CN104340992A - Metallic aluminum phosphate (MeAPO) molecular sieve with -CLO structure, and preparation method thereof - Google Patents
Metallic aluminum phosphate (MeAPO) molecular sieve with -CLO structure, and preparation method thereof Download PDFInfo
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- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
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Abstract
The invention relates to a metallic aluminum phosphate (MeAPO) molecular sieve with -CLO structure, and a preparation method thereof. According to the invention, a metal source, an aluminum source, a phosphorous source, a fluorine source, organic amine and ionic liquid are uniformly mixed according to a molar ratio that MeO:Al2O3:P2O5:F<->:organic amine:ionic liquid=0.002-6:1:0.1-20:0.1-10:0.1-10:2-1000, such that an initial reaction mixture is obtained; the initial reaction mixture is crystallized for 0.5-120h under a temperature of 100-300 DEG C; and filtering, washing and drying are carried out, such that a product is obtained. According to the invention, the prepared MeAPO molecular sieve has an vigesimal ring pore structure and good thermal stability. The molecular sieve has a good application prospect and can be widely applied in fields such as organic macromolecular catalysis and gas storage. The preparation method is characterized in simple, safe, and environment-friendly properties.
Description
Technical field
The present invention relates to a kind of metal tripolyphosphate aluminium (MeAPO) molecular sieve, specifically, relate to a kind of MeAPO molecular sieve with-CLO structure.
The invention still further relates to the preparation method of above-mentioned MeAPO molecular sieve.
Background technology
Molecular screen material because of the well-regulated pore passage structure of its tool and adjustable duct chemical constitution, and is widely used in the fields such as catalysis, absorption, ion-exchange.Nineteen eighty-two, the people such as Wilson, S.T. have synthesized aluminium phosphate molecular sieve (USP4310440) first, have opened up a frontier of molecular screen material.The skeleton of aluminium phosphate molecular sieve is formed by aluminum-oxygen tetrahedron and phosphorus oxygen tetrahedron alternate links, and skeleton is electric neutrality, does not thus have
acidity, limits its application in catalytic field.In order to improve the catalytic performance of aluminium phosphate molecular sieve, people use atoms metal to replace aluminium or the phosphorus atom of part in aluminium phosphate molecular sieve skeleton, obtain the Metal-aluminophosphate Molecular Siever with acid sites or redox center.
2004, the Morris of University of St Andrews of Britain, the people such as R.E. reported a kind of new molecular sieve methods, i.e. ion thermal synthesis (Nature, 2004,430,1012-1016).Compare with solvent-thermal process with traditional Hydrothermal Synthesis, ion thermal synthesis has following characteristics: in building-up process, and ionic liquid is reaction solvent, is also template, decreases the competition of solvent-skeleton structure and template-skeleton structure effect; Ionic liquid is of a great variety, and zwitterion all can selectivity modulation and design as required, and therefore ion thermal synthesis has shown great potential in synthesizing new structure and new ingredient sieve; The vapour pressure of ionic liquid is almost nil, and ion thermal synthesis can be carried out at ambient pressure, eliminates the potential safety hazard that the spontaneous high pressure of solvent in reaction process brings; After reaction, ionic liquid can be recycled, and reduces production cost, reduces environmental pollution.
At present existing many reports about ion thermal synthesis aluminium phosphate molecular sieve and Metal-aluminophosphate Molecular Siever.The people such as Morris, R.E. adopt the hot method of ion to synthesize aluminium phosphate molecular sieve and Metal-aluminophosphate Molecular Siever (Nature, 2004,430, the 1012-1016 of various new structure; J.Am.Chem.Soc., 2006,128,2204-2205), such as SIZ-1 and SIZ-7.The people such as Wang Lei adopt the hot method of ion to synthesize phosphoric acid magnalium (MgAPO) molecular sieve, and the Pt/MgAPO catalyzer prepared thus shows excellent catalytic performance (Chem.Eur.J., 2008,14,10551-10555) in normal paraffin hydroisomerization reaction.Recently, the people such as Wei Ying utilizes the hot method of ion to synthesize to have the oversized hole aluminium phosphate molecular sieve DNL-1(CN102139885A of-CLO structure; Angew.Chem.Int.Ed., 2010,49,5367-5370).DNL-1 has the 3 D pore canal system of two non-crossing, one individual system is via α cage and rpa cage, there is octatomic ring aperture, and another is via cubical, have the four-leaf clover shape aperture surrounded by 20 T atoms and 24 Sauerstoffatoms, the cross section in these ducts is the large cube supercages with pocket.In addition, DNL-1 has good thermostability, will be with a wide range of applications in fields such as organic macromolecule catalysis, atmosphere storage.Up to the present the hot method synthesis of ion is not also had to have the report of-CLO structural metal aluminium phosphate molecular sieve.
Summary of the invention
The object of the present invention is to provide a kind of metal tripolyphosphate aluminium (MeAPO) molecular sieve with-CLO structure and preparation method thereof.
For achieving the above object, MeAPO molecular sieve provided by the present invention, its X-ray diffraction spectrogram at least should have following characteristics diffraction peak (2 θ values represent the position of diffraction peak):
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 the-CLO structure that International Zeolite Association confirms by comparing with XRD powder diffraction data storehouse card, it has the 3 D pore canal system of two non-crossing, one individual system is via α cage and rpa cage, there is octatomic ring aperture, and another is via cubical, have the four-leaf clover shape aperture surrounded by 20 T atoms (Al, Me and P atom) and 24 Sauerstoffatoms, the cross section in these ducts is the large cube supercages 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 spacious skeleton structure and good thermostability, is expected to be used widely in fields such as organic macromolecule catalysis, atmosphere storage.
In above-mentioned MeAPO molecular sieve, Me is one or more in magnesium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zinc, gallium, germanium, zirconium, tin, one or more in preferably magnesium, titanium, manganese, iron, cobalt, nickel, zinc, gallium, one or more particularly preferably in magnesium, manganese, cobalt, nickel, zinc.
The method of the above-mentioned MeAPO molecular sieve of preparation provided by the invention, its step is as follows:
(1), after ionic liquid being warming up to 50 ~ 150 DEG C, adding phosphorus source, aluminium source, source metal, fluorine source and organic amine and stir, MeO:Al in the reaction mixture made
2o
3: P
2o
5: F
-: organic amine: the mol ratio of ionic liquid is 0.002 ~ 6:1:0.1 ~ 20:0.1 ~ 10:0.1 ~ 10:2 ~ 1000.
(2) by the reaction mixture of step (1) gained crystallization 0.5 ~ 120 hour at 100 ~ 300 DEG C.
(3) after step (2) terminates, product is cooled to room temperature, filters, wash and drying, namely be there is the MeAPO molecular sieve of-CLO structure.
MeO:Al in reaction mixture described in above-mentioned synthetic method step (1)
2o
3: P
2o
5: F
-: organic 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 adopts containing following positively charged ion: alkyl quaternary ammonium ion [NR
4]
+, alkyl quaternary phosphine ion [PR
4]
+, the imidazol ion [Rim] that alkyl replaces
+, the pyridinium ion [Rpy] that alkyl replaces
+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
-, BF
4 -, PF
6 -, PO
4 3-, SO
4 2-, NO
3 -, CF
3sO
3 -, N (CF
3sO
2)
2 -, C (CF
3sO
2)
3 -in one or more; Phosphorus source is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate; Aluminium source is one or more in aluminum isopropylate, pseudo-boehmite, Tai-Ace S 150, aluminum nitrate, hydrated aluminum oxide; Fluorine source is one or more in hydrofluoric acid, Neutral ammonium fluoride, Sodium Fluoride; Organic amine is one or more in aliphatic amide, aromatic amine, hydramine, quaternary ammonium compound.
In above-mentioned synthetic method, source metal is one or more in magnesium acetate, magnesium chloride, magnesium nitrate, magnesium oxide, manganous acetate, Manganous chloride tetrahydrate, manganese monoxide, manganous sulfate, manganous carbonate, cobaltous acetate, cobaltous carbonate, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride, cobaltous hydroxide, nickelous acetate, nickelous nitrate, nickel oxide, nickelous chloride, zinc acetate, zinc chloride, zinc nitrate, zinc oxide.
The preferred raw material mixing temperature of above-mentioned synthetic method step (1) is 70 ~ 110 DEG C, in step (2), preferred crystallization temperature is 150 ~ 250 DEG C, preferred crystallization time is 1h ~ 72h, the type of heating of crystallization process can adopt traditional heating mode, as: baking oven for heating, oil bath heating, also can adopt microwave heating.
A certain proportion of water can be contained in reaction mixture described in above-mentioned synthetic method step (1), water can be brought into by the raw material such as phosphoric acid solution or hydrofluoric acid solution, also additionally can add when adopting anhydrous raw material, water content is the 0-10wt% of reaction mixture gross weight.
The preparation method that the present invention uses has simply, safe and eco-friendly feature.The Metal-aluminophosphate Molecular Siever of-the CLO of having structure provided by the present invention has spacious skeleton structure and good thermostability, has potential application prospect in fields such as organic macromolecule catalysis, atmosphere storage.
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.
Embodiment
Below by embodiment, the present invention will be further described, but embodiments of the present invention are not limited thereto, and can not be interpreted as limiting the scope of the invention.
Embodiment 1
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.18 gram of Cobaltous diacetate is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 210 DEG C of baking ovens, crystallization 3h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain blue powder product.XRD spectra shows that this blue powder has-CLO topological framework, the Co of UV Diffuse Reflectance Spectroscopy spectrogram display simultaneously
2+be present in aluminium phosphate molecular sieve skeleton with the form of four-coordination.SEM photo shows, and products therefrom is cubes crystal grain, and size is about 30 μm.
Embodiment 2
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.18 gram of Cobaltous diacetate is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.84 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 210 DEG C of baking ovens, crystallization 3h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain blue powder product.XRD spectra shows that this blue powder has-CLO topological framework.
Embodiment 3
The phosphoric acid being 85wt% by 1.61 grams of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.18 gram of Cobaltous diacetate is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 210 DEG C of baking ovens, crystallization 3h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain blue powder product.XRD spectra shows that this blue powder has-CLO topological framework.
Embodiment 4
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 80.3 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.18 gram of Cobaltous diacetate is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 210 DEG C of baking ovens, crystallization 3h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain blue powder product.XRD spectra shows that this blue powder has-CLO topological framework.
Embodiment 5
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.09 gram of Cobaltous diacetate is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 210 DEG C of baking ovens, crystallization 3h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain blue powder product.XRD spectra shows that this blue powder has-CLO topological framework.
Embodiment 6
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.18 gram of Cobaltous diacetate is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 190 DEG C of baking ovens, crystallization 3h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain blue powder product.XRD spectra shows that this blue powder has-CLO topological framework
Embodiment 7
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.04 gram of manganese acetate is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 210 DEG C of baking ovens, crystallization 3h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.XRD spectra shows that this white powder has-CLO topological framework.
Embodiment 8
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.18 gram of nickel acetate is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 210 DEG C of baking ovens, crystallization 3h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain yellow greenish powder product.XRD spectra shows that this yellow greenish powder has-CLO topological framework.
Embodiment 9
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.16 gram of zinc acetate is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 210 DEG C of baking ovens, crystallization 3h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.XRD spectra shows that this white powder has-CLO topological framework.
Embodiment 10
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.15 gram of magnesium acetate is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.70 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 210 DEG C of baking ovens, crystallization 3h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.XRD spectra shows that this white powder has-CLO topological framework.
Claims (10)
1. metal tripolyphosphate aluminium (MeAPO) molecular sieve, is characterized in that: its X-ray diffraction spectrogram should at least have following characteristics diffraction peak:
2 θ values represent the position of diffraction peak, 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, simultaneously in this molecular sieve (Me+Al): P=0.8 ~ 1.2(mol ratio); This molecular sieve has the 3 D pore canal system of two non-crossing, one individual system is via α cage and rpa cage, there is octatomic ring aperture, and another is via cubical, have the four-leaf clover shape aperture surrounded by 20 T atoms (Al, Me and P atom) and 24 Sauerstoffatoms, the cross section in these ducts is the large cube supercages with pocket.
2. MeAPO molecular sieve according to claim 1, it is characterized in that: Me is one or more in magnesium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zinc, gallium, germanium, zirconium, tin, one or more in preferably magnesium, titanium, manganese, iron, cobalt, nickel, zinc, gallium, one or more particularly preferably in magnesium, manganese, cobalt, nickel, zinc.
3. 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, adding phosphorus source, aluminium source, source metal, fluorine source and organic amine and stir, MeO:Al in the reaction mixture made
2o
3: P
2o
5: F-: organic amine: the mol ratio of ionic liquid is 0.002 ~ 6:1:0.1 ~ 20:0.1 ~ 10:0.1 ~ 10:2 ~ 1000;
(2) by the reaction mixture of step (1) gained crystallization 0.5 ~ 120 hour at 100 ~ 300 DEG C;
(3) after step (2) terminates, product is cooled to room temperature, filters, wash and drying, namely be there is the MeAPO molecular sieve of-CLO structure.
4. method according to claim 3, is characterized in that: MeO:Al in step (1) described reaction mixture
2o
3: P
2o
5: 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.
5. method according to claim 3, is characterized in that: ionic liquid is for comprising following positively charged ion: alkyl quaternary ammonium ion [NR
4]
+, alkyl quaternary phosphine ion [PR
4]
+, the imidazol ion [Rim] that alkyl replaces
+, the pyridinium ion [Rpy] that alkyl replaces
+in one or more ionic liquids, R is the alkyl of C1-C16; Organic amine is one or more in aliphatic amide, aromatic amine, hydramine or quaternary ammonium compound.
6. method according to claim 3, is characterized in that: source metal is one or more in magnesium acetate, magnesium chloride, magnesium nitrate, magnesium oxide, manganous acetate, Manganous chloride tetrahydrate, manganese monoxide, manganous sulfate, manganous carbonate, cobaltous acetate, cobaltous carbonate, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride, cobaltous hydroxide, nickelous acetate, nickelous nitrate, nickel oxide, nickelous chloride, zinc acetate, zinc chloride, zinc nitrate, zinc oxide.
7. method according to claim 3, is characterized in that: phosphorus source is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate; Aluminium source is one or more in aluminum isopropylate, pseudo-boehmite, Tai-Ace S 150, aluminum nitrate, hydrated aluminum oxide; Fluorine source is one or more in hydrofluoric acid, Neutral ammonium fluoride, Sodium Fluoride.
8. method according to claim 3, is characterized in that: crystallization condition is: at 150 ~ 250 DEG C, and under normal pressure or autogenous pressure, crystallization time is 1h ~ 72h.
9. method according to claim 3, is characterized in that: step (1) described ionic liquid is warming up to 70 ~ 110 DEG C before raw material adds, and namely raw material mixing temperature is 70 ~ 110 DEG C.
10. method according to claim 3, is characterized in that: can contain a certain proportion of water in step (1) described reaction mixture, water can be brought into by raw material, also can additionally add, and water content is the 0-10wt% of reaction mixture gross weight.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106809860A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of ion process for thermosynthesizing of ATS types Metal-aluminophosphate Molecular Siever |
| 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 |
| CN109422279A (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 aluminium phosphate molecular sieve |
| CN109502602A (en) * | 2018-12-26 | 2019-03-22 | 北京化工大学 | A kind of preparation method of SiGe hydrochlorate 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 |
| CN112028087A (en) * | 2020-08-14 | 2020-12-04 | 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 |
| CN114213221A (en) * | 2022-01-12 | 2022-03-22 | 南昌大学 | Method for synthesizing unsaturated ether by catalyzing aldehyde and alcohol to be subjected to normal-pressure hydrogenation dehydration through Al-Ni-P compound |
| CN114700107A (en) * | 2022-03-28 | 2022-07-05 | 云南锡业集团（控股）有限责任公司研发中心 | Preparation method and application of aluminum tin phosphate molecular sieve catalyst |
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| WO2012056118A1 (en) * | 2010-10-28 | 2012-05-03 | IFP Energies Nouvelles | Izm-4 crystallized solid and process for preparing same |
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| WO2012056118A1 (en) * | 2010-10-28 | 2012-05-03 | IFP Energies Nouvelles | Izm-4 crystallized solid and process for preparing same |
| CN102173437A (en) * | 2011-02-01 | 2011-09-07 | 吉林大学 | Preparation method of controllable metal-doped aluminum phosphate molecular sieve |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106809860A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of ion process for thermosynthesizing of ATS types Metal-aluminophosphate Molecular Siever |
| CN106809860B (en) * | 2015-11-27 | 2019-03-19 | 中国科学院大连化学物理研究所 | A kind of ion process for thermosynthesizing of ATS type Metal-aluminophosphate Molecular Siever |
| 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 |
| CN109422279A (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 aluminium phosphate molecular sieve |
| CN109502602A (en) * | 2018-12-26 | 2019-03-22 | 北京化工大学 | A kind of preparation method of SiGe hydrochlorate 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 |
| CN112028087A (en) * | 2020-08-14 | 2020-12-04 | 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 |
| CN114213221A (en) * | 2022-01-12 | 2022-03-22 | 南昌大学 | Method for synthesizing unsaturated ether by catalyzing aldehyde and alcohol to be subjected to normal-pressure hydrogenation dehydration through Al-Ni-P compound |
| CN114213221B (en) * | 2022-01-12 | 2023-11-17 | 南昌大学 | Method for synthesizing unsaturated ether by catalyzing aldehyde and alcohol to be dehydrated under normal pressure by using Al-Ni-P compound |
| CN114700107A (en) * | 2022-03-28 | 2022-07-05 | 云南锡业集团（控股）有限责任公司研发中心 | Preparation method and application of aluminum tin phosphate molecular sieve catalyst |
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