CN105712367A - Core/shell-type micropore /mesoporous composite titanium silicon molecular sieve and preparation method thereof - Google Patents
Core/shell-type micropore /mesoporous composite titanium silicon molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a core / shell-type micropore /mesoporous composite titanium silicon molecular sieve and a preparation method thereof. The composite molecular sieve has a nearly spherical morphology, a specific surface area of 500-700m<2> / g, and a typical core-shell structure, an inner core is microporous titanium silicon molecular sieve TS-1 with a diameter of 200-300nm, an outer shell layer is hexagonal ordered mesoporous titanium-containing silica with the aperture of 2-3nm, a gap is between the inner core and the outer shell, and gap size and outer shell thickness both can be modulated. The composite molecular sieve is prepared by a two-step process, and the microporous titanium silicon molecular sieve TS-1 is first coated with a phenolic resin polymer as a hard template, and then coated with the mesoporous titanium-containing silica. The effects and benefits are as follows: the composite molecular sieve has multi levels of channels, the hollow core-shell structure is conducive to diffusion of guest molecules, and has good use prospects in catalysis, adsorption and separation and other fields, and the preparation process is simple, efficient and highly controllable.
Description
Technical field
The invention belongs to field of material preparation, be specifically related to a kind of multi-stage porous compound titanium silicon molecular sieve and preparation method thereof.
Background technology
HTS has the catalytic performance of excellence for the Organic substance selective oxidation carried out under temperate condition, receives the extensive concern of researcheres all the time.Although traditional micropore titanium silicon molecular sieve has higher activity, but narrow duct limits its application in macromolecular reaction.Although mesoporous titanium-silicon molecular screen duct is open, but it is amorphous, and to nature of its intrinsic activity relatively low.Therefore, how by micropore and meso titanium silica catalysis material phase compound so that it is have complementary advantages, become the focus of Recent study.
At present, middle mesoporous-microporous composite molecular sieve reported and preparation method thereof mainly includes three kinds.The first uses some certain moduli plate agent to introduce mesoporous in micro porous molecular sieve, although diffusion-restricted makes moderate progress, but this material preparation process is complicated, and need to use some expensive surfactants (NatureMater., 2006,5,718；Angew.Chem., Int.Ed., 2006,45,3090；Chem.Commun., 2011,47,3529.).It two is introduced in mesoporous material skeleton by micro porous molecular sieve construction unit, and activity and the stability of prepared material all increase, but still have obvious gap (J.Am.Chem.Soc., 2002,124,888 with general microporous zeolite facies ratio；Angew.Chem., 2001,113,1295；Chem.Mater., 2007,19,1664.).It is additionally that the feature making them have complementary advantages becomes apparent from by micro porous molecular sieve and mesoporous material direct combination in some way.Typical work has: Peng etc., with P123 for mesoporous template, have synthesized mesoporous silicon oxide cladding titanium-silicon molecular sieve TS-1 core-shell material (Micropor.Mesopor.Mater., 2012,153,8) by control ph；Qian etc. adopt similar method to synthesize ZSM-5SBA-15 micropore/mesoporous composite molecular sieve (Chem.Sci., 2011,2,2006.).But, in these materials, micropore kernel and mesoporous shell are all close contacts, are unfavorable for the diffusion of guest molecule.Composite molecular screen of development of new and preparation method thereof is still a challenge.
Summary of the invention
It is an object of the invention to provide a kind of core shell type micro-hole/composite mesoporous HTS and preparation method thereof.
A kind of core shell type micro-hole/composite mesoporous HTS is elementary composition by silicon, oxygen, titanium three kinds, for subsphaeroidal pattern, specific surface area 500～700m2/ g, has nucleocapsid structure, and kernel is the micropore titanium silicon molecular sieve TS-1 of particle diameter 200～300nm, and shell is the six order mesoporous titaniferous silicon dioxide of side of aperture 2～3nm, and thickness is 20～100nm, there is the gap of 20～200nm between kernel and shell.
The preparation method of a kind of core shell type micro-hole/composite mesoporous HTS is divided into two steps, particularly as follows:
(1) 0.25g micropore titanium silicon molecular sieve TS-1 being scattered in mol ratio is deionized water ethanol surfactant NH4In the reaction system of OH resorcinol formaldehyde=2.2～4.4 0.4～0.8 0.0014 0.0044 0.00045～0.0018 0.0009～0.0036, stirring 6～24h under room temperature, 25～100 DEG C stand 8～24h and prepare the titanium-silicon molecular sieve TS-1 of novalac polymer cladding；
(2) titanium-silicon molecular sieve TS-1 that 0.5g novalac polymer is coated with being scattered in mol ratio is deionized water ethanol surfactant NH4In the mixed system of OH=2.78～11.1 1.04～4.16 0.00015～0.0006 0.03～0.12, add the silicon source of 0.00096～0.0048mol and the titanium source of 0.0000048～0.000192mol, 40～80 DEG C stirring 8～72h, product through super-dry at 550 DEG C of roasting 5h.
Described micropore titanium silicon molecular sieve TS-1 is with silicon tetraethyl acid esters for silicon source, and positive four butyl esters of metatitanic acid are titanium source, and TPAOH is template, adopts hydro-thermal method to prepare.
Described surfactant is formula is CnH2n+1(CH3)3The quaternary ammonium salt cationic surfactant of NBr, wherein n=12～16.
Described silicon source is silicon tetraethyl acid esters, and titanium source is positive four butyl esters of metatitanic acid.
Nucleocapsid structure micropore provided by the invention/composite mesoporous HTS, compound with regular structure, Parameter adjustable, be conducive to guest molecule to spread, its preparation method is simple, efficient, controllability is strong.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the core shell type micro-hole/composite mesoporous HTS of the present invention, corresponding embodiment 2.
Fig. 2 is the X-ray diffractogram of the core shell type micro-hole/composite mesoporous HTS of the present invention, corresponding embodiment 2.
Detailed description of the invention
List of references prepares micropore titanium silicon molecular sieve TS-1
11.2ml silicon tetraethyl acid esters and the positive four butyl ester mixing of 0.34g metatitanic acid, jointly drop in 29.5ml TPAOH aqueous solution (mass concentration 9%), 1.5h is stirred under room temperature, 80 DEG C of stirring 4h, supplement deionized water to initial volume, reactant liquor is loaded with in teflon-lined stainless steel autoclave, 48h is stood at 170 DEG C, centrifugation goes out solid product, 120 DEG C of drying, the lower 550 DEG C of roasting 5h of air atmosphere, obtain the micropore titanium silicon molecular sieve TS-1 of particle diameter 200～300nm.
Embodiment 1
Take 0.25g micropore titanium silicon molecular sieve TS-1 and be scattered in 40ml deionized water and 20ml dehydrated alcohol, add 0.5g cetyl trimethylammonium bromide and 0.3g ammonia, stirring 0.5h, add 0.05g resorcinol and 0.075g mass concentration is the formalin of 37%, room temperature with constant stirring 8h, stands 14h, filters out product, 80 DEG C of drying, obtain the micropore titanium silicon molecular sieve TS-1 (TS-1RF) of novalac polymer cladding.Take 0.5gTS-1RF and be scattered in 100ml deionized water and 60ml dehydrated alcohol, add 0.05g cetyl trimethylammonium bromide and 2g ammonia, 40 DEG C of stirring 0.5h, add 0.57g silicon tetraethyl acid esters and positive four butyl esters of 0.018g metatitanic acid, continuously stirred 15h, filters, 80 DEG C of drying, the lower 550 DEG C of roasting 5h of air atmosphere, obtain core shell type micro-hole/composite mesoporous HTS.
Embodiment 2
Take 0.25g micropore titanium silicon molecular sieve TS-1 and be scattered in 40ml deionized water and 20ml dehydrated alcohol, add 0.5g cetyl trimethylammonium bromide and 0.3g ammonia, stirring 0.5h, add 0.1g resorcinol and 0.15g mass concentration is the formalin of 37%, room temperature with constant stirring 8h, stands 14h, filters out product, 80 DEG C of drying, obtain the micropore titanium silicon molecular sieve TS-1 (TS-1RF) of novalac polymer cladding.Take 0.5gTS-1RF and be scattered in 100ml deionized water and 60ml dehydrated alcohol, add 0.05g cetyl trimethylammonium bromide and 2g ammonia, 40 DEG C of stirring 0.5h, add 0.57g silicon tetraethyl acid esters and positive four butyl esters of 0.018g metatitanic acid, continuously stirred 15h, filters, 80 DEG C of drying, the lower 550 DEG C of roasting 5h of air atmosphere, obtain core shell type micro-hole/composite mesoporous HTS.
Embodiment 3
Take 0.25g micropore titanium silicon molecular sieve TS-1 and be scattered in 40ml deionized water and 20ml dehydrated alcohol, add 0.5g cetyl trimethylammonium bromide and 0.3g ammonia, stirring 0.5h, add 0.2g resorcinol and 0.3g mass concentration is the formalin of 37%, room temperature with constant stirring 8h, stands 14h, filters out product, 80 DEG C of drying, obtain the micropore titanium silicon molecular sieve TS-1 (TS-1RF) of novalac polymer cladding.Take 0.5gTS-1RF and be scattered in 100ml deionized water and 60ml dehydrated alcohol, add 0.05g cetyl trimethylammonium bromide and 2g ammonia, 40 DEG C of stirring 0.5h, add 0.57g silicon tetraethyl acid esters and positive four butyl esters of 0.018g metatitanic acid, continuously stirred 15h, filters, 80 DEG C of drying, the lower 550 DEG C of roasting 5h of air atmosphere, obtain core shell type micro-hole/composite mesoporous HTS that nucleocapsid gap is 20nm.
Embodiment 4
Take 0.25g micropore titanium silicon molecular sieve TS-1 and be scattered in 40ml deionized water and 20ml dehydrated alcohol, add 0.5g cetyl trimethylammonium bromide and 0.3g ammonia, stirring 0.5h, add 0.1g resorcinol and 0.15g mass concentration is the formalin of 37%, room temperature with constant stirring 8h, stands 14h, filters out product, 80 DEG C of drying, obtain the micropore titanium silicon molecular sieve TS-1 (TS-1RF) of novalac polymer cladding.Take 0.5gTS-1RF and be scattered in 100ml deionized water and 60ml dehydrated alcohol, add 0.05g cetyl trimethylammonium bromide and 2g ammonia, 40 DEG C of stirring 0.5h, add 0.2g silicon tetraethyl acid esters and positive four butyl esters of 0.006g metatitanic acid, continuously stirred 15h, filters, 80 DEG C of drying, the lower 550 DEG C of roasting 5h of air atmosphere, obtain core shell type micro-hole/composite mesoporous HTS.
Embodiment 5
Take 0.25g micropore titanium silicon molecular sieve TS-1 and be scattered in 40ml deionized water and 20ml dehydrated alcohol, add 0.5g cetyl trimethylammonium bromide and 0.3g ammonia, stirring 0.5h, add 0.1g resorcinol and 0.15g mass concentration is the formalin of 37%, room temperature with constant stirring 8h, stands 14h, filters out product, 80 DEG C of drying, obtain the micropore titanium silicon molecular sieve TS-1 (TS-1RF) of novalac polymer cladding.Take 0.5gTS-1RF and be scattered in 100ml deionized water and 60ml dehydrated alcohol, add 0.05g cetyl trimethylammonium bromide and 2g ammonia, 60 DEG C of stirring 0.5h, add 0.57g silicon tetraethyl acid esters and positive four butyl esters of 0.018g metatitanic acid, continuously stirred 15h, filters, 80 DEG C of drying, the lower 550 DEG C of roasting 5h of air atmosphere, obtain core shell type micro-hole/composite mesoporous HTS.
Application examples 1
Take 10 μ l thiophene to be dissolved in 10ml normal octane as analog fuel, join 100ml with in three mouthfuls of reactors of water-bath chuck, then middle micropore compound titanium silicon molecular sieve prepared by 50 μ l hydrogen peroxide (30 weight %), 10ml deionized water, 0.2g embodiment 2 is added sequentially in reactor, water-bath temperature control is at 60 DEG C, electromagnetic agitation 6h, upper oil phase Angilent company HP-6890N type gas chromatographic analysis is taken at interval of 1h, HP-5 capillary column, column length 30m, internal diameter 0.32mm, FPD detector.Reaction result: thiophene removal efficiency 98%.
Application examples 2
Take 10.56mg dibenzothiophenes to be dissolved in 10ml normal octane as analog fuel, join 100ml with in three mouthfuls of reactors of water-bath chuck, then middle micropore compound titanium silicon molecular sieve prepared by 50 μ l hydrogen peroxide (30 weight %), 10ml methanol, 0.2g embodiment 2 is added sequentially in reactor, water-bath temperature control is at 60 DEG C, electromagnetic agitation 6h, upper oil phase Angilent company HP-6890N type gas chromatographic analysis is taken at interval of 1h, HP-5 capillary column, column length 30m, internal diameter 0.32mm, FPD detector.Reaction result: dibenzothiophenes removal efficiency 100%.
Claims (6)
1. core shell type micro-hole/composite mesoporous HTS, it is characterized in that: there is nucleocapsid structure, kernel is the micropore titanium silicon molecular sieve TS-1 of particle diameter 200～300nm, and shell is the six order mesoporous titaniferous silicon dioxide of side of aperture 2～3nm, and outer casing thickness is 20～100nm.
2. core shell type micro-hole according to claim 1/composite mesoporous HTS, is characterized in that: this composite molecular screen is elementary composition by silicon, oxygen, titanium three kinds, for spherical morphology, specific surface area 500～700m2/ g, the internal diameter 220～500nm of shell.
3. a preparation for the core shell type micro-hole described in claim 1/composite mesoporous HTS, particularly as follows:
(1) mol ratio that 0.25g micropore titanium silicon molecular sieve TS-1 is scattered in 60～200ml is deionized water ethanol surfactant NH4In the reaction system of OH resorcinol formaldehyde=2.2～4.4 0.4～0.8 0.0014 0.0044 0.00045～0.0018 0.0009～0.0036, stirring 6～24h under room temperature, 25～100 DEG C stand 8～24h and prepare the titanium-silicon molecular sieve TS-1 of novalac polymer cladding；
(2) titanium-silicon molecular sieve TS-1 that 0.5g novalac polymer is coated with is scattered in the mixed system that mol ratio is deionized water ethanol surfactant NH4OH=2.78～11.1 1.04～4.16 0.00015～0.0006 0.03～0.12 of 80～480ml, add the silicon source of 0.00096～0.0048mol and the titanium source of 0.0000048～0.000192mol, 40～80 DEG C of stirring 8～72h, product passes through dried at 550 DEG C of roasting 5h.
4. preparation method according to claim 3, is characterized in that: described micropore titanium silicon molecular sieve TS-1 is with silicon tetraethyl acid esters for silicon source, and positive four butyl esters of metatitanic acid are titanium source, and TPAOH is template, adopts hydro-thermal method to prepare.
5. preparation method according to claim 3, is characterized in that: described surfactant is formula is CnH2n+1(CH3)3The quaternary cationics of NBr, wherein n=12～16.
6. preparation method according to claim 3, is characterized in that: the silicon source described in step (2) is silicon tetraethyl acid esters, and titanium source is positive four butyl esters of metatitanic acid.
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Cited By (7)
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| CN107999124A (en) * | 2017-12-14 | 2018-05-08 | 中触媒新材料股份有限公司 | A kind of core shell structure Ti-MWW@Si molecular sieves and its preparation and application |
| CN107999125A (en) * | 2017-12-14 | 2018-05-08 | 中触媒新材料股份有限公司 | A kind of core shell structure Ti-MWW system with molecular sieve for preparing containing micropore-mesopore is standby and applies |
| CN112007690A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime through macromolecular ketone ammoximation reaction |
| CN113318480A (en) * | 2020-02-28 | 2021-08-31 | 北方民族大学 | Hydrophilic nano core-shell material and preparation method and application thereof |
| CN113441168A (en) * | 2020-03-25 | 2021-09-28 | 中国科学院大连化学物理研究所 | Core-shell structure hierarchical pore catalytic material for adsorbing inactivated viruses and application |
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Cited By (12)
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| CN107999124A (en) * | 2017-12-14 | 2018-05-08 | 中触媒新材料股份有限公司 | A kind of core shell structure Ti-MWW@Si molecular sieves and its preparation and application |
| CN107999125A (en) * | 2017-12-14 | 2018-05-08 | 中触媒新材料股份有限公司 | A kind of core shell structure Ti-MWW system with molecular sieve for preparing containing micropore-mesopore is standby and applies |
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| CN112007690A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime through macromolecular ketone ammoximation reaction |
| CN112007690B (en) * | 2019-05-31 | 2022-12-09 | 中国石油化工股份有限公司 | Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime by macromolecular ketone ammoximation reaction |
| CN113318480A (en) * | 2020-02-28 | 2021-08-31 | 北方民族大学 | Hydrophilic nano core-shell material and preparation method and application thereof |
| CN113441168A (en) * | 2020-03-25 | 2021-09-28 | 中国科学院大连化学物理研究所 | Core-shell structure hierarchical pore catalytic material for adsorbing inactivated viruses and application |
| CN113441168B (en) * | 2020-03-25 | 2023-08-08 | 中国科学院大连化学物理研究所 | Core-shell structure hierarchical pore catalytic material for adsorbing inactivated virus and application thereof |
| CN114669287A (en) * | 2022-04-26 | 2022-06-28 | 西安科技大学 | Ordered mesoporous titanium-aluminum composite oxide coated TS-1 molecular sieve material and preparation method thereof |
| CN115557840A (en) * | 2022-11-04 | 2023-01-03 | 浙江新化化工股份有限公司 | Preparation method of 2-nitropropane and catalyst used in preparation method |
| CN115557840B (en) * | 2022-11-04 | 2023-11-10 | 浙江新化化工股份有限公司 | Preparation method of 2-nitropropane and catalyst used in preparation method |
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