CN103708499A - Preparation method of hierarchical pore heteroatom aluminophosphate molecular sieve MnAlPO-5 - Google Patents
Preparation method of hierarchical pore heteroatom aluminophosphate molecular sieve MnAlPO-5 Download PDFInfo
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- CN103708499A CN103708499A CN201410014856.4A CN201410014856A CN103708499A CN 103708499 A CN103708499 A CN 103708499A CN 201410014856 A CN201410014856 A CN 201410014856A CN 103708499 A CN103708499 A CN 103708499A
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Abstract
The invention provides a preparation method of a hierarchical pore heteroatom aluminophosphate molecular sieve MnAlPO-5. The preparation method comprises the following steps: (1) uniformly mixing eutectic Em, an aluminium source and a manganese source, adding phosphoric acid and hydrofluoric acid, wherein the obtained mixture is a: MnO.Al2O3.b:P2O.cHF.d:EM, coefficients are as follows according to a molar ratio: a=0.2-0.8, b=1.1-2.2, C=0.0-2.0, and d=62.0; heating at the temperature of 130 DEG C, and uniformly mixing to obtain the mixture; (2) heating the mixture to 170 DEG C through microwave radiation, and crystallizing for 30-90 minutes under the normal pressure or self-generated pressure; and (3) cooling the mixture to the room temperature, repeatedly centrifuging and washing the product with water and acetone, and drying for 3 hours at the temperature of 80 DEG C to obtain the powdery product of the heteroatom aluminophosphate molecular sieve MnAlPO-5.
Description
Technical field
The present invention relates to adopt the method for the synthetic multi-stage porous hetero-atom molecular-sieve material of carry out microwave radiation heating in eutectic mixture.
Background technology
AlPO
4-n skeleton structure is by PO
4and AlO
4the strict alternative arrangement of tetrahedron forms, and is electric neutrality, almost there is no ion-exchange performance and significantly acid.Therefore different heteroatoms (Si, transition metal etc.) is introduced in the middle of framework of molecular sieve, by the phosphorus in isomorphous substitution skeleton structure or aluminium atom, can obtain a series of hetero-atom molecular-sieve crystal with active centre, thereby improve the catalytic activity of aluminium phosphate molecular sieve.Nineteen eighty-two U.S. combinating carbide company reported first aluminium phosphate molecular sieve (AlPO
4the synthetic method of the aluminium phosphate molecular sieve (MeAlPO-n) that-n), the heteroatoms such as aluminium silicophosphate molecular sieve (SiAlPO-n) and Fe, Co, Mn replaces.MeAlPO-5 molecular sieve is very important a member in MeAlPO-n molecular sieve family, and its structure is similar to the pore canal system of ZSM-5 zeolite.Tradition micropore MeAlPO-5 molecular sieve has higher stability and acidity, but application and molecular mass-transfer effect in bulky molecular catalysis reaction have been limited in its relatively long and narrow duct, and mesoporous MeAlPO-5 molecular sieve can effectively address the above problem, but its lower hydrothermal stability and slightly acidic can not be applied in commercial run it well.And the multi-stage porous MeAlPO-5 molecular screen material rising is in recent years owing to combining the advantage of micropore and mesopore molecular sieve simultaneously, caused researchist's extensive concern.
The main synthetic method of the MeAlPO-5 molecular sieve of reporting at present has hydrothermal synthesis method and solvent thermal synthesis method.But these methods need to be carried out under the environment in High Temperature High Pressure when synthetic, have certain potential safety hazard, and crystallization time are longer, its application in many industrial circles is restricted.
Summary of the invention
the object of this invention is to provide a kind ofthe preparation method of multi-stage porous heteroatom phosphate aluminium molecular sieve MnAlPO-5.
The present invention is the preparation method of multi-stage porous heteroatom phosphate aluminium molecular sieve MnAlPO-5, the steps include:
(1) eutectic EM, He Meng source, aluminium source are mixed, add phosphoric acid and hydrofluoric acid, gained mixture is a: MnO
2al
2o
3b:P
2o
5c HFd:EM, wherein coefficient is counted in molar ratio, a=0.2 ~ 0.8, b=1.1 ~ 2.2, c=0.0 ~ 2.0, d=62.0, at 130 ℃, heating, mixes it, obtains mixture;
(2) mixture is heated to 170 ℃ under microwave radiation, under normal pressure or autogenous pressure, crystallization is 30 ~ 90 minutes;
(3) mixture is cooled to room temperature, water and acetone is centrifuge washing product repeatedly, then is dried 3 hours at 80 ℃, obtains the powdery product of heteroatom phosphate aluminium molecular sieve-MnAlPO-5.
The present invention adopts the eutectic mixture (Deep-eutectic solvents) of ionic state as solvent, under normal pressure, by carry out microwave radiation heating, has synthesized fast multi-stage porous MnAlPO-5 molecular sieve.In building-up process, eutectic mixture can, simultaneously as solvent and template, can synthesize the aluminium phosphate molecular sieve with hierarchical porous structure without the mesoporous template of extra interpolation.In addition, microwave irradiation of the present invention, except having heating effect, also can change the space structure of some molecules, makes some chemical bond ruptures and then activated molecule, thereby promotes the carrying out of polytype chemical reaction.The more important thing is, employing microwave-assisted ion thermal synthesis multi-stage porous molecular sieve can shorten the crystallization time of molecular sieve significantly, improves the combined coefficient of molecular sieve.
Accompanying drawing explanation
Fig. 1 is MnAlPO-5 type aluminium phosphate molecular sieve X-ray diffraction (XRD) spectrogram of synthesized of the present invention, and Fig. 2 is scanning electron microscope (SEM) figure, and Fig. 3 is transmission electron microscope (TEM) figure, and Fig. 4 is N
2physics adsorption desorption and graph of pore diameter distribution.
Embodiment
The present invention is the preparation method of multi-stage porous heteroatom phosphate aluminium molecular sieve MnAlPO-5, the steps include:
(1) eutectic EM, He Meng source, aluminium source are mixed, add phosphoric acid and hydrofluoric acid, gained mixture is a: MnO
2al
2o
3b:P
2o
5c HFd:EM, wherein coefficient is counted in molar ratio, a=0.2 ~ 0.8, b=1.1 ~ 2.2, c=0.0 ~ 2.0, d=62.0, at 130 ℃, heating, mixes it, obtains mixture;
(2) mixture is heated to 170 ℃ under microwave radiation, under normal pressure or autogenous pressure, crystallization is 30 ~ 90 minutes;
(3) mixture is cooled to room temperature, water and acetone is centrifuge washing product repeatedly, then is dried 3 hours at 80 ℃, obtains the powdery product of heteroatom phosphate aluminium molecular sieve-MnAlPO-5.
According to above-described preparation method, eutectic is the mixture of succinic acid, choline chloride 60 and tetraethylammonium bromide, and the mol ratio of three kinds of materials is 8: 8: 1.
According to above-described preparation method, phosphorus source is 85% phosphoric acid.
According to above-described preparation method, aluminium source is pseudo-boehmite, or aluminum isopropylate.
According to above-described preparation method, manganese source is Mn (NO
3)
2, or manganese acetate, or manganese citrate.
According to above-described preparation method, in mixed system, adopt hydrofluoric acid to make mineralizer.
According to above-described preparation method, above step (2) is to adopt at carry out microwave radiation heating to 170 ℃, crystallization 30-90 minute.
With embodiment more specifically, further launch the present invention below.
Embodiment 1:
(1) ground and mixed in succinic acid, choline chloride 60, tetraethylammonium bromide, aluminum isopropylate and manganous nitrate and mortar is even, proceed in 50 ml there-necked flasks, add phosphoric acid and hydrofluoric acid, gained mixture is a MnO
2al
2o
3b P
2o
5c HFd EM, wherein coefficient is counted in molar ratio, a=0.4, b=1.1, c=1.0, d=62, heat at 130 ℃ with electric mantle, and it is mixed, and obtain mixture;
(2)mixture is heated to 170 ℃ under microwave radiation, and under normal pressure or autogenous pressure, crystallization is 60 minutes;
(3) above crystallization product is cooled to room temperature, water and acetone is centrifuge washing product repeatedly, then is dried 3 hours at 80 ℃, can obtain the powdery product of heteroatom phosphate aluminium molecular sieve-MnAlPO-5;
(4)through XRD, SEM, TEM and N
2physics adsorption desorption detects, and this powdery product is the multi-stage porous MnAlPO-5 molecular sieve with AFI topological framework.
Fig. 1 is the XRD figure spectrum of the multi-stage porous molecular screen material of the present embodiment gained; Fig. 4 is the N of the multi-stage porous molecular screen material of the present embodiment gained
2physics adsorption desorption and graph of pore diameter distribution.
Embodiment 2:
The difference of the present embodiment and embodiment 1 is only: ratio c=0 of HF in step (1).
Embodiment 3:
The difference of the present embodiment and embodiment 1 is only: the manganese source in step (1) is manganese citrate, ratio c=0.5 of HF.
Fig. 2 is scanning electron microscope (SEM) figure of the multi-stage porous molecular screen material of the present embodiment gained.
Embodiment 4:
The difference of the present embodiment and embodiment 1 is only: ratio c=2.0 of HF in step (1).
Embodiment 5:
The difference of the present embodiment and embodiment 1 is only: ratio b=2.2 of the phosphoric acid in step (1).
Embodiment 6:
The difference of the present embodiment and embodiment 1 is only: the aluminium source in step (1) is pseudo-boehmite.
Embodiment 7:
The difference of the present embodiment and embodiment 1 is only: the ratio of the manganous nitrate in step (1) is a=0.2.
Fig. 3 is transmission electron microscope (TEM) figure of the multi-stage porous molecular screen material of the implementation case gained.
Embodiment 8:
The difference of the present embodiment and embodiment 1 is only: ratio c=2.0 that the ratio of the manganous nitrate in step (1) is 0.8, HF.
Embodiment 9:
The difference of the present embodiment and embodiment 1 is only: the manganese source in step (1) is manganous acetate, and the crystallization time in step (2) is 90 min.
Embodiment 10:
The difference of the present embodiment and embodiment 1 is only: the ratio of the manganous nitrate in step (1) is 0.6, and the crystallization time in step (2) is 90 min.
Embodiment 11:
The difference of the present embodiment and embodiment 1 is only: the crystallization time in step (2) is 30 min.
Table 1 is the structural parameter data of the multi-stage porous molecular screen material of embodiment 1-11 gained:
The N of table 1 microwave synthetic sample
2physics adsorption desorption characterization data
From table 1: the heteroatoms MnAlPO-5 molecular sieve of synthesized of the present invention is the material with hierarchical porous structure.
Claims (7)
1. the preparation method of multi-stage porous heteroatom phosphate aluminium molecular sieve MnAlPO-5, the steps include:
(1) eutectic EM, He Meng source, aluminium source are mixed, add phosphoric acid and hydrofluoric acid, gained mixture is a: MnO
2al
2o
3b:P
2o
5c HFd:EM, wherein coefficient is counted in molar ratio, a=0.2 ~ 0.8, b=1.1 ~ 2.2, c=0.0 ~ 2.0, d=62.0, at 130 ℃, heating, mixes it, obtains mixture;
(2) mixture is heated to 170 ℃ under microwave radiation, under normal pressure or autogenous pressure, crystallization is 30 ~ 90 minutes;
(3) mixture is cooled to room temperature, water and acetone is centrifuge washing product repeatedly, then is dried 3 hours at 80 ℃, obtains the powdery product of heteroatom phosphate aluminium molecular sieve-MnAlPO-5.
2. the preparation method of multi-stage porous heteroatom phosphate aluminium molecular sieve MnAlPO-5 according to claim 1, it is characterized in that: eutectic is the mixture of succinic acid, choline chloride 60 and tetraethylammonium bromide, and the mol ratio of three kinds of materials is 8: 8: 1.
3. the preparation method of multi-stage porous heteroatom phosphate aluminium molecular sieve MnAlPO-5 according to claim 1, is characterized in that: phosphorus source is 85% phosphoric acid.
4. the preparation method of multi-stage porous heteroatom phosphate aluminium molecular sieve MnAlPO-5 according to claim 1, is characterized in that: aluminium source is pseudo-boehmite, or aluminum isopropylate.
5. the preparation method of multi-stage porous heteroatom phosphate aluminium molecular sieve MnAlPO-5 according to claim 1, is characterized in that: manganese source is Mn (NO
3)
2, or manganese acetate, or manganese citrate.
6. the preparation method of multi-stage porous heteroatom phosphate aluminium molecular sieve MnAlPO-5 according to claim 1, is characterized in that: in mixed system, adopt hydrofluoric acid to make mineralizer.
7. the preparation method of multi-stage porous heteroatom phosphate aluminium molecular sieve MnAlPO-5 according to claim 1, is characterized in that: step (2) is to adopt at carry out microwave radiation heating to 170 ℃, crystallization 30-90 minute.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646223A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing succinic acid diester via catalytic oxidation esterification of levulinic acid |
| CN107777702A (en) * | 2017-11-09 | 2018-03-09 | 常州大学 | A kind of preparation method of multi-stage porous hetero atom aluminium phosphate molecular sieve for oxidation sweetening |
| CN116119679A (en) * | 2023-01-17 | 2023-05-16 | 西南科技大学 | High-purity 4A zeolite and room-temperature normal-pressure synthesis method thereof |
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| US4801364A (en) * | 1983-07-15 | 1989-01-31 | Uop | Separation and conversion processes using metal aluminophosphates |
| CN101602513A (en) * | 2009-07-18 | 2009-12-16 | 太原理工大学 | The method that in eutectic mixture, prepares aluminium phosphate molecular sieve |
| CN102583436A (en) * | 2011-01-06 | 2012-07-18 | 兰州理工大学 | Quick synthesis method of heteroatomic aluminophosphate molecular sieve SAPO-5 in eutectic body |
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2014
- 2014-01-14 CN CN201410014856.4A patent/CN103708499A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801364A (en) * | 1983-07-15 | 1989-01-31 | Uop | Separation and conversion processes using metal aluminophosphates |
| CN101602513A (en) * | 2009-07-18 | 2009-12-16 | 太原理工大学 | The method that in eutectic mixture, prepares aluminium phosphate molecular sieve |
| CN102583436A (en) * | 2011-01-06 | 2012-07-18 | 兰州理工大学 | Quick synthesis method of heteroatomic aluminophosphate molecular sieve SAPO-5 in eutectic body |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646223A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing succinic acid diester via catalytic oxidation esterification of levulinic acid |
| CN105646223B (en) * | 2014-12-04 | 2017-12-26 | 中国科学院大连化学物理研究所 | A kind of method that levulic acid catalysis oxidation esterification prepares succinate |
| CN107777702A (en) * | 2017-11-09 | 2018-03-09 | 常州大学 | A kind of preparation method of multi-stage porous hetero atom aluminium phosphate molecular sieve for oxidation sweetening |
| CN107777702B (en) * | 2017-11-09 | 2020-05-26 | 常州大学 | Preparation method of hierarchical-pore heteroatom aluminum phosphate molecular sieve for oxidative desulfurization |
| CN116119679A (en) * | 2023-01-17 | 2023-05-16 | 西南科技大学 | High-purity 4A zeolite and room-temperature normal-pressure synthesis method thereof |
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Application publication date: 20140409 |