CN105174279B - The preparation method of nano-scale aluminium phosphate molecular sieve - Google Patents
The preparation method of nano-scale aluminium phosphate molecular sieve Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of nano-scale aluminium phosphate molecular sieve, belong to new catalytic material synthesis, derived energy chemical field.With boehmite, hetero atom source, phosphoric acid, organic amine as raw material, the mixture that feeds intake carries out freeze-drying and obtains dry glue, and then carrying out heating crystallization treatment to dry glue again obtains aluminium phosphate molecular sieve.The preparation method of the nano-scale aluminium phosphate molecular sieve that the present invention is provided, it is dry glue by colloid freeze-drying first to use Freeze Drying Technique, and crystallization is then being carried out to dry glue, and aluminium phosphate molecular sieve prepared by the method has nanoscale, and specific surface area is high.
Description
Technical field
The present invention relates to a kind of preparation method of nano-scale aluminium phosphate molecular sieve, belong to new catalytic material synthesis, the energy
Chemical field.
Background technology
By same order elements to introducing hetero-atoms in skeleton, phosphate aluminium molecular sieve surface acidity, wherein Me/ can be assigned
SAPO-11, Me/SAPO-34, Me/SAPO-5 molecular sieve etc. is widely used.Me/SAPO-11 molecular sieves are suitable because of its
One-dimensional ten-ring structure and gentle Acidity show excellent reactivity in direct-connected alkane isomerization field；Me/
SAPO-34 molecular sieves have chabasie octatomic ring pore passage structure, and high ethene, propylene are shown in MTO technology
Selectivity；SAPO-5 is twelve-ring pore passage structure, has catalytic capability higher in the reaction such as alkylation.Heterogeneous catalysis is anti-
Ying Zhong, reactant is notable with the diffusion couple catalytic reaction influence of product.Preparing nanoscale molecular sieve, can to increase outer surface sudden and violent
Dew rate, shortens orifice throat length, reduces diffusional resistance, increases the engagement capacity of reactant and catalytic active site, promotes product to depart from
Catalysis body phase, suppresses side reaction and occurs.The synthesis of nanoscale molecular sieve is sieved nucleus and is generated by acceleration molecular, is suppressed particle and is gathered
The control devices such as conjunction are realized that common method has dry gel method, synthetic method, space restriction method etc..Synthesis is heated by introducing
The decomposition of gel can be strengthened, nucleus quantity is reached the state close to saturation, ensuing crystallization speed in a short time
Degree is accelerated, and the molecular sieve particle diameter for synthesizing can also be controlled, and the crystallinity of synthetic sample is high, and can save conventional adding
Low temperature aging program necessary to hot method, but its synthesis condition comparatively harsh, space limits method and is defined in molecular sieve
In limited space, hinder it to grow and prevent the polymerization of its crystal grain.Mainly include micro emulsion method, inert media steric hindrance
Method, three kinds of hydrogel constraint rule are, it is necessary to additionally add hard mould agent.
The content of the invention
For above-mentioned technical problem, the present invention provides a kind of preparation method of nano-scale aluminium phosphate molecular sieve, using dry
Gel method has solid-to-liquid ratio higher, easily induces the generation of small crystal grain molecular sieve, and possesses that water consumption is less, template can be again
The multiple advantage for utilizing, the present invention prepares a nanometer chi on the basis of xerogel advantage is played by regulating and controlling dry glue preparation condition
Degree, the sieve sample than specific surface area high.
Specifically technical scheme is：
The preparation method of nano-scale aluminium phosphate 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=0.8~1.0：0~0.6：1.0：0.8~1.2；
Raw material and deionized water are mixed 10-60 minutes, regulation system pH value 3.5~8.0, then by gained colloid
Dry glue is prepared in freeze-drying at -80~-40 DEG C within 1~4 day；
(2) by step (1) gained dry glue in autoclave in after crystallization at 160~200 DEG C 8~72 hours, obtain
Crystallization product；Gained crystallization product is washed and filtered with 6~11 times of deionized waters of crystallization product of mass ratio, Ran Houyu
It is dried at 60~120 DEG C 2~12 hours, the molecular sieve of aluminum phosphate 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
The elements such as hydrolyzable compound, such as Si, Ge, Fe, Mg, Ca, Zn, Fe, Co, Cu, Ni, Ti, Zr, Mn, Y, La and Ce can
Dissolve compound and/or hydrolyzable compound.
Described organic amine is that di-n-butylamine, triethylamine, Tri-n-Propylamine, tetraethyl ammonium hydroxide, di-n-propylamine and two are different
The mixture of one or both of propylamine.
The preparation method of the nano-scale aluminium phosphate molecular sieve that the present invention is provided, it is first using Freeze Drying Technique that colloid is cold
It is dry glue to freeze dry, and crystallization is then being carried out to dry glue, and aluminium phosphate molecular sieve prepared by the method has nanoscale, specific surface
Product is high.
Specific embodiment
It is described in conjunction with the embodiments specific embodiment of the invention.
Raw material used by embodiment：
Boehmite, the production of Yantai Heng Hui Chemical Co., Ltd.s, Al2O3Content 70wt%；
Phosphoric acid, Xilong Chemical Co., Ltd's production, analyzes pure；
Di-n-propylamine and diisopropylamine, deionized water, N, N- diisopropylethylamine, magnesium chloride, cobalt chloride, oxychlorination
Zirconium, tetraethyl ammonium hydroxide, Chemical Reagent Co., Ltd., Sinopharm Group's production, analyze 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；Phosphoric acid, with P2O5Meter；
Boehmite：Phosphoric acid：Organic amine=1.0:1.0:1.0；
Organic amine is di-n-propylamine and diisopropylamine mass ratio 1:1 mixture；
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 is 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 aluminum phosphate 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；Magnesium chloride, in terms of MgO；Phosphoric acid, with P2O5
Meter；
Boehmite：Magnesium chloride：Phosphoric acid：N, N- diisopropylethylamine=1.0:0.1:0.4:0.9；
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 is 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 aluminum phosphate MgAPSO-18 molecular sieves, its particle size is 200nm, and specific surface area is
220m2/g。
Embodiment 3
Following raw material is matched according to mol ratio, boehmite, with Al2O3Meter；Cobalt chloride, in terms of CoO；Phosphoric acid, with
P2O5Meter；
Boehmite：Cobalt chloride：Phosphoric acid：Tri-n-Propylamine=0.9:0.1:1.0:0.8；
Regulation system pH value is 6.0 after being mixed 40 minutes with deionized water, then by gained colloid at -60 DEG C
Freeze-drying prepares dry glue in 2.5 days；By gained dry glue in autoclave in after crystallization at 170 DEG C 36 hours, obtain crystallization
Product；It is washed and is filtered with the deionized water that quality is 8 times of crystallization product, it is small to be then dried 12 in 60 DEG C
When, then at 650 DEG C after fired 2 hours aluminum phosphate CoAPO-5 molecular sieves, its particle size is 300nm, and specific surface area is
235m2/g。
Embodiment 4
Following raw material is matched according to mol ratio, boehmite, with Al2O3Meter；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 is 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 aluminum phosphate 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；Acidic silicasol, with SiO2Meter；Phosphoric acid,
With P2O5Meter；
Boehmite：Acidic silicasol：Phosphoric acid：Tetraethyl ammonium hydroxide=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 is 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 aluminum phosphate SAPO-34 molecular sieves, its particle size is 150nm, and specific surface area is 218m2/
g。
Embodiment 6
Following raw material is matched according to mol ratio, boehmite, with Al2O3Meter；Magnesium chloride, in terms of MgO；Phosphoric acid, with P2O5
Meter；
Boehmite：Magnesium chloride：Phosphoric acid：Organic amine=1.0:0.05:1.0:1.2；
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 is 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 aluminum phosphate MgAPO-31 molecular sieves, its particle size is 400nm, and specific surface area is
205m2/g。
Claims (4)
1. the preparation method of nano-scale aluminium phosphate 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=0.8~1.0：0~0.6：1.0：0.8~1.2；
Raw material and deionized water are mixed 10-60 minutes, regulation system pH value 3.5~8.0, then by gained colloid in-
Freeze-drying prepares dry glue in 1~4 day at 80~-40 DEG C；
(2) by step (1) gained dry glue in autoclave in after crystallization at 160~200 DEG C 8~72 hours, obtain crystallization
Product；Gained crystallization product is washed and filtered with 6~11 times of deionized waters of crystallization product of mass ratio, then in 60~
It is dried at 120 DEG C 2~12 hours, the molecular sieve of aluminum phosphate is obtained after being calcined 2~10 hours at 350~650 DEG C.
2. the preparation method of nano-scale aluminium phosphate molecular sieve according to claim 1, it is characterised in that described miscellaneous original
Component includes Si, alkaline-earth metal, the soluble compounds of transition metal and/or hydrolyzable compound.
3. the preparation method of nano-scale aluminium phosphate molecular sieve according to claim 1, it is characterised in that described miscellaneous original
Component is the soluble compounds and/or hydrolyzable compound of thulium.
4. the preparation method of nano-scale aluminium phosphate molecular sieve according to claim 1, it is characterised in that described is organic
Amine is one or both of di-n-butylamine, triethylamine, Tri-n-Propylamine, tetraethyl ammonium hydroxide, di-n-propylamine and diisopropylamine
Mixture.
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| CN108147422A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of CHA types Activity of Magnesium Aluminophosphate Molecular Sieve and preforming synthetic method |
| CN108147427A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of CHA types hetero atom Metal-aluminophosphate Molecular Siever and preforming synthetic method |
| CN108147428A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of aluminium phosphate molecular sieve with CHA structure and preforming synthetic method |
| CN109422280A (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 AFI structure aluminium phosphate molecular sieve |
| CN109422272A (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 AFI structure hetero atom Metal-aluminophosphate Molecular Siever |
| CN109354035B (en) * | 2018-11-24 | 2023-01-24 | 江西师范大学 | Method for preparing AlPO-18 molecular sieve by using double templates |
| CN109759129A (en) * | 2019-01-15 | 2019-05-17 | 昆明理工大学 | A kind of Modification on Al PO4The preparation method and application of multistage porous molecular sieve |
| 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 |
| CN113104860B (en) * | 2020-05-14 | 2024-01-30 | 青岛大学威海创新研究院 | Preparation method of SAPO-34 molecular sieve with bionic pore structure |
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| CN100560494C (en) * | 2006-12-21 | 2009-11-18 | 中国石油天然气集团公司 | A kind of preparation method of little crystal grain SAPO-11 molecular sieve |
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