CN105110349A - Preparation method for nano-sized AEL-structure molecular sieve - Google Patents
Preparation method for nano-sized AEL-structure molecular sieve Download PDFInfo
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Abstract
The invention relates to a preparation method for a nano-sized AEL-structure molecular sieve and belongs to the new catalytic material synthesis field and the energy and chemical industry field. Pseudo-boehmite, a heteroatom source, phosphoric acid and organic amine are used as raw materials, the raw materials are mixed, frozen and dried so that dry gel can be obtained, and then crystallization is performed on the dry gel, so that the AEL-structure molecular sieve is obtained. According to the preparation method for the nano-sized AEL-structure molecular sieve, at first, the gel is frozen and dried through a freeze drying technology to become dry gel, and then crystallization is performed on the dry gel. The AEL-structure molecular sieve prepared through the method has the advantages of achieving nanometer sizes and being high in specific area.
Description
Technical field
The present invention relates to a kind of preparation method of nano-scale AEL structure molecular sieve, belong to new catalytic material synthesis, derived energy chemical field.
Background technology
By isomorphous substitution form to introducing hetero-atoms in skeleton, give phosphate aluminium molecular sieve surface acidity, wherein MeAPO-11 molecular sieve is widely used in fields such as direct-connected alkane isomerizations because of its suitable one dimension ten-ring structure and gentle Acidity.Isomerization reaction belongs to aperture catalyzed reaction, and higher aperture exposure can improve isomeric hydrocarbon selectivity, and reduce Size of Zeolite, preparing nanoscale molecular sieve is the effective means realizing this target.Less molecular sieve particle diameter effectively can improve external surface area, shortens orifice throat length, reduce diffusional resistance, suppresses the generation of side reaction.The synthesis of nanoscale molecular sieve is generated by acceleration molecular sieve nucleus, and suppress the control devices such as aggregation of particles to be realized, common method has dry gel method, microwave process for synthesizing, space boundary method etc.Microwave synthesize can strengthen the Decomposition of gel by introducing microwave heating, nucleus quantity is made to reach close to saturated state at short notice, ensuing crystallization rate is accelerated, the molecular sieve particle diameter synthesized also can be controlled, the degree of crystallinity of synthetic sample is high, and can save the necessary low temperature aging program of conventional heating methods, but its synthesis condition is comparatively harsh, molecular sieve is defined in limited space by space boundary method, hinders it to grow and prevents the polymerization of its crystal grain.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of preparation method of nano-scale AEL structure molecular sieve, utilize dry gel method to have benefited from generation that its higher solid-to-liquid ratio easily brings out small crystal grain molecular sieve, the method possesses the advantage that water consumption is less, template can reuse, the present invention, on the basis playing xerogel advantage, prepares nanoscale, the high sieve sample than specific surface area by regulating and controlling dry glue preparation condition.
Concrete technical scheme is:
The preparation method of nano-scale AEL structure molecular sieve, comprises the following steps:
(1) following raw material is according to mol ratio proportioning, pseudo-boehmite, with Al
2o
3meter; Heteroatoms source, is designated as M, with oxide basis; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: heteroatoms source: phosphoric acid: organic amine=0.8 ~ 1.0:0 ~ 0.5:1.0:0.8 ~ 1.2;
Raw material and deionized water mix and blend are after 10-60 minute, and the lyophilize at-80 ~-40 DEG C of gained mixture, at 3.5-8.0, is then prepared dry glue in 1 ~ 4 day by regulation system pH value;
(2) by the dry glue of step (1) gained in autoclave at 160 ~ 200 DEG C crystallization 8 ~ 72 hours, obtain crystallization product; With the deionized water of mass ratio 6 ~ 11 times of crystallization products, gained crystallization product is washed and filtered, then at 60 ~ 120 DEG C, carry out drying 2 ~ 12 hours, then roasting obtains the molecular sieve of AEL structure after 2 ~ 10 hours at 350 ~ 650 DEG C.
Described heteroatoms source comprises Si, alkaline-earth metal, transition metal, the soluble compounds of thulium and/or hydrolyzable compound, the soluble compounds of the elements such as such as Si, Ge, Mg, Ca, Zn, Fe, Co, Cu, Ni, Ti, Zr, Mn, Y, La and Ce and/or hydrolyzable compound.
Described organic amine is a kind of in di-n-propylamine and Diisopropylamine or both mixtures.
The preparation method of nano-scale AEL structure molecular sieve provided by the invention, first Freeze Drying Technique is adopted to be dry glue by colloid lyophilize, then carrying out crystallization to dry glue, AEL structure molecular sieve prepared by the method has nanoscale, the feature that specific surface area is high.
Embodiment
The specific embodiment of the present invention is described in conjunction with the embodiments.
The raw material that embodiment is used:
Pseudo-boehmite, Yantai Heng Hui Chemical Co., Ltd. produces, Al
2o
3content 70wt%;
Phosphoric acid, Xilong Chemical Co., Ltd produces, analytical pure;
Di-n-propylamine and Diisopropylamine, deionized water, magnesium chloride, cobaltous chloride, zirconium oxychloride, Lanthanum trichloride, Chemical Reagent Co., Ltd., Sinopharm Group produces, analytical pure;
Acidic silicasol, Qingdao Marine Chemical Co., Ltd. produces, SiO
2content 25%.
Embodiment 1
Following raw material is according to mol ratio proportioning, and pseudo-boehmite, with Al
2o
3meter; Heteroatoms source, is designated as M, with oxide basis; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: phosphoric acid: di-n-propylamine=1.0:1.0:1.0;
With deionized water mix and blend after 30 minutes regulation system pH value be 5.5, then the lyophilize at-80 DEG C of gained colloid is prepared dry glue in 1 day; By dry for gained glue in autoclave at 160 DEG C crystallization after 54 hours, obtain crystallization product; Be that the deionized water of crystallization product 6 times to wash it and filters by quality, then carry out drying 4 hours in 100 DEG C, then in 550 DEG C through roasting after 4 hours the AlPO-11 molecular sieve of AEL structure, its particle size is 100nm, and specific surface area is 250m
2/ g.
Embodiment 2
Following raw material is according to mol ratio proportioning, and pseudo-boehmite, with Al
2o
3meter; Heteroatoms source magnesium chloride, in MgO; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: magnesium chloride: phosphoric acid: di-n-propylamine=0.8:0.15:1.0:1.1;
With deionized water mix and blend after 20 minutes regulation system pH value be 7.0, then the lyophilize at-70 DEG C of gained colloid is prepared dry glue in 2 days; By dry for gained glue in autoclave at 160 DEG C crystallization after 72 hours, obtain crystallization product; Be that the deionized water of crystallization product 7 times to wash it and filters by quality, then carry out drying 6 hours in 80 DEG C, then in 600 DEG C through roasting after 3 hours the MgAPO-11 molecular sieve of AEL structure, its particle size is 200nm, and specific surface area is 230m
2/ g.
Embodiment 3
Following raw material is according to mol ratio proportioning, and pseudo-boehmite, with Al
2o
3meter; Heteroatoms source cobaltous chloride, in CoO; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: cobaltous chloride: phosphoric acid: organic amine=0.9:0.1:1.0:0.8;
Organic amine is the mixture of di-n-propylamine and Diisopropylamine mass ratio 1:1;
With deionized water mix and blend after 40 minutes regulation system pH value be 6.0, then the lyophilize at-60 DEG C of gained colloid is prepared dry glue in 2.5 days; By dry for gained glue in autoclave at 170 DEG C crystallization after 36 hours, obtain crystallization product; Be that the deionized water of crystallization product 8 times to wash it and filters by quality, then carry out drying 12 hours in 60 DEG C, then in 650 DEG C through roasting after 2 hours the CoAPO-11 molecular sieve of AEL structure, its particle size is 300nm, and specific surface area is 220m
2/ g.
Embodiment 4
Following raw material is according to mol ratio proportioning, and pseudo-boehmite, with Al
2o
3meter; Heteroatoms source zirconium oxychloride, with ZrO
2meter; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: zirconium oxychloride: phosphoric acid: di-n-propylamine=1.0:0.05:1.0:1.2;
With deionized water mix and blend after 60 minutes regulation system pH value be 4.0, then the lyophilize at-40 DEG C of gained colloid is prepared dry glue in 4 days; By dry for gained glue in autoclave at 200 DEG C crystallization after 24 hours, obtain crystallization product; Be that the deionized water of crystallization product 11 times to wash it and filters by quality, then carry out drying 2 hours in 120 DEG C, then in 500 DEG C through roasting after 6 hours the ZrAPO-11 molecular sieve of AEL structure, its particle size is 500nm, and specific surface area is 215m
2/ g.
Embodiment 5
Following raw material is according to mol ratio proportioning, and pseudo-boehmite, with Al
2o
3meter; Heteroatoms source acidic silicasol, with SiO
2meter; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: acidic silicasol: phosphoric acid: di-n-propylamine=1.0:0.5:1.0:1.0;
With deionized water mix and blend after 30 minutes regulation system pH value be 5.0, then the lyophilize at-80 DEG C of gained colloid is prepared dry glue in 1 day; By dry for gained glue in autoclave at 170 DEG C crystallization after 48 hours, obtain crystallization product; Be that the deionized water of crystallization product 9 times to wash it and filters by quality, then carry out drying 4 hours in 100 DEG C, then in 450 DEG C through roasting after 6 hours the SAPO-11 molecular sieve of AEL structure, its particle size is 150nm, and specific surface area is 260m
2/ g.
Embodiment 6
Following raw material is according to mol ratio proportioning, and pseudo-boehmite, with Al
2o
3meter; Heteroatoms source Lanthanum trichloride, with La
2o
3meter; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: Lanthanum trichloride: phosphoric acid: organic amine=1.0:0.01:1.0:1.2;
Organic amine is the mixture of di-n-propylamine and Diisopropylamine mass ratio 1:1;
With deionized water mix and blend after 10 minutes regulation system pH value be 3.5, then the lyophilize at-50 DEG C of gained colloid is prepared dry glue in 3 days; By dry for gained glue in autoclave at 200 DEG C crystallization after 8 hours, obtain crystallization product; Be that the deionized water of crystallization product 11 times to wash it and filters by quality, then carry out drying 5 hours in 90 DEG C, then in 350 DEG C through roasting after 10 hours the LaAPO-11 molecular sieve of AEL structure, its particle size is 400nm, and specific surface area is 205m
2/ g.
Claims (3)
1. the preparation method of nano-scale AEL structure molecular sieve, is characterized in that, comprises the following steps:
(1) following raw material is according to mol ratio proportioning, pseudo-boehmite, with Al
2o
3meter; Heteroatoms source, is designated as M, with oxide basis; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: heteroatoms source: phosphoric acid: organic amine=0.8 ~ 1.0:0 ~ 0.5:1.0:0.8 ~ 1.2;
Raw material and deionized water mix and blend are after 10-60 minute, and the lyophilize at-80 ~-40 DEG C of gained mixture, at 3.5-8.0, is then prepared dry glue in 1 ~ 4 day by regulation system pH value;
(2) by the dry glue of step (1) gained in autoclave at 160 ~ 200 DEG C crystallization 8 ~ 72 hours, obtain crystallization product; With the deionized water of mass ratio 6 ~ 11 times of crystallization products, gained crystallization product is washed and filtered, then at 60 ~ 120 DEG C, carry out drying 2 ~ 12 hours, then roasting obtains the molecular sieve of AEL structure after 2 ~ 10 hours at 350 ~ 650 DEG C.
2. the preparation method of nano-scale AEL structure molecular sieve according to claim 1, is characterized in that, described heteroatoms source comprises Si, alkaline-earth metal, transition metal, the soluble compounds of thulium and/or hydrolyzable compound.
3. the preparation method of nano-scale AEL structure molecular sieve according to claim 1, is characterized in that, described organic amine is a kind of in di-n-propylamine and Diisopropylamine or both mixtures.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629759A (en) * | 2017-01-03 | 2017-05-10 | 兰州理工大学 | Synthetic method of AEL type silicoaluminophosphate molecular sieve |
| CN108751223A (en) * | 2018-06-06 | 2018-11-06 | 清华大学盐城环境工程技术研发中心 | A kind of AEL structure CeAPO-11 molecular sieves and preparation method |
| CN109422277A (en) * | 2017-08-31 | 2019-03-05 | 中国科学院大连化学物理研究所 | A method of synthesis has AEL structure aluminium phosphate molecular sieve |
| CN112250083A (en) * | 2019-07-22 | 2021-01-22 | 青岛科技大学 | Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof |
| CN112279270A (en) * | 2019-07-22 | 2021-01-29 | 青岛科技大学 | Aluminum phosphate molecular sieve and preparation method thereof |
| CN112456512A (en) * | 2020-12-10 | 2021-03-09 | 聊城大学 | AEL structure hierarchical pore integral silicoaluminophosphate molecular sieve and preparation method and application thereof |
| CN115636423A (en) * | 2021-07-19 | 2023-01-24 | 中国石油化工股份有限公司 | MgAPO-11 molecular sieve and preparation method and application thereof |
| CN115636423B (en) * | 2021-07-19 | 2024-05-10 | 中国石油化工股份有限公司 | MgAPO-11 molecular sieve and preparation method and application thereof |
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| CN101205076A (en) * | 2006-12-21 | 2008-06-25 | 中国石油天然气集团公司 | Method for preparing small-grain SAPO-11 molecular sieve |
| CN101269822A (en) * | 2008-05-09 | 2008-09-24 | 中国石油天然气股份有限公司 | Process for synthesizing heteroatom substituted AEL cage construction aluminophosphates molecular sieve |
| CN102530986A (en) * | 2012-01-10 | 2012-07-04 | 复旦大学 | Method for producing MFI type zeolites |
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| CN101205076A (en) * | 2006-12-21 | 2008-06-25 | 中国石油天然气集团公司 | Method for preparing small-grain SAPO-11 molecular sieve |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629759A (en) * | 2017-01-03 | 2017-05-10 | 兰州理工大学 | Synthetic method of AEL type silicoaluminophosphate molecular sieve |
| CN106629759B (en) * | 2017-01-03 | 2018-10-02 | 兰州理工大学 | A kind of synthetic method of AEL types silicoaluminophosphamolecular molecular sieves |
| CN109422277A (en) * | 2017-08-31 | 2019-03-05 | 中国科学院大连化学物理研究所 | A method of synthesis has AEL structure aluminium phosphate molecular sieve |
| CN109422277B (en) * | 2017-08-31 | 2022-08-02 | 中国科学院大连化学物理研究所 | Method for synthesizing aluminum phosphate molecular sieve with AEL structure |
| CN108751223A (en) * | 2018-06-06 | 2018-11-06 | 清华大学盐城环境工程技术研发中心 | A kind of AEL structure CeAPO-11 molecular sieves and preparation method |
| CN108751223B (en) * | 2018-06-06 | 2021-07-20 | 清华大学盐城环境工程技术研发中心 | AEL structure CeAPO-11 molecular sieve and preparation method thereof |
| CN112250083A (en) * | 2019-07-22 | 2021-01-22 | 青岛科技大学 | Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof |
| CN112279270A (en) * | 2019-07-22 | 2021-01-29 | 青岛科技大学 | Aluminum phosphate molecular sieve and preparation method thereof |
| CN112456512A (en) * | 2020-12-10 | 2021-03-09 | 聊城大学 | AEL structure hierarchical pore integral silicoaluminophosphate molecular sieve and preparation method and application thereof |
| CN112456512B (en) * | 2020-12-10 | 2023-03-21 | 聊城大学 | AEL structure hierarchical pore integral silicoaluminophosphate molecular sieve and preparation method and application thereof |
| CN115636423A (en) * | 2021-07-19 | 2023-01-24 | 中国石油化工股份有限公司 | MgAPO-11 molecular sieve and preparation method and application thereof |
| CN115636423B (en) * | 2021-07-19 | 2024-05-10 | 中国石油化工股份有限公司 | MgAPO-11 molecular sieve and preparation method and application thereof |
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