CN104340992B - A kind of metal tripolyphosphate aluminium (MeAPO) molecular sieve with-CLO structure and preparation method thereof - Google Patents
A kind of metal tripolyphosphate aluminium (MeAPO) molecular sieve with-CLO structure and preparation method thereof Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/065—Aluminophosphates containing other elements, e.g. metals, boron the other elements being metals only
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The present invention relates to a kind of metal tripolyphosphate aluminium (MeAPO) molecular sieve with CLO structure and preparation method thereof.By source metal, aluminium source, phosphorus source, fluorine source, organic amine and ionic liquid according to MeO:Al2O3: P2O5: F‑: organic amine: ionic liquid=0.002～6:1:0.1～20:0.1～10:0.1～10:2～1000 molar ratio mix, obtain initial reaction mixture.By initial reaction mixture crystallization 0.5～120 hours at 100～300 DEG C, then filter, wash and be dried, i.e. obtain product.MeAPO molecular sieve prepared by the present invention has two ten-ring pore passage structures and good heat endurance, being with a wide range of applications in fields such as organic macromolecule catalysis, gas storages, the preparation method that the present invention uses has simple, safety and eco-friendly feature.
Description
Technical field
The present invention relates to a kind of metal tripolyphosphate aluminium (MeAPO) molecular sieve, specifically, relate to one and there is-CLO
The MeAPO molecular sieve of structure.
The invention still further relates to the preparation method of above-mentioned MeAPO molecular sieve.
Background technology
Molecular screen material has well-regulated pore passage structure and adjustable duct chemical composition because of it, and by extensively
It is applied to the fields such as catalysis, absorption, ion exchange.Nineteen eighty-two, Wilson, S.T. et al. synthesize first
Aluminium phosphate molecular sieve (USP4310440), has opened up a frontier of molecular screen material.Aluminium phosphate molecular sieve
Skeleton be to be formed by aluminum-oxygen tetrahedron and phosphorus oxygen tetrahedron alternate links, skeleton is electroneutral, thus does not has
HaveAcidity, limits its application in catalytic field.In order to improve urging of aluminium phosphate molecular sieve
Changing performance, people use metallic atom to replace aluminium or the phosphorus atoms of part in aluminium phosphate molecular sieve skeleton, obtain
There is the Metal-aluminophosphate Molecular Siever of acid centre or redox center.
2004, the Morris of University of St Andrews of Britain, R.E. et al. reported a kind of new molecule
Screen method, i.e. ion thermal synthesis (Nature, 2004,430,1012-1016).With traditional Hydrothermal Synthesis
Comparing with solvent-thermal process, ion thermal synthesis has the following characteristics that in building-up process, and ionic liquid is
Reaction dissolvent, is also template, decreases solvent-skeleton structure and the competition of template-skeleton structure effect；
Ionic liquid is of a great variety, and zwitterion all can selective modulation and design, therefore ion heat seal as required
Become to have shown great potential in terms of synthesizing new structure and new ingredient sieve；The vapour pressure of ionic liquid
Almost nil, ion thermal synthesis can be carried out at ambient pressure, eliminates solvent in course of reaction spontaneous high pressure institute
The potential safety hazard brought；After reaction, ionic liquid can recycle, and reduces production cost, reduces environment dirty
Dye.
The most existing many about ion thermal synthesis aluminium phosphate molecular sieve and the report of Metal-aluminophosphate Molecular Siever.
Morris, R.E. et al. use the hot method of ion to synthesize aluminium phosphate molecular sieve and the metal phosphorus of various new structure
Acid aluminum molecular screen (Nature, 2004,430,1012-1016;J.Am.Chem.Soc.,2006,128,
2204-2205), such as SIZ-1 and SIZ-7.Wang Lei et al. uses the hot method of ion to synthesize phosphoric acid magnalium
(MgAPO) molecular sieve, the Pt/MgAPO catalyst thus prepared is in n-alkane hydroisomerization reaction
Show the catalytic performance (Chem.Eur.J., 2008,14,10551-10555) of excellence.Recently,
Wei Ying et al. utilizes the hot method of ion to synthesize the super big hole aluminium phosphate molecular sieve DNL-1 with-CLO structure
(CN102139885A；Angew.Chem.Int.Ed., 2010,49,5367-5370).DNL-1 has
Having the 3 D pore canal system of two non-crossing, an individual system, via α cage and rpa cage, has octatomic ring aperture,
And another is via cubical, there is the four-leaf clover surrounded by 20 T atom and 24 oxygen atoms
Shape aperture, the cross section in these ducts is a big cube supercage with pocket.Additionally, DNL-1 tool
There is good heat endurance, will be catalyzed at organic macromolecule, before the field such as gas storage has a wide range of applications
Scape.The synthesis of ion hot method is not the most also had to have the report of-CLO structural metal aluminium phosphate molecular sieve.
Summary of the invention
It is an object of the invention to provide a kind of metal tripolyphosphate aluminium (MeAPO) molecular sieve with-CLO structure and
Its preparation method.
For achieving the above object, MeAPO molecular sieve provided by the present invention, its X-ray diffraction spectrogram should be extremely
Have less following characteristics diffraction maximum (2 θ values represent diffraction maximums positions):
2θ/°:3.37±0.2,4.79±0.2,5.89±0.2,6.82±0.2,7.63±0.2,8.36
±0.2,9.67±0.2,10.27±0.2,11.37±0.2,11.87±0.2,12.37±0.2,12.83
±0.2,13.74±0.2,14.17±0.2,14.58±0.2,20.72±0.2；
Determine that its structure is that International Zeolite Association confirms by comparing with XRD powder diffraction data storehouse card
-CLO structure, it has the 3 D pore canal system of two non-crossing, an individual system via α cage and rpa cage,
There is octatomic ring aperture, and another is via cubical, has by 20 T atom (Al, Me and P
Atom) and the four-leaf clover shape aperture that surrounds of 24 oxygen atoms, the cross section in these ducts be one big
Cube supercage with pocket；X-ray fluorescence spectra constituent content analysis determines (Me+Al) in this molecular sieve:
P=0.8～1.2(mol ratio).This molecular sieve has the skeleton structure of spaciousness and good heat endurance, has
Hope and be used widely in fields such as organic macromolecule catalysis, gas storages.
In above-mentioned MeAPO molecular sieve Me be magnesium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zinc, gallium, germanium,
One or more in zirconium, tin, the one in preferably magnesium, titanium, manganese, iron, cobalt, nickel, zinc, gallium or two
More than Zhong, one or more in particularly preferred magnesium, manganese, cobalt, nickel, zinc.
The method preparing above-mentioned MeAPO molecular sieve that the present invention provides, its step is as follows:
(1) after ionic liquid being warming up to 50～150 DEG C, add phosphorus source, aluminium source, source metal, fluorine source and
Organic amine stirs, MeO:Al in the reactant mixture made2O3: P2O5: F-: organic amine: from
The mol ratio of sub-liquid is 0.002～6:1:0.1～20:0.1～10:0.1～10:2～1000.
(2) by the reactant mixture of step (1) gained crystallization 0.5～120 hours at 100～300 DEG C.
(3), after step (2) terminates, product is cooled to room temperature, is filtered, washed and dried, i.e. obtain
There is the MeAPO molecular sieve of-CLO structure.
MeO:Al in reactant mixture described in above-mentioned synthetic method step (1)2O3: P2O5: F-: have
Machine amine: the preferred proportion (mol ratio) of ionic liquid is: 0.002～2:1:0.5～12:0.5～
6:0.4～4:10～200.
Above-mentioned synthetic method intermediate ion liquid uses containing following cation: alkyl quaternary ammonium ion [NR4]+, alkyl
Season phosphine ion [PR4]+, the substituted imidazol ion of alkyl [Rim]+, the substituted pyridinium ion of alkyl [Rpy]+In
The ionic liquid of one or more mixtures, R is the alkyl of C1-C16, and ionic liquid anion can be: F-、
Cl-、Br-、I-、BF4 -、PF6 -、PO4 3-、SO4 2-、NO3 -、CF3SO3 -、N(CF3SO2)2 -、C(CF3SO2)3 -In
One or more；Phosphorus source be the one in phosphoric acid, ammonium phosphate, monoammonium phosphate, ammonium dihydrogen phosphate or
Two or more；Aluminium source is in aluminium isopropoxide, boehmite, aluminum sulfate, aluminum nitrate, hydrated alumina
One or more；Fluorine source is one or more in hydrofluoric acid, ammonium fluoride, sodium fluoride；Organic
Amine is one or more in fatty amine, aromatic amine, hydramine, quaternary ammonium compound.
In above-mentioned synthetic method, source metal is magnesium acetate, magnesium chloride, magnesium nitrate, magnesia, manganese acetate, chlorine
Change manganese, manganese monoxide, manganese sulfate, manganese carbonate, cobalt acetate, cobalt carbonate, cobaltous sulfate, cobalt nitrate, chlorination
Cobalt, cobalt hydroxide, nickel acetate, nickel nitrate, nickel oxide, nickel chloride, zinc acetate, zinc chloride, zinc nitrate,
One or more in zinc oxide.
Above-mentioned synthetic method step (1) preferably raw material mixing temperature is 70～110 DEG C, excellent in step (2)
The crystallization temperature of choosing is 150～250 DEG C, and preferred crystallization time is 1h～72h, the heating side of crystallization process
Formula can use traditional heating mode, such as: baking oven heating, oil bath heating, it would however also be possible to employ heating using microwave.
Can contain a certain proportion of water in reactant mixture described in above-mentioned synthetic method step (1), water can
To be brought into by the raw material such as phosphoric acid solution or hydrofluoric acid solution, it is possible to additionally add when using anhydrous raw material, contain
The water yield is the 0-10wt% of reactant mixture gross weight.
The preparation method that the present invention uses has simple, safety and eco-friendly feature.Provided by the present invention
The Metal-aluminophosphate Molecular Siever with-CLO structure have spaciousness skeleton structure and good heat endurance,
In fields such as organic macromolecule catalysis, gas storages, there is potential application prospect.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of sample in the embodiment of the present invention 1.
Fig. 2 is the XRD spectra of sample in the embodiment of the present invention 2.
Fig. 3 is the XRD spectra of sample in the embodiment of the present invention 3.
Fig. 4 is the XRD spectra of sample in the embodiment of the present invention 4.
Fig. 5 is the XRD spectra of sample in the embodiment of the present invention 5.
Fig. 6 is the XRD spectra of sample in the embodiment of the present invention 6.
Fig. 7 is the XRD spectra of sample in the embodiment of the present invention 7.
Fig. 8 is the XRD spectra of sample in the embodiment of the present invention 8.
Fig. 9 is the XRD spectra of sample in the embodiment of the present invention 9.
Figure 10 is the XRD spectra of sample in the embodiment of the present invention 10.
Figure 11 is the UV-Vis DRS spectrogram of sample in the embodiment of the present invention 1.
Figure 12 is the SEM electromicroscopic photograph of sample in the embodiment of the present invention 1.
Detailed description of the invention
Below by embodiment, the present invention will be further described, but embodiments of the present invention are not limited to this,
It is not intended that limiting the scope of the invention.
Embodiment 1
The phosphoric acid that 0.89 gram of concentration is 85wt% is joined equipped with 53.5 grams of 1-ethyl-3-methy limidazolium
In 100 milliliters of beakers of ionic liquid, under 90 DEG C and stirring condition, add 1.43 grams of aluminium isopropoxides and 0.18
Gram cobalt acetate, after stirring 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continues stirring 30
After minute, add 0.50 gram 1,6-hexamethylene diamine, it is stirred until homogeneous and obtains initial reaction mixture.By above-mentioned mixed
Compound is transferred in the stainless steel cauldron that 100ml polytetrafluoroethylene (PTFE) is lining, puts into 210 DEG C of baking ovens after sealing
In, crystallization 3h.
Reactor taking-up is cooled to room temperature after terminating by crystallization, leaches crystallization product.By product deionized water
With ethanol cyclic washing, it is dried at 90 DEG C, i.e. obtains blue powder product.XRD spectra shows this blueness
Powder has-CLO topological structure, the Co of UV Diffuse Reflectance Spectroscopy spectrogram display simultaneously2+Presented in four-coordination
In aluminium phosphate molecular sieve skeleton.SEM photograph shows, products therefrom is cube crystal grain, and size is about 30
μm。
Embodiment 2
The phosphoric acid that 0.89 gram of concentration is 85wt% is joined equipped with 53.5 grams of 1-ethyl-3-methy limidazolium
In 100 milliliters of beakers of ionic liquid, under 90 DEG C and stirring condition, add 1.43 grams of aluminium isopropoxides and 0.18
Gram cobalt acetate, after stirring 30 minutes, adding 0.84 gram of concentration is the hydrofluoric acid of 40wt%, continues stirring 30
After minute, add 0.50 gram 1,6-hexamethylene diamine, it is stirred until homogeneous and obtains initial reaction mixture.By above-mentioned mixed
Compound is transferred in the stainless steel cauldron that 100ml polytetrafluoroethylene (PTFE) is lining, puts into 210 DEG C of baking ovens after sealing
In, crystallization 3h.
Reactor taking-up is cooled to room temperature after terminating by crystallization, leaches crystallization product.By product deionized water
With ethanol cyclic washing, it is dried at 90 DEG C, i.e. obtains blue powder product.XRD spectra shows this blueness
Powder has-CLO topological structure.
Embodiment 3
The phosphoric acid that 1.61 grams of concentration is 85wt% is joined equipped with 53.5 grams of 1-ethyl-3-methy limidazolium
In 100 milliliters of beakers of ionic liquid, under 90 DEG C and stirring condition, add 1.43 grams of aluminium isopropoxides and 0.18
Gram cobalt acetate, after stirring 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continues stirring 30
After minute, add 0.50 gram 1,6-hexamethylene diamine, it is stirred until homogeneous and obtains initial reaction mixture.By above-mentioned mixed
Compound is transferred in the stainless steel cauldron that 100ml polytetrafluoroethylene (PTFE) is lining, puts into 210 DEG C of baking ovens after sealing
In, crystallization 3h.
Reactor taking-up is cooled to room temperature after terminating by crystallization, leaches crystallization product.By product deionized water
With ethanol cyclic washing, it is dried at 90 DEG C, i.e. obtains blue powder product.XRD spectra shows this blueness
Powder has-CLO topological structure.
Embodiment 4
The phosphoric acid that 0.89 gram of concentration is 85wt% is joined equipped with 80.3 grams of 1-ethyl-3-methy limidazolium
In 100 milliliters of beakers of ionic liquid, under 90 DEG C and stirring condition, add 1.43 grams of aluminium isopropoxides and 0.18
Gram cobalt acetate, after stirring 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continues stirring 30
After minute, add 0.50 gram 1,6-hexamethylene diamine, it is stirred until homogeneous and obtains initial reaction mixture.By above-mentioned mixed
Compound is transferred in the stainless steel cauldron that 100ml polytetrafluoroethylene (PTFE) is lining, puts into 210 DEG C of baking ovens after sealing
In, crystallization 3h.
Reactor taking-up is cooled to room temperature after terminating by crystallization, leaches crystallization product.By product deionized water
With ethanol cyclic washing, it is dried at 90 DEG C, i.e. obtains blue powder product.XRD spectra shows this blueness
Powder has-CLO topological structure.
Embodiment 5
The phosphoric acid that 0.89 gram of concentration is 85wt% is joined equipped with 53.5 grams of 1-ethyl-3-methy limidazolium
In 100 milliliters of beakers of ionic liquid, under 90 DEG C and stirring condition, add 1.43 grams of aluminium isopropoxides and 0.09
Gram cobalt acetate, after stirring 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continues stirring 30
After minute, add 0.50 gram 1,6-hexamethylene diamine, it is stirred until homogeneous and obtains initial reaction mixture.By above-mentioned mixed
Compound is transferred in the stainless steel cauldron that 100ml polytetrafluoroethylene (PTFE) is lining, puts into 210 DEG C of baking ovens after sealing
In, crystallization 3h.
Reactor taking-up is cooled to room temperature after terminating by crystallization, leaches crystallization product.By product deionized water
With ethanol cyclic washing, it is dried at 90 DEG C, i.e. obtains blue powder product.XRD spectra shows this blueness
Powder has-CLO topological structure.
Embodiment 6
The phosphoric acid that 0.89 gram of concentration is 85wt% is joined equipped with 53.5 grams of 1-ethyl-3-methy limidazolium
In 100 milliliters of beakers of ionic liquid, under 90 DEG C and stirring condition, add 1.43 grams of aluminium isopropoxides and 0.18
Gram cobalt acetate, after stirring 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continues stirring 30
After minute, add 0.50 gram 1,6-hexamethylene diamine, it is stirred until homogeneous and obtains initial reaction mixture.By above-mentioned mixed
Compound is transferred in the stainless steel cauldron that 100ml polytetrafluoroethylene (PTFE) is lining, puts into 190 DEG C of baking ovens after sealing
In, crystallization 3h.
Reactor taking-up is cooled to room temperature after terminating by crystallization, leaches crystallization product.By product deionized water
With ethanol cyclic washing, it is dried at 90 DEG C, i.e. obtains blue powder product.XRD spectra shows this blueness
Powder has-CLO topological structure
Embodiment 7
The phosphoric acid that 0.89 gram of concentration is 85wt% is joined equipped with 53.5 grams of 1-ethyl-3-methy limidazolium
In 100 milliliters of beakers of ionic liquid, under 90 DEG C and stirring condition, add 1.43 grams of aluminium isopropoxides and 0.04
Gram manganese acetate, after stirring 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continues stirring 30
After minute, add 0.50 gram 1,6-hexamethylene diamine, it is stirred until homogeneous and obtains initial reaction mixture.By above-mentioned mixed
Compound is transferred in the stainless steel cauldron that 100ml polytetrafluoroethylene (PTFE) is lining, puts into 210 DEG C of baking ovens after sealing
In, crystallization 3h.
Reactor taking-up is cooled to room temperature after terminating by crystallization, leaches crystallization product.By product deionized water
With ethanol cyclic washing, it is dried at 90 DEG C, i.e. obtains white powder product.XRD spectra shows this white
Powder has-CLO topological structure.
Embodiment 8
The phosphoric acid that 0.89 gram of concentration is 85wt% is joined equipped with 53.5 grams of 1-ethyl-3-methy limidazolium
In 100 milliliters of beakers of ionic liquid, under 90 DEG C and stirring condition, add 1.43 grams of aluminium isopropoxides and 0.18
Gram nickel acetate, after stirring 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continues stirring 30
After minute, add 0.50 gram 1,6-hexamethylene diamine, it is stirred until homogeneous and obtains initial reaction mixture.By above-mentioned mixed
Compound is transferred in the stainless steel cauldron that 100ml polytetrafluoroethylene (PTFE) is lining, puts into 210 DEG C of baking ovens after sealing
In, crystallization 3h.
Reactor taking-up is cooled to room temperature after terminating by crystallization, leaches crystallization product.By product deionized water
With ethanol cyclic washing, it is dried at 90 DEG C, i.e. obtains yellow greenish powder product.XRD spectra shows this Huang
Green powder has-CLO topological structure.
Embodiment 9
The phosphoric acid that 0.89 gram of concentration is 85wt% is joined equipped with 53.5 grams of 1-ethyl-3-methy limidazolium
In 100 milliliters of beakers of ionic liquid, under 90 DEG C and stirring condition, add 1.43 grams of aluminium isopropoxides and 0.16
Gram zinc acetate, after stirring 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continues stirring 30
After minute, add 0.50 gram 1,6-hexamethylene diamine, it is stirred until homogeneous and obtains initial reaction mixture.By above-mentioned mixed
Compound is transferred in the stainless steel cauldron that 100ml polytetrafluoroethylene (PTFE) is lining, puts into 210 DEG C of baking ovens after sealing
In, crystallization 3h.
Reactor taking-up is cooled to room temperature after terminating by crystallization, leaches crystallization product.By product deionized water
With ethanol cyclic washing, it is dried at 90 DEG C, i.e. obtains white powder product.XRD spectra shows this white
Powder has-CLO topological structure.
Embodiment 10
The phosphoric acid that 0.89 gram of concentration is 85wt% is joined equipped with 53.5 grams of 1-ethyl-3-methy limidazolium
In 100 milliliters of beakers of ionic liquid, under 90 DEG C and stirring condition, add 1.43 grams of aluminium isopropoxides and 0.15
Gram magnesium acetate, after stirring 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continues stirring 30
After minute, add 0.50 gram 1,6-hexamethylene diamine, it is stirred until homogeneous and obtains initial reaction mixture.By above-mentioned mixed
Compound is transferred in the stainless steel cauldron that 100ml polytetrafluoroethylene (PTFE) is lining, puts into 210 DEG C of baking ovens after sealing
In, crystallization 3h.
Reactor taking-up is cooled to room temperature after terminating by crystallization, leaches crystallization product.By product deionized water
With ethanol cyclic washing, it is dried at 90 DEG C, i.e. obtains white powder product.XRD spectra shows this white
Powder has-CLO topological structure.
Claims (11)
1. metal tripolyphosphate aluminium (MeAPO) molecular sieve, it is characterised in that: its x-ray diffraction pattern
Figure should at least have a following characteristics diffraction maximum:
The position of 2 θ values expression diffraction maximums, 2 θ/°: 3.37 ± 0.2,4.79 ± 0.2,5.89 ± 0.2,
6.82±0.2,7.63±0.2,8.36±0.2,9.67±0.2,10.27±0.2,11.37±0.2,
11.87±0.2,12.37±0.2,12.83±0.2,13.74±0.2,14.17±0.2,14.58±
0.2,20.72±0.2；
Its structure is the-CLO structure that International Zeolite Association confirms, (Me+Al): P in this molecular sieve simultaneously
Mol ratio=0.8～1.2；This molecular sieve has the 3 D pore canal system of two non-crossing, an individual system
Via α cage and rpa cage, there is octatomic ring aperture, and another is via cubical, has by 20
The four-leaf clover shape aperture that individual T atom Al, Me and P atom and 24 oxygen atoms surround, these ducts
Cross section be a big cube supercage with pocket.
MeAPO molecular sieve the most according to claim 1, it is characterised in that: Me be magnesium, titanium, vanadium,
One or more in chromium, manganese, iron, cobalt, nickel, zinc, gallium, germanium, zirconium, tin.
MeAPO molecular sieve the most according to claim 2, it is characterised in that: Me be preferably magnesium, titanium,
One or more in manganese, iron, cobalt, nickel, zinc, gallium.
MeAPO molecular sieve the most according to claim 3, it is characterised in that: Me be particularly preferably magnesium,
One or more in manganese, cobalt, nickel, zinc.
5. a preparation method for MeAPO molecular sieve described in claim 1 or 2, its step is as follows:
(1), after ionic liquid being warming up to 50～150 DEG C, phosphorus source, aluminium source, source metal, fluorine source are added
Stir with organic amine, MeO:Al in the reactant mixture made2O3: P2O5: F-: organic amine:
The mol ratio of ionic liquid be 0.002～6:1:0.1～20:0.1～10:0.1～10:2～
1000；
(2) by the reactant mixture of step (1) gained crystallization 0.5～120 hours at 100～300 DEG C；
(3), after step (2) terminates, product is cooled to room temperature, is filtered, washed and dried, to obtain final product
To the MeAPO molecular sieve with-CLO structure；
Ionic liquid is for comprising following cation: alkyl quaternary ammonium ion [NR4]+, alkyl quaternary phosphine ion [PR4]+,
The substituted imidazol ion of alkyl [Rim]+, the substituted pyridinium ion of alkyl [Rpy]+In one or both with
Upper ionic liquid, R is the alkyl of C1-C16；Organic amine is fatty amine, aromatic amine, hydramine or quaternary ammonium salt
One or more in compounds.
Method the most according to claim 5, it is characterised in that: step (1) described reaction mixing
MeO:Al in thing2O3: P2O5: F-: organic amine: the molar ratio of ionic liquid is 0.002～2:
1:0.5～12:0.5～6:0.4～4:10～200.
Method the most according to claim 5, it is characterised in that: source metal be magnesium acetate, magnesium chloride,
Magnesium nitrate, magnesia, manganese acetate, manganese chloride, manganese monoxide, manganese sulfate, manganese carbonate, cobalt acetate,
Cobalt carbonate, cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt hydroxide, nickel acetate, nickel nitrate, nickel oxide,
One or more in nickel chloride, zinc acetate, zinc chloride, zinc nitrate, zinc oxide.
Method the most according to claim 5, it is characterised in that: phosphorus source is phosphoric acid, ammonium phosphate, phosphorus
Acid one hydrogen ammonium, ammonium dihydrogen phosphate in one or more；Aluminium source be aluminium isopropoxide, boehmite,
One or more in aluminum sulfate, aluminum nitrate, hydrated alumina；Fluorine source be hydrofluoric acid, ammonium fluoride,
One or more in sodium fluoride.
Method the most according to claim 5, it is characterised in that: crystallization condition is: 150～250 DEG C
Under, under normal pressure or self-generated pressure, crystallization time is 1h～72h.
Method the most according to claim 5, it is characterised in that: step (1) described ionic liquid
Be warming up to 70～110 DEG C before raw material adds, i.e. raw material mixing temperature is 70～110 DEG C.
11. methods according to claim 5, it is characterised in that: step (1) described reaction mixing
Containing a certain proportion of water in thing, water is brought into by raw material or additionally adds, and water content is that reactant mixture is total
The 0-10wt% of weight.
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| CN201310335637.1A CN104340992B (en) | 2013-08-02 | 2013-08-02 | A kind of metal tripolyphosphate aluminium (MeAPO) molecular sieve with-CLO structure and preparation method thereof |
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| CN104340992B true CN104340992B (en) | 2016-08-24 |
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| CN109422281A (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 LTA structure hetero atom Metal-aluminophosphate Molecular Siever |
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| CN109502602B (en) * | 2018-12-26 | 2021-12-07 | 北京化工大学 | Preparation method of silicon silicate molecular sieve |
| CN111498866A (en) * | 2020-04-27 | 2020-08-07 | 北京化工大学 | Organic hybrid-C L O structure silicoaluminophosphate molecular sieve and preparation method thereof |
| CN112028087B (en) * | 2020-08-14 | 2022-01-07 | 深圳技术大学 | Transition metal element doped AlPO-15 molecular sieve and preparation method thereof |
| CN112939005A (en) * | 2021-03-30 | 2021-06-11 | 北京化工大学 | Synthesis method of-CLO structure ultra-large pore aluminum phosphate and heteroatom aluminum phosphate molecular sieve |
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