarchical pores |
| CN110330025A (en) * | 2019-06-15 | 2019-10-15 | 武汉理工大学 | Silicon titanium is than the adjustable TS-1 zeolite single crystal and preparation method thereof with orderly multi-stage porous |
| CN110330025B (en) * | 2019-06-15 | 2023-04-07 | 武汉理工大学 | TS-1 molecular sieve single crystal with ordered hierarchical pores and adjustable silicon-titanium ratio and preparation method thereof |
| CN113492017A (en) * | 2020-04-08 | 2021-10-12 | 中国石油天然气股份有限公司 | Supported catalyst for preparing acrylic acid by catalytic oxidation of propane, and preparation method and application thereof |
| CN114768748A (en) * | 2022-04-22 | 2022-07-22 | 山东亮剑环保新材料有限公司 | Preparation method of all-silicon micro-mesoporous composite molecular sieve VOCs adsorbent |
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Application publication date: 20130206 |