CN1122637C - Method for synthesizing new-type beryllium phosphate molecular sieve by using concentrated amine system - Google Patents
Method for synthesizing new-type beryllium phosphate molecular sieve by using concentrated amine system Download PDFInfo
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- CN1122637C CN1122637C CN01126584A CN01126584A CN1122637C CN 1122637 C CN1122637 C CN 1122637C CN 01126584 A CN01126584 A CN 01126584A CN 01126584 A CN01126584 A CN 01126584A CN 1122637 C CN1122637 C CN 1122637C
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- molecular sieve
- beryllium phosphate
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Abstract
The present invention relates to a method for synthesizing beryllium phosphate molecular sieves with a novel structure, which belongs to the technical field of inorganic molecular sieves. Concentrated amine is used as a template for synthesizing pure phase large monocrystal beryllium phosphate molecules under the hydrothermal condition. Through adopting triethylenetetraamine, pyridine and piperazine as template agents, controlling the sol concentration and regulating the pH value, the beryllium phosphate molecular sieves with topology structures of GME (12 primary rings), GIS (8 primary rings), ABW (8 primary rings), etc. can be synthesized, and the monocrystal dimension is between 50 and 400 mum.
Description
Technical field
The invention belongs to inorganic molecule sieve technical field, be specifically related to a kind of method of synthesizing new-type beryllium phosphate molecular sieve by using concentrated amine system.
Technical background
Because zeolite molecular sieve has unique skeleton and pore passage structure, has been widely used at present in the industrial circle, as catalyzer, sorbent material and ion-exchanger etc.Along with the continuous development of industry, people have proposed new requirement to the 26S Proteasome Structure and Function of molecular sieve.Since nineteen eighty-two, aluminum phosphate type molecular sieve was synthetic first, the molecular sieve of this type had been subjected to paying close attention to widely, has synthesized a large amount of micro porous molecular sieves with novel texture up till now.But, therefore do not possess surface acidity because aluminum phosphate type framework of molecular sieve is electric neutrality.Utilize the Be of lower valency to replace the synthetic beryllium phosphate type micro porous molecular sieve of Al will make negative charge on the skeleton band.This material will be widely used in catalyzed reactions such as redox.
Because the skeleton of beryllium phosphate is an electronegativity, synthetic at present type beryllium phosphate molecular sieve by using mostly adopts univalent positively charged ion such as Na
+, K
+, Rb
+Isoequilibrium skeleton electric charge, prepared beryllium phosphate mostly are not pure single phases, and the size of monocrystalline is also less.In existing type beryllium phosphate molecular sieve by using, great majority are the pore material that contain 6 yuan of rings or 8 yuan of rings in addition.Along with industrial expansion, the molecular screen material with macropore (12 yuan more than the ring) will have tempting application prospect in fields such as biological medicine, protein separation.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of pure phase, large single crystal, wide aperture type beryllium phosphate molecular sieve by using.
The synthetic method of the type beryllium phosphate molecular sieve by using that the present invention proposes is to be template with dense amine, and synthetic under hydrothermal condition, concrete steps are as follows: at a certain amount of Be (OH)
2In, the concentration that adds its 3-10 times weight is 85% H
3PO
4With the water of 20-50 times of weight, at room temperature stirred 1-2 hour, until dissolving fully; Add organic amine R, and satisfy R/H
2O=1: (100-1), mixture finally meets mol ratio BeO: P
2O
5: R: H
2O=1: (1-2): (0.5-55): (50-100); Add sodium ion Na then
+, potassium ion K
+Or ammonium ion NH
4 +, control pH value at room temperature stirred the above-mentioned solution of preparing 2-3 hour, until homogeneous phase; Again above-mentioned colloidal sol is placed in the tetrafluoroethylene autoclave, crystallization under 140-180 ℃ of temperature, time 4-15 days, until complete crystallization; At last after filtration, washing, drying treatment, promptly get target product.
In the aforesaid method, the organic amine of adding can be triethylene tetramine, and at this moment the pH value is controlled between the 9-10.5, and obtaining topological framework is the wide aperture type beryllium phosphate molecular sieve by using of GME: BePO
4-GME.
In the aforesaid method, the organic amine of adding can be polyethylene polyamine or piperazine, and at this moment the pH value is controlled to be between the 6.2-6.6, obtains the type beryllium phosphate molecular sieve by using that topological framework is respectively GIS or ABW: BePO
4-GIS or BePO
4-ABW.
In the aforesaid method, the positively charged ion Na of adding
+, K
+Or NH
4 +, can obtain to add in corresponding sodium salts, sylvite or the ammonium salt respectively.
Be pure phase by aforesaid method institute synthetic type beryllium phosphate molecular sieve by using, monocrystalline size maximum can reach 400 μ m, and the aperture can reach 12 yuan of rings.Measure by X-ray single crystal diffraction, the synthetic beryllium phosphate has GME respectively, three kinds of topological frameworks of GIS and ABW.Now respectively with its called after FDU-5, FDU-6 and FDU-7.Set forth its structure and nature and characteristic below.
BePO4-GME is by BeO
4Tetrahedron and PO
4The three-dimensional net structure that the common summit of tetrahedron links to each other and formed, its structure contain 12 yuan of rings-dimension duct, and its template triethylene tetramine is positioned in the middle of 12 yuan of rings.It is that structural motif is piled up according to the AABB sequence and formed that its structure also can be described as with 6 yuan of rings, contains the 4.8.8 network structure in the skeleton.Its tetrahedron skeletal density (the tetrahedron atom number that unit volume contains) is 17.1.Investigate its stability as can be known by roasting in air, BePO
4-GME can be stabilized in 400 ℃.More than 400 ℃, BePO
4The skeleton of-GME caves in.Owing to can not remove the organic amine template fully, therefore can not show the good adsorption performance.
Be the BePO that template obtains by pyridine and piperazine respectively
4-GIS and BePO
4-ABW equally also is by BeO
4Tetrahedron and PO
4Tetrahedron connects the three-dimensional net structure of being formed, wherein BePO
4-GIS is in crystalline phase [001], and [010] and [111] direction all can be observed the duct of 8 yuan of rings, and the aperture is 5.7 * 7.8 .The tetrahedron skeletal density is 19.1.BePO
4-ABW equally also is the molecular sieve with 8 membered ring channels, and its tetrahedron skeletal density is 21.5.And BePO
4-GME is similar, at BePO
4-GIS and BePO
4All there is the 4.8.8 network in the structure of-ABW.
Embodiment
Further specify the present invention by the following examples.
Embodiment 1, takes by weighing 0.27 gram Be (OH)
2, adding concentration is 85% H
3PO4 1.65 grams add 10 distilled water that restrain again, at room temperature stir 1 hour.After treating to dissolve fully, add 2.74 gram triethylene tetramines (TETA), regulating the pH value is 10.0.The solution for preparing at room temperature stirs 2 hours until homogeneous phase.Be BeO: P with ratio at last
2O
5: TETA: H
2O=1: 1.25: 3.1: 95.8 the colloidal sol capacity of being transferred to was in the autoclave of tetrafluoroethylene of 33ml, 160 ℃ of following crystallization 8 days.Crystallization fully after, after filtration, the product that obtains after the washing, drying after measured structure be BePO
4-GME.Monocrystalline is of a size of 150 μ m.
Embodiment 2, and the solution of preparing according to the method for example 1 adds 0.02 gram NaOH (Na again
+/ Be
2+=0.1), regulate pH value and be 10.4. with the solution for preparing at room temperature restir be transferred to after 1 hour in the autoclave of tetrafluoroethylene, 160 ℃ of following crystallization 8 days.Crystallization fully after, after filtration, the product that obtains after the washing, drying after measured structure be BePO
4-GME.Monocrystalline is of a size of 50 μ m.
Embodiment 3, and the solution of preparing according to the method for example 1 adds 0.02 gram KOH (K again
+/ Be
2+=0.1), regulate pH value and be 10.4. with the solution for preparing at room temperature restir be transferred to after 1 hour in the autoclave of tetrafluoroethylene, 160 ℃ of following crystallization 8 days.Crystallization fully after, after filtration, the product that obtains after the washing, drying after measured structure be BePO
4-GME.Monocrystalline is of a size of 100 μ m.
Embodiment 4, and the solution of preparing according to the method for example 1 adds 0.02 gram NH again
4H
2PO
4(NH
4 +/ Be
2+=0.1), regulate pH value and be 10.4. with the solution for preparing at room temperature restir be transferred to after 1 hour in the autoclave of tetrafluoroethylene, 160 ℃ of following crystallization 8 days.Crystallization fully after, after filtration, the product that obtains after the washing, drying after measured structure be BePO
4-GME.Monocrystalline size maximum can reach 400 μ m.
Embodiment 5, take by weighing 0.27 gram Be (OH) according to the method for example 1
2, the H of 1.65 grams 85%
3PO4 adds 10 distilled water that restrain, and at room temperature stirs to add 2.74 gram polyethylene polyamines (PEPA) after 1 hour, and the pH value is 6.6.The solution for preparing at room temperature stirs 2 hours until homogeneous phase.Be BeO: P with ratio at last
2O
5: PEPA: H
2O=1: 1.25: 0.86: 97.7 the colloidal sol capacity of being transferred to was in the autoclave of tetrafluoroethylene of 33ml, 160 ℃ of following crystallization 8 days.Crystallization fully after, after filtration, the product that obtains after the washing, drying after measured structure be BePO
4-GME.Monocrystalline is of a size of 200 μ m.
Embodiment 6, and the solution according to the method for example 1 preparation pH=9.9 is transferred to the solution for preparing in the autoclave of tetrafluoroethylene at last, 140 ℃ of following crystallization 15 days.Crystallization fully after, after filtration, the product that obtains after the washing, drying after measured structure be BePO
4-GME.Monocrystalline is of a size of 100 μ m.
Embodiment 7, and the solution according to the method for example 1 preparation pH=9.7 is transferred to the solution for preparing in the autoclave of tetrafluoroethylene at last, 160 ℃ of following crystallization 10 days.Crystallization fully after, after filtration, the product that obtains after the washing, drying after measured structure be BePO
4-GME.Monocrystalline is of a size of 50 μ m.
Embodiment 8, and the solution according to the method for example 1 preparation pH=10.0 is transferred to the solution for preparing in the autoclave of tetrafluoroethylene at last, 180 ℃ of following crystallization 4 days.Crystallization fully after, after filtration, the product that obtains after the washing, drying after measured structure be BePO
4-GME.Monocrystalline is of a size of 50 μ m.
Embodiment 9, take by weighing 0.2 gram Be (OH)
2, adding concentration is 85% H
3PO4 0.9 gram adds 6 distilled water that restrain again, at room temperature stirs 2 hours.After treating to dissolve fully, add 2.8 gram pyridines (Py), regulating the pH value is 9.3.The solution for preparing at room temperature stirs 2 hours until homogeneous phase.Be BeO: P with ratio at last
2O
5: Py: H
2O=1: 1.7: 3.14: 71.8 the colloidal sol capacity of being transferred to was in the autoclave of tetrafluoroethylene of 33ml, 160 ℃ of following crystallization 8 days.Crystallization fully after, after filtration, the product that obtains after the washing, drying after measured structure be BePO
4-GIS.Monocrystalline is of a size of 100 μ m.
Embodiment 10, take by weighing 0.2 gram Be (OH)
2, adding concentration is 85% H
3PO4 1.0 grams add 6 distilled water that restrain again, at room temperature stir 2 hours.After treating to dissolve fully, add 20 gram piperazines (PIP), regulating the pH value is 6.4.The solution for preparing at room temperature stirs 2 hours until homogeneous phase.Be BeO: P with ratio at last
2O
5: PIP: H
2O=1: 1.6: 54.5: 71.8 the colloidal sol capacity of being transferred to was in the autoclave of tetrafluoroethylene of 33ml, 160 ℃ of following crystallization 8 days.Crystallization fully after, after filtration, the product that obtains after the washing, drying after measured structure be BePO
4-ABW.Monocrystalline is of a size of 100 μ m.
Claims (3)
1, a kind of synthetic method of type beryllium phosphate molecular sieve by using is characterized in that with dense amine be template, and synthetic under hydrothermal condition, concrete steps are as follows: at a certain amount of Be (OH)
2In, the concentration that adds its 3-10 times weight is 85% H
3PO
4With the water of 20-50 times of weight, at room temperature stirred 1-2 hour, until dissolving fully; Add organic amine R, and satisfy R/H
2O=1: (100-1), mixture finally meets mol ratio BeO: P
2O
5: R: H
2O=1: (1-2): (0.5-55): (50-100); Add sodium salt, sylvite or ammonium salt then, control pH value at room temperature stirred the above-mentioned solution of preparing 2-3 hour, until homogeneous phase; Again above-mentioned colloidal sol is placed in the tetrafluoroethylene autoclave, crystallization under 140-180 ℃ of temperature, time 4-15 days, until complete crystallization; At last after filtration, washing, drying treatment, promptly get target product.
2, the synthetic method of type beryllium phosphate molecular sieve by using according to claim 1 is characterized in that the organic amine that adds is a triethylene tetramine, and control pH value is 9-10.5.
3, the synthetic method of type beryllium phosphate molecular sieve by using according to claim 1 is characterized in that the organic amine that adds is polyethylene polyamine or sends piperazine, and control pH value is 6.2-6.6.
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| CN01126584A CN1122637C (en) | 2001-08-29 | 2001-08-29 | Method for synthesizing new-type beryllium phosphate molecular sieve by using concentrated amine system |
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| CN103073025B (en) * | 2011-10-25 | 2016-01-20 | 华东师范大学 | A kind of FER molecular sieve and synthetic method thereof |
| CN105129816B (en) * | 2015-08-19 | 2017-02-22 | 青岛大学 | 18-membered super-large-channel beryllium phosphate molecular sieve and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1034679A (en) * | 1984-12-18 | 1989-08-16 | 联合碳化公司 | The catalyzer that contains alumo-silicate molecular sieve |
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2001
- 2001-08-29 CN CN01126584A patent/CN1122637C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1034679A (en) * | 1984-12-18 | 1989-08-16 | 联合碳化公司 | The catalyzer that contains alumo-silicate molecular sieve |
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