CN105712367B - A kind of core shell type micro-hole/composite mesoporous Titanium Sieve Molecular Sieve and preparation method thereof - Google Patents
A kind of core shell type micro-hole/composite mesoporous Titanium Sieve Molecular Sieve and preparation method thereof Download PDFInfo
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- CN105712367B CN105712367B CN201410720705.0A CN201410720705A CN105712367B CN 105712367 B CN105712367 B CN 105712367B CN 201410720705 A CN201410720705 A CN 201410720705A CN 105712367 B CN105712367 B CN 105712367B
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Abstract
The present invention provides a kind of core shell type micro-hole/composite mesoporous Titanium Sieve Molecular Sieve and preparation method thereof.The composite molecular screen be subsphaeroidal pattern, 500~700m of specific surface area2/ g, with typical core shell structure, kernel is the micropore titanium silicon molecular sieve TS 1 of 200~300nm of grain size, and outer shell is the order mesoporous titaniferous silica of six sides of 2~3nm of aperture, there are certain gap between kernel and shell, the size in gap and the thickness of shell can be with modulations.The composite molecular screen is prepared by two-step method, and novalac polymer is first coated on 1 surfaces of micropore titanium silicon molecular sieve TS as hard template, then coating mesoporous titaniferous silica.The invention has the advantages that the composite molecular screen provided has multistage pore canal, hollow nucleocapsid is conducive to guest molecule diffusion, has good application prospect in fields such as catalysis, adsorbing separations, and preparation process is simple, efficient, controllability is strong.
Description
Technical field
The invention belongs to field of material preparation, and in particular to a kind of multi-stage porous compound titanium silicon molecular sieve and preparation method thereof.
Background technology
Titanium Sieve Molecular Sieve has excellent catalytic performance for the organic matter selective oxidation that is carried out under temperate condition, always with
To receive the extensive concern of researchers.Although traditional micropore titanium silicon molecular sieve is with higher activity, narrow
Duct limits its application in macromolecular reaction.Although mesoporous titanium-silicon molecular screen duct is open, its amorphous essence
Determine that its intrinsic activity is relatively low.Therefore, it is how that micropore and meso titanium silica catalysis material is mutually compound, make its mutual supplement with each other's advantages, into
For the hot spot of Recent study.
At present, middle mesoporous-microporous composite molecular sieve reported and preparation method thereof mainly includes three kinds.One is use some
Certain moduli plate agent introduced in micro porous molecular sieve it is mesoporous, although diffusion limitation make moderate progress, this material preparation process
Complexity, and need to use some expensive surfactants (Nature Mater., 2006,5,718；Angew.Chem.,
Int.Ed.,2006,45,3090；Chem.Commun.,2011,47,3529.).The second is micro porous molecular sieve structural unit is drawn
Entering in mesoporous material skeleton, the activity and stability of prepared material increase, but compared with general microporous zeolite
Still have apparent gap (J.Am.Chem.Soc., 2002,124,888；Angew.Chem.,2001,113,1295；
Chem.Mater.,2007,19,1664.).In addition it is by micro porous molecular sieve and mesoporous material direct combination in some way, makes
The feature that they have complementary advantages is more obvious.Typical work has：Peng etc. passes through control ph using P123 as mesoporous template
Synthesized mesoporous silicon oxide cladding titanium-silicon molecular sieve TS-1 core-shell material (Micropor.Mesopor.Mater., 2012,
153,8)；Qian etc. using similar method synthesize ZSM-5@SBA-15 micropores/mesoporous composite molecular sieve (Chem.Sci.,
2011,2,2006.).But micropore kernel and mesoporous shell are to be in close contact in these materials, are unfavorable for guest molecule
Diffusion.It is still a challenge to develop new composite molecular screen and preparation method thereof.
The content of the invention
The object of the present invention is to provide a kind of core shell type micro-hole/composite mesoporous Titanium Sieve Molecular Sieve and preparation method thereof.
A kind of core shell type micro-hole/composite mesoporous Titanium Sieve Molecular Sieve is made of three kinds of silicon, oxygen, titanium elements, is subsphaeroidal shape
Looks, 500~700m of specific surface area2/ g, has nucleocapsid, and kernel is the micropore titanium silicon molecular sieve TS- of 200~300nm of grain size
1, shell is the order mesoporous titaniferous silica of six sides of 2~3nm of aperture, and thickness is 20~100nm, is deposited between kernel and shell
In the gap of 20~200nm.
A kind of preparation method of core shell type micro-hole/composite mesoporous Titanium Sieve Molecular Sieve is divided into two steps, is specially：
(1) 0.25g micropore titanium silicon molecular sieves TS-1 is scattered in molar ratio for Qu Li Shui ﹕ Yi Chun ﹕ Biao face Huo Ji ﹕
NH40.00045~0.0018 ﹕ 0.0009 of OH ﹕ Jian Ben bis- Fen ﹕ formaldehyde=2.2~4.4 ﹕, 0.4~0.8 ﹕, 0.0014 ﹕, 0.0044 ﹕~
In 0.0036 reaction system, 6 are stirred at room temperature~for 24 hours, 25~100 DEG C stand 8~prepare novalac polymer bag for 24 hours
The titanium-silicon molecular sieve TS-1 covered；
(2) titanium-silicon molecular sieve TS-1 that 0.5g novalac polymers coat is scattered in molar ratio for Qu Li Shui ﹕ second
Chun ﹕ Biao faces Huo Ji ﹕ NH4The mixture of OH=2.78~11.1 ﹕, 1.04~4.16 ﹕, 0.00015~0.0006 ﹕ 0.03~0.12
In system, the silicon source of 0.00096~0.0048mol and the titanium source of 0.0000048~0.000192mol, 40~80 DEG C of stirrings 8 are added in
~72h, product roast 5h by dry at 550 DEG C.
The micropore titanium silicon molecular sieve TS-1 be using silicon tetraethyl acid esters as silicon source, positive four butyl ester of metatitanic acid be titanium source, four
Propyl ammonium hydroxide is template, is prepared using hydro-thermal method.
The surfactant is that general formula is CnH2n+1(CH3)3The quaternary ammonium salt cationic surfactant of NBr, wherein
N=12~16.
The silicon source is silicon tetraethyl acid esters, and titanium source is positive four butyl ester of metatitanic acid.
Nucleocapsid micropore provided by the invention/composite mesoporous Titanium Sieve Molecular Sieve, compound with regular structure, Parameter adjustable are conducive to
Guest molecule is spread, and its preparation method is simple, efficient, controllability is strong.
Description of the drawings
Fig. 1 is the transmission electron microscope photo of core shell type micro-hole/composite mesoporous Titanium Sieve Molecular Sieve of the present invention, corresponding embodiment
2。
Fig. 2 is the X-ray diffractogram of core shell type micro-hole/composite mesoporous Titanium Sieve Molecular Sieve of the present invention, corresponding embodiment 2.
Specific embodiment
Bibliography prepares micropore titanium silicon molecular sieve TS-1
11.2ml silicon tetraethyls acid esters and the positive four butyl esters mixing of 0.34g metatitanic acids, are added dropwise to 29.5ml tetrapropyl hydrogen-oxygens jointly
Change in aqueous ammonium (mass concentration 9%), stir 1.5h at room temperature, 80 DEG C of stirring 4h, supplement deionized water to initial volume will
Reaction solution is fitted into the stainless steel autoclave with polytetrafluoroethyllining lining, and 48h is stood at 170 DEG C, centrifuges out solid production
Object, 120 DEG C of drying, the lower 550 DEG C of roastings 5h of air atmosphere obtain the micropore titanium silicon molecular sieve TS-1 of 200~300nm of grain size.
Embodiment 1
0.25g micropore titanium silicon molecular sieves TS-1 is taken to be scattered in 40ml deionized waters and 20ml absolute ethyl alcohols, adds in 0.5g ten
Six alkyl trimethyl ammonium bromides and 0.3g ammonium hydroxide stir 0.5h, and it is 37% to add in 0.05g resorcinols and 0.075g mass concentrations
Formalin, persistently stir 8h at room temperature, stand 14h, filter out product, in 80 DEG C of drying, obtain novalac polymer
The micropore titanium silicon molecular sieve TS-1 (TS-1@RF) of cladding.Take that 0.5g TS-1@RF are scattered in 100ml deionized waters and 60ml is anhydrous
In ethyl alcohol, 0.05g cetyl trimethylammonium bromides and 2g ammonium hydroxide are added in, 40 DEG C of stirring 0.5h add in 0.57g tetraethyl silicic acid
Ester and positive four butyl ester of 0.018g metatitanic acids, persistently stir 15h, filtering, 80 DEG C of drying, and the lower 550 DEG C of roastings 5h of air atmosphere is obtained
Core shell type micro-hole/composite mesoporous Titanium Sieve Molecular Sieve.
Embodiment 2
0.25g micropore titanium silicon molecular sieves TS-1 is taken to be scattered in 40ml deionized waters and 20ml absolute ethyl alcohols, adds in 0.5g ten
Six alkyl trimethyl ammonium bromides and 0.3g ammonium hydroxide stir 0.5h, and it is 37% to add in 0.1g resorcinols and 0.15g mass concentrations
Formalin persistently stirs 8h at room temperature, stands 14h, filters out product, in 80 DEG C of drying, obtains novalac polymer bag
The micropore titanium silicon molecular sieve TS-1 (TS-1@RF) covered.0.5g TS-1@RF is taken to be scattered in 100ml deionized waters and the anhydrous second of 60ml
In alcohol, 0.05g cetyl trimethylammonium bromides and 2g ammonium hydroxide are added in, 40 DEG C of stirring 0.5h add in 0.57g silicon tetraethyl acid esters
With positive four butyl ester of 0.018g metatitanic acids, persistently stir 15h, filter, 80 DEG C drying, air atmosphere it is lower 550 DEG C roasting 5h, obtain core/
Shell-type micropore/composite mesoporous Titanium Sieve Molecular Sieve.
Embodiment 3
0.25g micropore titanium silicon molecular sieves TS-1 is taken to be scattered in 40ml deionized waters and 20ml absolute ethyl alcohols, adds in 0.5g ten
Six alkyl trimethyl ammonium bromides and 0.3g ammonium hydroxide stir 0.5h, and it is 37% to add in 0.2g resorcinols and 0.3g mass concentrations
Formalin persistently stirs 8h at room temperature, stands 14h, filters out product, in 80 DEG C of drying, obtains novalac polymer bag
The micropore titanium silicon molecular sieve TS-1 (TS-1@RF) covered.0.5g TS-1@RF is taken to be scattered in 100ml deionized waters and the anhydrous second of 60ml
In alcohol, 0.05g cetyl trimethylammonium bromides and 2g ammonium hydroxide are added in, 40 DEG C of stirring 0.5h add in 0.57g silicon tetraethyl acid esters
With positive four butyl ester of 0.018g metatitanic acids, 15h is persistently stirred, is filtered, 80 DEG C of drying, the lower 550 DEG C of roastings 5h of air atmosphere obtains nucleocapsid
Gap is core shell type micro-hole/composite mesoporous Titanium Sieve Molecular Sieve of 20nm.
Embodiment 4
0.25g micropore titanium silicon molecular sieves TS-1 is taken to be scattered in 40ml deionized waters and 20ml absolute ethyl alcohols, adds in 0.5g ten
Six alkyl trimethyl ammonium bromides and 0.3g ammonium hydroxide stir 0.5h, and it is 37% to add in 0.1g resorcinols and 0.15g mass concentrations
Formalin persistently stirs 8h at room temperature, stands 14h, filters out product, in 80 DEG C of drying, obtains novalac polymer bag
The micropore titanium silicon molecular sieve TS-1 (TS-1@RF) covered.0.5g TS-1@RF is taken to be scattered in 100ml deionized waters and the anhydrous second of 60ml
In alcohol, 0.05g cetyl trimethylammonium bromides and 2g ammonium hydroxide are added in, 40 DEG C of stirring 0.5h add in 0.2g silicon tetraethyl acid esters
With positive four butyl ester of 0.006g metatitanic acids, persistently stir 15h, filter, 80 DEG C drying, air atmosphere it is lower 550 DEG C roasting 5h, obtain core/
Shell-type micropore/composite mesoporous Titanium Sieve Molecular Sieve.
Embodiment 5
0.25g micropore titanium silicon molecular sieves TS-1 is taken to be scattered in 40ml deionized waters and 20ml absolute ethyl alcohols, adds in 0.5g ten
Six alkyl trimethyl ammonium bromides and 0.3g ammonium hydroxide stir 0.5h, and it is 37% to add in 0.1g resorcinols and 0.15g mass concentrations
Formalin persistently stirs 8h at room temperature, stands 14h, filters out product, in 80 DEG C of drying, obtains novalac polymer bag
The micropore titanium silicon molecular sieve TS-1 (TS-1@RF) covered.0.5g TS-1@RF is taken to be scattered in 100ml deionized waters and the anhydrous second of 60ml
In alcohol, 0.05g cetyl trimethylammonium bromides and 2g ammonium hydroxide are added in, 60 DEG C of stirring 0.5h add in 0.57g silicon tetraethyl acid esters
With positive four butyl ester of 0.018g metatitanic acids, persistently stir 15h, filter, 80 DEG C drying, air atmosphere it is lower 550 DEG C roasting 5h, obtain core/
Shell-type micropore/composite mesoporous Titanium Sieve Molecular Sieve.
Application examples 1
10 μ l thiophene is taken to be dissolved in 10ml normal octanes as analog fuel, it is anti-to be added to three mouthfuls with water-bath chuck of 100ml
It answers in device, the middle micropore composite Ti-Si for then preparing 50 μ l hydrogen peroxide (30 heavy %), 10ml deionized waters, 0.2g embodiments 2
Molecular sieve is added sequentially in reactor, and water-bath temperature control takes upper oil phase to use in 60 DEG C, electromagnetic agitation 6h at interval of 1h
Angilent companies HP-6890N type gas chromatographic analysis, HP-5 capillary columns, column length 30m, internal diameter 0.32mm, FPD detector.
Reaction result：Thiophene removal efficiency 98%.
Application examples 2
10.56mg dibenzothiophenes is taken to be dissolved in 10ml normal octanes as analog fuel, is added to 100ml band water-bath chucks
Three mouthfuls of reactors in, then by 50 μ l hydrogen peroxide (30 heavy %), 10ml methanol, 0.2g embodiments 2 prepare middle micropore it is compound
Titanium Sieve Molecular Sieve is added sequentially in reactor, and water-bath temperature control takes upper oil phase to use in 60 DEG C, electromagnetic agitation 6h at interval of 1h
Angilent companies HP-6890N type gas chromatographic analysis, HP-5 capillary columns, column length 30m, internal diameter 0.32mm, FPD detector.
Reaction result：Dibenzothiophenes removal efficiency 100%.
Claims (6)
1. a kind of core shell type micro-hole/composite mesoporous Titanium Sieve Molecular Sieve, it is characterized in that：With nucleocapsid, kernel for grain size 200 ~
The micropore titanium silicon molecular sieve TS-1 of 300nm, shell be 2 ~ 3nm of aperture the order mesoporous titaniferous silica of six sides, outer casing thickness
For 20 ~ 100nm.
2. core shell type micro-hole according to claim 1/composite mesoporous Titanium Sieve Molecular Sieve, it is characterized in that：The composite molecular screen
It is made of three kinds of silicon, oxygen, titanium elements, for spherical morphology, 500 ~ 700m of specific surface area2/ g, 220 ~ 500nm of internal diameter of shell.
3. a kind of preparation method of core shell type micro-hole described in claim 1/composite mesoporous Titanium Sieve Molecular Sieve is specially：
（1）0.25g micropore titanium silicon molecular sieves TS-1 is scattered in the molar ratio of 60 ~ 200mL to live for Qu Li Shui ﹕ Yi Chun ﹕ surfaces
Xing Ji ﹕ NH4OH ﹕ Jian Ben bis- Fen ﹕ formaldehyde=2.2 ~ 4.4 ﹕, 0.4 ~ 0.8 ﹕, 0.0014 ﹕, 0.0044 ﹕, 0.00045 ~ 0.0018 ﹕
In 0.0009 ~ 0.0036 reaction system, at room temperature stir 6 ~ for 24 hours, 25 ~ 100 DEG C stand 8 ~ prepare for 24 hours phenolic resin polymerization
The titanium-silicon molecular sieve TS-1 of object cladding；
（2）The titanium-silicon molecular sieve TS-1 that 0.5g novalac polymers coat is scattered in the molar ratio of 80 ~ 480mL for go from
Sub- Shui ﹕ Yi Chun ﹕ Biao face Huo Ji ﹕ NH4The mixing of OH=2.78 ~ 11.1 ﹕, 1.04 ~ 4.16 ﹕, 0.00015 ~ 0.0006 ﹕ 0.03 ~ 0.12
In system, the silicon source of 0.00096 ~ 0.0048mol of addition and the titanium source of 0.0000048 ~ 0.000192mol, 40 ~ 80 DEG C of stirrings 8 ~
72h, product roast 5h after drying at 550 DEG C.
4. preparation method according to claim 3, it is characterized in that：The micropore titanium silicon molecular sieve TS-1 is with tetraethyl
Esters of silicon acis is silicon source, and positive four butyl ester of metatitanic acid is titanium source, and tetrapropylammonium hydroxide is template, is prepared using hydro-thermal method.
5. preparation method according to claim 3, it is characterized in that：The surfactant is that general formula is CnH2n+1(CH3)3The quaternary cationics of NBr, wherein n=12 ~ 16.
6. preparation method according to claim 3, it is characterized in that：Step（2）The silicon source be silicon tetraethyl acid esters, titanium
Source is positive four butyl ester of metatitanic acid.
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| CN107999125B (en) * | 2017-12-14 | 2020-09-08 | 中触媒新材料股份有限公司 | Preparation and application of microporous-mesoporous-containing Ti-MWW molecular sieve with core-shell structure |
| CN107999124B (en) * | 2017-12-14 | 2020-11-24 | 中触媒新材料股份有限公司 | Core-shell structure Ti-MWW @ Si molecular sieve and preparation and application thereof |
| 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 |
| CN113318480B (en) * | 2020-02-28 | 2022-12-30 | 北方民族大学 | Hydrophilic nano core-shell material and preparation method and application thereof |
| 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 |
| CN114669287B (en) * | 2022-04-26 | 2024-09-24 | 西安科技大学 | Ordered mesoporous titanium aluminum composite oxide coated TS-1 molecular sieve material and preparation method thereof |
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