CN105110349B - The preparation method of nano-scale AEL structure molecular sieve - Google Patents
The preparation method of nano-scale AEL structure molecular sieve Download PDFInfo
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Abstract
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.Using boehmite, hetero atom source, phosphoric acid, organic amine as raw material, raw material mixed freezing is dried to obtain dry glue, then carries out the molecular sieve that Crystallizing treatment obtains AEL structure to dry glue again.The preparation method for the nano-scale AEL structure molecular sieve that the present invention is provided, first uses Freeze Drying Technique that colloid is freeze-dried as dry glue, crystallization is then being carried out to dry glue, AEL structure molecular sieve prepared by this method has nanoscale, the characteristics of specific surface area is high.
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, the energy
Chemical field.
Background technology
By same order elements form into skeleton introducing hetero-atoms, assign phosphate aluminium molecular sieve surface acidity, wherein
MeAPO-11 molecular sieves are because its suitable one-dimensional ten-ring structure and gentle Acidity are in fields such as direct-connected alkane isomerizations
It is widely used.Isomerization reaction belongs to aperture catalytic reaction, and higher aperture exposure can improve isohydrocarbon choosing
Selecting property, reduces Size of Zeolite, it is the effective means for realizing this target to prepare nanoscale molecular sieve.Less molecular sieve particle diameter
External surface area can be effectively improved, shorten orifice throat length, reduction diffusional resistance, suppress the generation of side reaction.Nanoscale point
The synthesis of son sieve is sieved nucleus by acceleration molecular and generated, and suppresses the control devices such as aggregation of particles and is realized that common method has dry
Gel method, microwave process for synthesizing, space restriction method etc..The decomposition that microwave synthesis can strengthen gel by introducing microwave heating is made
With making nucleus quantity reach the state close to saturation in a short time, ensuing crystallization rate is accelerated, the molecular sieve synthesized
Particle diameter can also be controlled, and the crystallinity of synthetic sample is high, and can save low temperature aging necessary to conventional heating methods
Program, but its synthesis condition comparatively harsh, space limits method and is defined in molecular sieve in limited space, hinders it to give birth to
Grow and prevent the polymerization of its crystal grain.
The content of the invention
For above-mentioned technical problem, the present invention provides a kind of preparation method of nano-scale AEL structure molecular sieve, using dry
Gel method has benefited from the generation that its higher solid-to-liquid ratio easily induces small crystal grain molecular sieve, and this method possesses that water consumption is less, mould
The advantage that plate agent can be reused, the present invention is on the basis of xerogel advantage is played, by regulating and controlling dry glue preparation condition system
It is standby go out nanoscale, the high sieve sample than specific surface area.
Specifically technical scheme is：
The preparation method of nano-scale AEL structure molecular sieve, comprises the following steps：
(1) following raw material is matched according to mol ratio, boehmite, with Al2O3Meter；Hetero atom source, is designated as M, with oxide
Meter；Phosphoric acid, with P2O5Meter；
Boehmite：Hetero atom source：Phosphoric acid：Organic amine=0.8~1.0：0~0.5：1.0：0.8~1.2；
After raw material is mixed 10-60 minutes with deionized water, then regulation system pH value mixes gained in 3.5-8.0
Compound prepares dry glue in 1~4 day in freeze-drying at -80~-40 DEG C；
(2) by dry glue obtained by step (1) in autoclave in crystallization 8~72 hours at 160~200 DEG C, obtain crystalline substance
Change product；Gained crystallization product is washed and filtered with the deionized water of 6~11 times of crystallization products of mass ratio, then in 60
It is dried at~120 DEG C 2~12 hours, the molecular sieve of AEL structure is obtained after being calcined 2~10 hours at 350~650 DEG C.
Described hetero atom source include Si, alkaline-earth metal, transition metal, the soluble compounds of thulium and/or
Hydrolyzable compound, the element such as Si, Ge, Mg, Ca, Zn, Fe, Co, Cu, Ni, Ti, Zr, Mn, Y, La and Ce it is solubilized
Compound and/or hydrolyzable compound.
Described organic amine is the mixture of one or both of di-n-propylamine and diisopropylamine.
The preparation method for the nano-scale AEL structure molecular sieve that the present invention is provided, first using Freeze Drying Technique by colloid
It is freeze-dried as dry glue, crystallization is then being carried out to dry glue, AEL structure molecular sieve prepared by this method has nanoscale, than
The characteristics of surface area is high.
Embodiment
It is described in conjunction with the embodiments the embodiment of the present invention.
Raw material used in embodiment：
Boehmite, the production of Yantai Heng Hui Chemical Co., Ltd.s, Al2O3Content 70wt%；
Phosphoric acid, Xilong Chemical Co., Ltd's production, is analyzed pure；
Di-n-propylamine and diisopropylamine, deionized water, magnesium chloride, cobalt chloride, zirconium oxychloride, lanthanum chloride, Chinese medicines group
Chemical reagent Co., Ltd produces, and analyzes pure；
Acidic silicasol, Qingdao Marine Chemical Co., Ltd.'s production, SiO2Content 25%.
Embodiment 1
Following raw material is matched according to mol ratio, boehmite, with Al2O3Meter；Hetero atom source, is designated as M, in terms of oxide；
Phosphoric acid, with P2O5Meter；
Boehmite：Phosphoric acid：Di-n-propylamine=1.0：1.0：1.0；
Regulation system pH value is 5.5 after being mixed 30 minutes with deionized water, then by gained colloid in cold at -80 DEG C
Prepare dry glue within lyophilized dry 1 day；By gained dry glue in autoclave in after crystallization at 160 DEG C 54 hours, obtain crystallization product；
It is washed and filtered with the deionized water that quality is 6 times of crystallization product, is then dried 4 hours in 100 DEG C, then at
550 DEG C after fired 4 hours AEL structure AlPO-11 molecular sieves, its particle size is 100nm, and specific surface area is 250m2/
g。
Embodiment 2
Following raw material is matched according to mol ratio, boehmite, with Al2O3Meter；Hetero atom source magnesium chloride, in terms of MgO；Phosphorus
Acid, with P2O5Meter；
Boehmite：Magnesium chloride：Phosphoric acid：Di-n-propylamine=0.8:0.15:1.0:1.1；
Regulation system pH value is 7.0 after being mixed 20 minutes with deionized water, then by gained colloid in cold at -70 DEG C
Prepare dry glue within lyophilized dry 2 days；By gained dry glue in autoclave in after crystallization at 160 DEG C 72 hours, obtain crystallization product；
It is washed and filtered with the deionized water that quality is 7 times of crystallization product, is then dried 6 hours in 80 DEG C, then at
600 DEG C after fired 3 hours AEL structure MgAPO-11 molecular sieves, its particle size is 200nm, and specific surface area is
230m2/g。
Embodiment 3
Following raw material is matched according to mol ratio, boehmite, with Al2O3Meter；Hetero atom source cobalt chloride, in terms of CoO；
Phosphoric acid, with P2O5Meter；
Boehmite：Cobalt chloride：Phosphoric acid：Organic amine=0.9:0.1:1.0:0.8；
Organic amine is di-n-propylamine and diisopropylamine mass ratio 1:1 mixture；
Regulation system pH value is 6.0 after being mixed 40 minutes with deionized water, then by gained colloid in cold at -60 DEG C
Prepare dry glue within lyophilized dry 2.5 days；By gained dry glue in autoclave in after crystallization at 170 DEG C 36 hours, obtain crystallization production
Thing；It is washed and filtered with the deionized water that quality is 8 times of crystallization product, is then dried 12 hours in 60 DEG C,
Then at 650 DEG C after fired 2 hours AEL structure CoAPO-11 molecular sieves, its particle size is 300nm, and specific surface area is
220m2/g。
Embodiment 4
Following raw material is matched according to mol ratio, boehmite, with Al2O3Meter；Hetero atom source zirconium oxychloride, with ZrO2Meter；
Phosphoric acid, with P2O5Meter；
Boehmite：Zirconium oxychloride：Phosphoric acid：Di-n-propylamine=1.0:0.05:1.0:1.2；
Regulation system pH value is 4.0 after being mixed 60 minutes with deionized water, then by gained colloid in cold at -40 DEG C
Prepare dry glue within lyophilized dry 4 days；By gained dry glue in autoclave in after crystallization at 200 DEG C 24 hours, obtain crystallization product；
It is washed and filtered with the deionized water that quality is 11 times of crystallization product, is then dried 2 hours in 120 DEG C, then
In 500 DEG C after fired 6 hours AEL structure ZrAPO-11 molecular sieves, its particle size is 500nm, and specific surface area is
215m2/g。
Embodiment 5
Following raw material is matched according to mol ratio, boehmite, with Al2O3Meter；Hetero atom source acidic silicasol, with SiO2
Meter；Phosphoric acid, with P2O5Meter；
Boehmite：Acidic silicasol：Phosphoric acid：Di-n-propylamine=1.0:0.5:1.0:1.0；
Regulation system pH value is 5.0 after being mixed 30 minutes with deionized water, then by gained colloid in cold at -80 DEG C
Prepare dry glue within lyophilized dry 1 day；By gained dry glue in autoclave in after crystallization at 170 DEG C 48 hours, obtain crystallization product；
It is washed and filtered with the deionized water that quality is 9 times of crystallization product, is then dried 4 hours in 100 DEG C, then at
450 DEG C after fired 6 hours AEL structure SAPO-11 molecular sieves, its particle size is 150nm, and specific surface area is 260m2/
g。
Embodiment 6
Following raw material is matched according to mol ratio, boehmite, with Al2O3Meter；Hetero atom source lanthanum chloride, with La2O3Meter；
Phosphoric acid, with P2O5Meter；
Boehmite：Lanthanum chloride：Phosphoric acid：Organic amine=1.0:0.01:1.0:1.2；
Organic amine is di-n-propylamine and diisopropylamine mass ratio 1:1 mixture；
Regulation system pH value is 3.5 after being mixed 10 minutes with deionized water, then by gained colloid in cold at -50 DEG C
Prepare dry glue within lyophilized dry 3 days；By gained dry glue in autoclave in after crystallization at 200 DEG C 8 hours, obtain crystallization product；
It is washed and filtered with the deionized water that quality is 11 times of crystallization product, is then dried 5 hours in 90 DEG C, then at
350 DEG C after fired 10 hours AEL structure LaAPO-11 molecular sieves, its particle size is 400nm, and specific surface area is
205m2/g。
Claims (4)
1. the preparation method of nano-scale AEL structure molecular sieve, it is characterised in that comprise the following steps：
(1) following raw material is matched according to mol ratio, boehmite, with Al2O3Meter；Hetero atom source, is designated as M, in terms of oxide；
Phosphoric acid, with P2O5Meter；
Boehmite：Hetero atom source：Phosphoric acid：Organic amine=0.8~1.0：0~0.5：1.0：0.8~1.2；
After raw material is mixed 10-60 minutes with deionized water, regulation system pH value is in 3.5-8.0, then by gained mixture
Dry glue is prepared in being freeze-dried 1~4 day at -80~-40 DEG C；
(2) by dry glue obtained by step (1) in autoclave in crystallization 8~72 hours at 160~200 DEG C, obtain crystallization production
Thing；Gained crystallization product is washed and filtered with the deionized water of 6~11 times of crystallization products of mass ratio, then in 60~
It is dried at 120 DEG C 2~12 hours, the molecular sieve of AEL structure is obtained after being calcined 2~10 hours at 350~650 DEG C.
2. the preparation method of nano-scale AEL structure molecular sieve according to claim 1, it is characterised in that described is miscellaneous
Atomic source includes Si, alkaline-earth metal, the soluble compounds of transition metal and/or hydrolyzable compound.
3. the preparation method of nano-scale AEL structure molecular sieve according to claim 1, it is characterised in that described is miscellaneous
Atomic source is the soluble compounds and/or hydrolyzable compound of thulium.
4. the preparation method of nano-scale AEL structure molecular sieve according to claim 1, it is characterised in that described has
Machine amine is the mixture of one or both of di-n-propylamine and diisopropylamine.
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| 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 |
| 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 |
| 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 |
| CN112279270B (en) * | 2019-07-22 | 2022-12-09 | 青岛科技大学 | Aluminum phosphate molecular sieve and preparation method thereof |
| CN112250083B (en) * | 2019-07-22 | 2022-12-09 | 青岛科技大学 | Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method 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 |
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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 |
| 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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