CN107954448A - Mesoporous-SAPO-34 molecular sieves of straight channels and preparation method thereof - Google Patents
Mesoporous-SAPO-34 molecular sieves of straight channels and preparation method thereof Download PDFInfo
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- CN107954448A CN107954448A CN201610895858.8A CN201610895858A CN107954448A CN 107954448 A CN107954448 A CN 107954448A CN 201610895858 A CN201610895858 A CN 201610895858A CN 107954448 A CN107954448 A CN 107954448A
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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Abstract
The present invention relates to mesoporous 34 molecular sieves of SAPO of a kind of straight channels and preparation method thereof.The problems such as mainly solution conventional art its micropore when preparation has mesoporous 34 molecular sieves of SAPO can not connect completely with mesopore orbit, and mesopore orbit easily caves in.The present invention is by using secondary treatment method, microemulsion of the dipping rich in silicon/aluminium/phosphorus/34 templates of SAPO/structure directing agent in mesopore molecular sieve, adjust suitable acid-base value, at a certain temperature, pass through secondary crystallization, in 34 molecular sieves of mesopore molecular sieve inner surface epitaxial growth SAPO, then technical solution of the generation with through-type 34 molecular sieves of mesoporous SAPO, available for preparing in a variety of straight-through mesopore molecular sieve industrial productions.
Description
Technical field
The present invention relates to mesoporous-SAPO-34 molecular sieves of a kind of straight channels and preparation method thereof.
Background technology
SAPO-34 molecular sieves belong to micro porous molecular sieve series, belong to chabasie class, its skeleton is mainly made of sial phosphorus oxygen,
The CHA cages and three dimensional intersection pore passage structure formed with double hexatomic rings, octatomic ring and four-membered ring.SAPO-34 has high selection
Property, high hydrothermal stability, suitable acidity, excellent catalytic performance is shown in MTO reactions.SAPO-34 molecular sieves in
Developed first by U.S. combinating carbide company (UCC) within 1984, using triethylamine as structure directing agent, at 100-180 DEG C
Lower crystallization is prepared for 6h-10 days.The activated centre of micro porous molecular sieve is more inside duct.Molecular sieve main aperture road is longer to be increased
Diffusional resistance of the molecule inside its duct, prevents target product molecule finally to occur secondary from diffusing out in time inside duct
Reaction generates other molecules.Therefore diffusion path is shortened, reduction diffusional resistance has great importance.In one piece of micro porous molecular sieve
Introduced in crystal it is mesoporous come reduce diffusional resistance, accelerate diffusion：That is, point of synthetic microporous-composite mesoporous multi-stage artery structure
Son sieve material has become the hot spot studied at present.The method of common synthesis multi-stage porous SAPO-34 molecular sieves is in synthetic system
In not only add the micropore template agent for promoting SAPO-34 skeletons to be formed, be additionally added the mesoporous template for induce mesoporous formation, including work
Cationic polymerization for the carbon black pellet of hard template, carbon nanotubes, charcoal-aero gel, polysaccharide compound etc. and as soft template
Organosilan of thing and amphiphatic molecule etc.；The refined grade of model (《Materials Science and Engineering journal》, 2015,33,382) and by introducing silicon
Alkane coupling agent KH550 is to prepare mesoporous SAPO-34 molecular sieves；Yang et al. induces synthesising mesoporous SAPO-34 using microwave mode
Molecular sieve (S.T.Yang et al, J.Mater.Res.Bull.2012,47,3888)；Askari(Askari et al.,
J.Mater.Res.Bull, 2013,48,1851) et al. accumulate to form tool with nanometer SAPO-34 crystallites using Taguchi methods
There are the SAPO-34 molecular sieves of mesoporous distribution.Although above method can obtain mesoporous distribution, the use of mesoporous template is not only
The complication that cost also results in synthesis step is added, is not appropriate for industrializing.Also, although above-mentioned various methods are prepared for
The mesopore molecular sieve of SAPO-34, but the microporous mesoporous mesoporous SAPO-34 directly connected research hotspot and difficult point always, are reported
Or the method preparation process in road is complicated, it is necessary to introduce the surfactant of price costly, complicated large scale template
Deng so that cost is high, post processing is cumbersome and causes environmental pollution., the multi-stage porous of gained is not truly straight
Lead in succession.Therefore, also there is very big challenge, conventional synthesis process limit for the preparation with the mesoporous SAPO-34 directly connected
Development and the commercial Application of through-type mesoporous SAPO-34 molecular sieves are made.
The content of the invention
The technical problems to be solved by the invention, that is, of high cost, the mesoporous SAPO-34 molecules of gained existing in the prior art
Sieve the problem of low, the straight-through property of crystallinity is poor, there is provided a kind of new straight-through mesoporous SAPO-34 molecular sieves.This method is located after having
Reason process is simple；Manufacturing cost is low, and any mesopore molecular sieve can serve as directly connecting；Environmental-friendly, microemulsion all soaks
Stain, has reached Zero discharge；The mesoporous SAPO-34 of gained reaches the features such as real micropore-mesopore unbounded connection.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：One kind leads directly to mesoporous-SAPO-34 molecules
Sieve, the spontaneous straight channels constructed along b- directions in mesopore molecular sieve duct, straight channels and the mesopore orbit in b- directions are put down
Row orientation.
In above-mentioned technical proposal, at least one in SBA, MCM that mesoporous molecular is 2~10 nanometers screened from channel diameter
Kind, and there are straight channels.
In above-mentioned technical proposal, mesoporous molecular has straight-through screened from the SBA and MCM that channel diameter is 2~8 nanometers
Duct.
In above-mentioned technical proposal, the mesopore molecular sieve is SBA-15 or MCM-41 or MCM-48.
In above-mentioned technical proposal, preferred technical solution, is that mesopore molecular sieve is SBA-15 and MCM-48, wherein, it is situated between
Porous molecular sieve is SBA-15 and the mass ratio of MCM-48 is 1~2：1
The present invention also provides a kind of preparation method for leading directly to mesoporous SAPO-34 molecular sieves, comprise the following steps：
A) synthesising mesoporous molecular sieve, its duct size are adjusted by surfactant；
B) template, surfactant, water, silicon source, silicon source and organic solvent are mixed, it is micro- prepares SAPO-34 molecular sieves
Lotion；
C) the SAPO-34 molecular sieve microemulsions of preparation are impregnated into the mesopore molecular sieve described in step a) and obtain precursor
A；
D) at 95~255 DEG C, under certain pressure, SAPO-34 microemulsions in mesopore molecular sieve slow crystallization and be situated between
Hole-SAPO-34 molecular sieves；
E) roasted under the conditions of 310~590 DEG C 1~70 it is small when through-type mesoporous-SAPO-34 molecular sieves are made.
In above-mentioned technical proposal, the surfactant is selected from amphipathic polyethers, the aminated compounds of C8~C18.
In above-mentioned technical proposal, organic solvent is selected from benzene, toluene, at least one for the alkane that carbon number is more than 6.
The silicon source is included selected from ethyl orthosilicate, butyl silicate, white carbon, at least one of waterglass；
Source of aluminium is included selected from aluminium isopropoxide, aluminum nitrate, at least one of boehmite.
The silicon source：Silicon source：The molar ratio of template is 10:(1-8):(1-4)；The organic solvent, surfactant
Molar ratio with water is (2-18):(1-9):1.
The SAPO-34 molecular sieves microemulsion is 1 in mass ratio with mesopore molecular sieve:0.5~5.
In above-mentioned technical proposal, preferred scheme is that the organic solvent, surfactant are selected from trimethylbenzene and just
Octylame.
In above-mentioned technical proposal, the SAPO-34 molecular sieves microemulsion is water in oil microemulsion.
In above-mentioned technical proposal, in the SAPO-34 molecular sieves microemulsion, template, surfactant and water are mixed into
Water phase, silicon source, silicon source and organic solvent are mixed into oil phase, and mixing water phase and oil phase obtain microemulsion.
In above-mentioned technical proposal, crystallization temperature is 95~210 DEG C, and the reaction time is 6~40h.
Technical solution using the present invention, due to the use of the method for mesopore molecular sieve inner wall epitaxial growth, during crystallization, one
Divide mesoporous wall to serve as silicon source and enter microcellular structure, reach the seamless connection of micropore-mesopore hole wall；In crystallization process, SAPO-34 exists
" circle " mesoporous inner wall is slowly grown along a-, c- directions in a manner of LBL, finally spontaneous in mesopore orbit to construct along b-
The straight hole road in direction, the straight hole road in this direction is parallel-oriented with mesopore orbit and shorter than mesopore orbit, directly connects so foring
Logical micropore~mesoporous part.Template and directed agents containing N, O are removed by roasting, that is, is produced highly uniform mesoporous-micro-
Hole connectivity structure.Since whole process uses the method for complete wetting, the microemulsion of SAPO-34 is not unnecessary and needs blowdown
Part, greatly reduces the cost of reaction, while also environmentally friendly.Achieve preferable technique effect.
Attached drawing and explanation
Fig. 1 is the high-resolution-ration transmission electric-lens of the straight-through mesoporous SAPO-34 molecular sieves prepared in embodiment 1 under the conditions of 150 DEG C
Figure.The fine and close micropore canals with apparent 0.4nm and the of a relatively loose mesopore orbit parallel with apparent 2.1nm in figure
Row, and cover wherein, clearly disclose micropore and connected with the unbounded of mesoporous part, refer to Fig. 1.Fig. 1 leads directly to mesoporous SAPO-34
The high resolution electron microscopy photo of molecular sieve.Fig. 1-1 is the micropore-mesopore straight channels structure of SAPO-34 molecular sieves；Fig. 1-2 is Fig. 1
In the red corresponding Fourier transformation figure of frame, match with XRD results, show that micropore-mesopore duct is arranged in parallel.
Fig. 2 is small angle and the wide-angle x-ray of the straight-through mesoporous SAPO-34 molecular sieves prepared in embodiment 1 under the conditions of 150 DEG C
Diffraction spectrogram.What the mesoporous part that XRD discloses the material was ordered into, the main diffraction peak of celled portion and the mark of SAPO-34
The principal character peak of quasi- spectrogram is consistent.
Fig. 3 is the mesoporous schematic diagram of straight channels of molecular sieve.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
The preparation for leading directly to mesoporous SAPO-34 molecular sieves carries out according to the following steps：SAPO-34 water-in-oil microemulsions are prepared first
Liquid, triethylamine (TEA) are micro emulsion water phase, ethyl orthosilicate (TEOS) and aluminium isopropoxide with the aqueous solution that phosphoric acid, tri-n-octyl amine are matched somebody with somebody
Toluene solution be oil phase, mixing water phase and an oil phase obtain clear microemulsion I.Si in microemulsion I：Al：The molar ratio of TEA is 1：
1：3；Toluene is 2 with the molar ratio of tri-n-octyl amine and water：1：1；Lower microemulsion I of normal temperature condition and baked molecular sieve pore passage
A diameter of 4~8 nanometers of SBA-15 molecular sieves in mass ratio 0.5：1 dipping obtains precursor II.After when aging 1 is small at 60 DEG C,
Precursor II is loaded stainless steel cauldron, under the conditions of 180 DEG C, crystallization 48 obtains the mesoporous SAPO-34 containing template when small
Molecular sieve.After product takes out, the mesoporous-SAPO-34 molecular sieves of straight channels are obtained when roasting 6 is small under the conditions of 550 DEG C, wherein
The void ratio of mesopore molecular sieve and SAPO-34 molecular sieves is 1.3.Data refer to table 1.
【Embodiment 2】
The preparation for leading directly to mesoporous SAPO-34 molecular sieves carries out according to the following steps：SAPO-34 water-in-oil microemulsions are prepared first
Liquid, triethylamine (TEA) are micro emulsion water phase, ethyl orthosilicate (TEOS) and aluminium isopropoxide with the aqueous solution that phosphoric acid, tri-n-octyl amine are matched somebody with somebody
Toluene solution be oil phase, mixing water phase and an oil phase obtain clear microemulsion I.Si in microemulsion I：Al：The molar ratio of TEA is 1：
1：3；Toluene is 2 with the molar ratio of tri-n-octyl amine and water：1：1；Lower microemulsion I of normal temperature condition and baked molecular sieve pore passage
A diameter of 2~6 nanometers of six side's shape MCM-41 in mass ratio 0.5：1 dipping obtains precursor II.After when aging 1 is small at 60 DEG C,
Precursor II is loaded stainless steel cauldron, under the conditions of 180 DEG C, crystallization 48 obtains the mesoporous SAPO-34 containing template when small
Molecular sieve.After product takes out, straight-through mesoporous SAPO-34 molecular sieves are obtained when roasting 6 is small under the conditions of 550 DEG C.Its intermediary hole
The void ratio of molecular sieve and SAPO-34 molecular sieves is 1.25.Data refer to table 1.
【Embodiment 3】
The preparation for leading directly to mesoporous SAPO-34 molecular sieves carries out according to the following steps：SAPO-34 water-in-oil microemulsions are prepared first
Liquid, triethylamine (TEA) are micro emulsion water phase, ethyl orthosilicate (TEOS) and aluminium isopropoxide with the aqueous solution that phosphoric acid, tri-n-octyl amine are matched somebody with somebody
Toluene solution be oil phase, mixing water phase and an oil phase obtain clear microemulsion I.Si in microemulsion I：Al：The molar ratio of TEA is 1：
1：3；Toluene is 2 with the molar ratio of tri-n-octyl amine and water：1：1；Lower microemulsion I of normal temperature condition and baked mesopore molecular sieve
In mass ratio 0.5：1 dipping obtains precursor II, and wherein mesopore molecular sieve is the cubic MCM-48 that channel diameter is 2~4 nanometers
Molecular sieve.After when aging 1 is small at 60 DEG C, precursor II is loaded stainless steel cauldron, under the conditions of 180 DEG C, when crystallization 48 is small
Obtain the mesoporous SAPO-34 molecular sieves containing template.After product takes out, obtained when roasting 6 is small under the conditions of 550 DEG C straight-through
Mesoporous SAPO-34 molecular sieves.The void ratio of wherein mesopore molecular sieve and SAPO-34 molecular sieves is 1.1.Data refer to table 1.
【Comparative example 1-2】
According to the method for embodiment 1, simply change the water and oil balance of microemulsion, then can obtain mesoporous SAPO-34 molecular sieves,
But duct is disconnected.Refer to table 2
Table 1
| Embodiment | 1 | 2 | 3 |
| Synthesis temperature (℃) | 180 | 180 | 180 |
| Reaction time (h) | 48 | 48 | 48 |
| Calcination temperature (℃) | 550 | 550 | 550 |
| Mesopore molecular sieve type | SBA-15 | MCM-41 | MCM-48 |
| Than surface (m2/g) | 370 | 330 | 300 |
| Whether lead directly to | It is | It is | It is |
| It is situated between/micro- (void ratio) | 1.3 | 1.25 | 1.1 |
Table 2
| Comparative example | 1 | 2 |
| Synthesis temperature (℃) | 180 | 180 |
| Reaction time (h) | 48 | 48 |
| Calcination temperature (℃) | 550 | 550 |
| Microemulsion type | Water oil is continuous | Oil-in-water |
| With the presence or absence of mesoporous and SAPO-34 | It is | It is |
| Whether connect | It is non- | It is non- |
Claims (10)
1. a kind of mesoporous-SAPO-34 molecular sieves of straight channels, it is characterised in that spontaneous in mesopore molecular sieve duct to construct edge
The straight channels in b- directions, the straight channels and mesopore orbit in b- directions are parallel-oriented.
2. mesoporous-SAPO-34 the molecular sieves of straight channels according to claim 1, it is characterised in that mesoporous molecular is screened from hole
At least one of SBA, MCM that a diameter of 2~10 nanometers of road, and there are straight channels.
3. mesoporous-SAPO-34 the molecular sieves of straight channels according to claim 2, it is characterised in that mesoporous molecular is screened from hole
The SBA and MCM in a diameter of 2~8 nanometers of road, and there are straight channels.
4. mesoporous-SAPO-34 the molecular sieves of straight channels according to claim 1, it is characterised in that mesopore molecular sieve with
The void ratio of SAPO-34 molecular sieves is 1.0~2.5.
A kind of 5. preparation method of the mesoporous-SAPO-34 molecular sieves of straight channels as claimed in claim 1, it is characterised in that bag
Include following steps：
A) synthesising mesoporous molecular sieve, its duct size are adjusted by surfactant；
B) template, surfactant, water, silicon source, silicon source and organic solvent are mixed, prepares SAPO-34 molecular sieve microemulsions；
C) the SAPO-34 molecular sieve microemulsions prepared in b) step are impregnated into the mesopore molecular sieve described in step a) and obtained
Precursor A；
D) at 95~255 DEG C, SAPO-34 microemulsions in mesopore molecular sieve slow crystallization and obtain mesoporous-SAPO-34 molecules
Sieve；
E) roasted under the conditions of 310~590 DEG C 1~70 it is small when through-type mesoporous-SAPO-34 molecular sieves are made.
6. the preparation method of the mesoporous-SAPO-34 molecular sieves of straight channels according to claim 5, it is characterised in that described
Surfactant is selected from amphipathic polyethers, the aminated compounds of C8~C18.
7. the preparation method of the mesoporous-SAPO-34 molecular sieves of straight channels according to claim 5, it is characterised in that You Jirong
Agent is selected from least one of benzene, toluene, alkane that carbon number is more than 6.
8. the preparation method of the mesoporous-SAPO-34 molecular sieves of straight channels according to claim 5, it is characterised in that the silicon
Source is included selected from ethyl orthosilicate, butyl silicate, white carbon, at least one of waterglass；Source of aluminium includes being selected from isopropyl
Aluminium alcoholates, aluminum nitrate, at least one of boehmite.
9. the preparation method of the mesoporous-SAPO-34 molecular sieves of straight channels according to claim 5, it is characterised in that described
Silicon source：Silicon source：The molar ratio of template is 10：(1-8)：(1-4)；The molar ratio of the organic solvent, surfactant and water
For (2-18)：(1-9)：1.
10. the preparation method of the mesoporous-SAPO-34 molecular sieves of straight channels according to claim 5, it is characterised in that institute
It is 1 in mass ratio that SAPO-34 molecular sieves microemulsion, which is stated, with mesopore molecular sieve：0.5~5.
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Cited By (2)
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| CN110026235A (en) * | 2019-05-27 | 2019-07-19 | 泰州禾益新材料科技有限公司 | A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane |
| CN112744841A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Mesoporous SAPO-34 molecular sieve and synthetic method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110026235A (en) * | 2019-05-27 | 2019-07-19 | 泰州禾益新材料科技有限公司 | A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane |
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| CN112744841A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Mesoporous SAPO-34 molecular sieve and synthetic method thereof |
| CN112744841B (en) * | 2019-10-30 | 2022-07-12 | 中国石油化工股份有限公司 | Mesoporous SAPO-34 molecular sieve and synthetic method thereof |
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