CN108217685A - A kind of preforming synthetic method of the hetero atom Metal-aluminophosphate Molecular Siever with AFO structure - Google Patents
A kind of preforming synthetic method of the hetero atom Metal-aluminophosphate Molecular Siever with AFO structure Download PDFInfo
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- CN108217685A CN108217685A CN201810039960.7A CN201810039960A CN108217685A CN 108217685 A CN108217685 A CN 108217685A CN 201810039960 A CN201810039960 A CN 201810039960A CN 108217685 A CN108217685 A CN 108217685A
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- C01—INORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
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- C01P2002/00—Crystal-structural characteristics
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
Abstract
A kind of preforming synthetic method of the hetero atom Metal-aluminophosphate Molecular Siever with AFO structure belongs to the technical field of catalyst preparation.This method is that silicon source, phosphorus source, source metal, Fluorine source, organic amine, ionic liquid and water are mixed to prepare gel in proportion, then by gained gel by intended shape processing molding, formed gel crystallization under certain condition, you can obtain the formed body being made of completely molecular sieve.Molding AFO type hetero atom Metal-aluminophosphate Molecular Sievers are made in a step of the invention, can be used directly as catalyst carrier or adsorbent, simplify catalyst or adsorbent preparation process.Compared with conventional method, this method preparation process is simple, and raw material availability is high, and waste liquid discharging amount is low, has broad application prospects.
Description
Technical field
The present invention relates to technical field of molecular sieve preparation, provide a kind of hetero atom metal tripolyphosphate aluminium point with AFO structure
The preforming synthetic method of son sieve.
Background technology
With AFO structure hetero atom Metal-aluminophosphate Molecular Siever (Atlas of Zeolite Framework Types,
6th ed.,Elsevier,Amsterdam,2017 ；http://www.iza-structure.org/databases/) tool
There is one-dimensional oval 10 round rings straight hole road, aperture size is 0.43nm × 0.70nm.Due to the pore passage structure ruler of this molecular sieve
The very little formation for being very beneficial for single branched paraffin isomers with geometric configuration, the Pt-Pd/AFO silicon phosphates of Supported Pt Nanoparticles palladium noble metal
Aluminum molecular screen shows good catalytic activity and selectivity in the isomerization reaction of linear paraffin.
1984, Flanigen et al. disclosed AFO structure silicoaluminophosphate in patent US4,440,871 for the first time
The synthesis of molecular sieve, however the AFO structure molecular screens of pure phase are hardly resulted in building-up process, often there is AEL in product
With the dephasigns such as ATO structure silicoaluminophosphate.The much synthetic method about AFO structure silicoaluminophosphamolecular molecular sieves or improvement later
Method appearance (J.Catal., 1997,169,55-66；Microporous Mesoporous Mater.,1998,26,
161-173 ；CN1448336A ；CN1456502A ；CN1194890C ；CN1541942A ；CN1923688A).
These methods prepare molecular sieve powder using hydrothermal synthesis method, and this method using water as solvent, by certain matched by material
Than being mixed to prepare colloidal sol, colloidal sol carries out crystallization between 80 ~ 200 °C and under the self-generated pressure of water, after crystallization, product warp
It is filtered, washed and is dried to obtain molecular sieve powder.Adsorbent, shaping of catalyst are needed molecular sieve powder and binding agent, plasticising
The additives such as agent, extrusion aid, pore creating material are mixed to get plastic body, are then obtained by kneaded and formed, health, drying and roasting
Product.
Above method first prepares molecular sieve powder, then is made and urges with additives mixed-forming, drying and roastings such as binding agents
Agent, adsorbent finished product, technological process is long, and process is complicated.In addition, molecular sieve water heat crystallization process carries out under high pressure, exist
Security risk；The filtration washing process of powder generates a large amount of waste water, causes environmental pollution；Due to the introducing of binding agent, molecular sieve
The content of molecular sieve is unable to reach 100% generally 60 ~ 80% in catalyst, adsorbent finished product, influences molecular sieve performance performance.
In order to solve problem above, people are directed to simplify molecular sieve catalyst, adsorbent preparation process and improve and be molded
Two aspect of content of molecular sieve has done numerous studies in body.
Using having effigurate raw material rather than powder, molecular sieve catalyst, adsorbent preparation process can be simplified.
Such as Sachse et al. is with SiO2Integral material is prepared for molding ZSM-5 catalyst for raw material.This method is by SiO2It is whole
Body material is placed in molar ratio as SiO2:NaOH:NaAlO2:TPAOH:H2O =1:0.15:0.09:0.004:In 33 solution, in
150 °C of lower 24 h of crystallization obtain preformed catalyst (Micropor. Mesopor. Mater., 2011,140 (1-3):
58-68).The method uses SiO2Silicon source of the integral material as Zeolite synthesis, crystallization process keep solid phase, but silicon source NaAlO2
Still exist in aqueous solution Deng other raw materials, crystallization is still water-heat process.Although molecular sieve finished product maintains integral material
Shape, but due to reaction raw materials office solid-liquid two-phase, reaction process cannot be complete by mass transfer and limit, crystallization, ZSM-5 in finished product
Content be only 38%.
Barg, S. et al. are prepared for molding X-type molecular sieve adsorbent by raw material of foamed aluminium integral material.This method will
Foamed aluminium integral material is placed under 820 °C handles 2 h in air atmosphere, and part Al is converted to Al3O2, then place it in and rub
You are than being Na2O:K2O:SiO2:H2O=70:20:10:In 1500 solution, in 80 °C of lower crystallization, obtained formed absorbent is
By X-type molecular sieve and Al2O3(J. Porous Mat., 2011,18 (1) formed: 89-98).
By part material, monolithic devices catalysis has been made in crystallization, a step to above method under hydrothermal conditions in the form of integral material
Agent, adsorbent, simplify preparation process.But other raw materials still exist in aqueous solution, crystallization is still water-heat process, is existed
Security risk；Reaction raw materials office solid-liquid two-phase, reaction process is by mass transfer and limit, containing the raw material not changed in finished product, point
Son sieve content is not high.In addition, these methods use integral material shape raw material, limited by raw material material, shape is single.And mesh
The practical finished form of preceding preformed catalyst, adsorbent enriches, and includes spherical shape, bar shaped, cylinder, honeycombed, bunge bedstraw herb shape, three
Clover shape, external tooth wheel shape, non-porous external tooth wheel shape, it is quincunx, porous it is quincunx, seven apertures in the human head is spherical, non-porous spherical, seven muscle wheel shapes,
Four hole shapes, four leaf butterfly shapes etc..
In order to improve the content of molecular sieve in molecular sieve catalyst, adsorbent finished product, researchers do a lot of work, will
The additives crystallization such as the binding agent of forming process addition are molecular sieve.
Such as patent CN1105906A discloses a kind of preparation method of zeolite catalyst.This method is by ZSM-5 powders
With silica binder mixed-forming, in organic amine or organic quaternary ammonium aqueous alkali or steam, hydrothermal treatment obtains one
Body chemoattractant molecule sieves, and finished catalyst is obtained using roasting.
Patent CN1915820A discloses a kind of preparation method of little crystal grain zeolite catalyst.This method is by molecular sieve seed
With silicon source, binding agent mixed-forming, integrated molecular sieve then is converted into organic amine and water vapour gas-solid phase processor, using
Roasting obtains finished catalyst.
Above method formed body obtained crystallization again after molecular sieve powder is mixed with binding agent, is transformed into binding agent
Molecular sieve.Though the method can obtain the formed body being made of completely molecular sieve, there is still a need for synthesis of molecular sieve original powders；Forming process
Crystallization steps are increased, improve manufacture cost.
The present invention proposes a kind of complete preforming synthetic method of molecular sieve, can reach simplified molecular sieve catalyst, suction simultaneously
Attached dose of preparation process and the target for improving molecular sieve content in formed body.Present invention is particularly directed to the hetero atom metals of AFO structure
Aluminium phosphate molecular sieve provides a kind of preforming synthetic method.
Invention content
Present invention aims at the technological processes for simplifying molecular sieve catalyst, prepared by adsorbent, directly prepare to have and it is expected
The pure molecular screen material of shape provides a kind of preforming synthesis side of the hetero atom Metal-aluminophosphate Molecular Siever with AFO structure
Method.
The scheme that the present invention solves above-mentioned technical problem is as follows：
A kind of synthetic method of the AFO structure hetero atom Metal-aluminophosphate Molecular Siever confirmed with International Zeolite Association, feature
It is：Synthesized gel rubber is obtained into molding point consistent with formed gel shape by expectation shape processing processing molding, then direct crystallization
Son sieve, includes the following steps,
(1) silicon source, phosphorus source, source metal, Fluorine source, organic amine, ionic liquid and water are pressed into Al2O3:P2O5:MeO:F-:Organic amine:
Ionic liquid:H2O=1:0.2~5:0.002~6:0.01~9:0.01~10:0.005~5:2 ~ 100 molar ratio is mixed to prepare solidifying
Glue,
(2) gel made from step (1) is processed into the formed gel with required shape, gel is suitably aged or in not
More than 110 °C Temperature Treatments remove water a part of in gel, obtain the solid of plasticity, then processing and forming.
(3) formed gel made from step (2) is placed in closed container, in 100 ~ 260 °C of lower 10 min ~ 10 of crystallization
D obtains the molded molecular sieve with AFO topological structures.
The preparation of gel of the present invention uses this field routine operation method, for example in certain temperature and strong stirring bar
Under part, silicon source, phosphorus source, source metal, Fluorine source, organic amine, ionic liquid are added in deionized water mix according to a certain percentage, is obtained
To the uniformly mixed aqueous gel containing silicon source, phosphorus source, source metal, Fluorine source, organic amine and ionic liquid.
Gel forming of the present invention be this field routine operation, be for example extruded moulding, compression forming, oil column into
Type, rotational forming, spray shaping, granulating, the shape of obtained formed gel can be spherical shape, bar shaped, cylinder, honeycombed,
Bunge bedstraw herb shape, cloverleaf pattern, external tooth wheel shape, non-porous external tooth wheel shape, it is quincunx, porous it is quincunx, seven apertures in the human head is spherical, non-porous spherical,
Seven muscle wheel shapes, four hole shapes, four leaf butterfly shapes etc..The shape and size specifically used select true according to actual service conditions requirement
It is fixed.Gel of the present invention can carry out the pretreatment of certain forms before forming operation, its plasticity be improved, to ensure to be molded
The convenient operation of process.For example gel can be suitably aged or in no more than 110 °C Temperature Treatments, remove in gel one
The water divided, obtains the solid of plasticity, then processing and forming.
Silicon source of the present invention, phosphorus source, source metal, Fluorine source, organic amine, ionic liquid and water molar ratio be preferably
Al2O3:P2O5:Source metal:F-:Organic amine:Ionic liquid:H2O=1: 0.4~2.0 : 0.002~1: 0.02~2.0 : 0.1~
6.0 : 0.01~3.0 : 25~60。
It needs to add ionic liquid in gel synthesized by the present invention, one or more kinds of ionic liquids can be added
Body.The anion of the ionic liquid added can be、、、、、One or both of
More than；Cation is alkyl-substituted imidazol ion, alkyl-substituted pyridinium ion, quaternary ammonium alkyl salt ionOne or more of, R is the alkyl of C1-C16.
Organic amine of the present invention is one or more of 2-methylimidazole, pyridine, 1- methyl piperidines.
Silicon source of the present invention is boehmite, activated alumina, aluminium hydroxide, in aluminium isopropoxide, aluminum sulfate or
The one or more of aluminum nitrate.
Phosphorus source of the present invention is phosphoric acid, monoammonium phosphate, ammonium dihydrogen phosphate, one or both of triammonium phosphate with
On.
Fluorine source of the present invention is one or more of hydrofluoric acid, sodium fluoride, ammonium fluoride.
The preferred crystallization temperature of crystallization process of the present invention is 110 ~ 220 °C, and preferably crystallization time is the d of 30 min ~ 7.
Formed gel is placed in the pressure resistant vessel of this field routine and carries out by crystallization process, can be pre-placed in container a certain amount of
Water, but it is not necessary to water and formed gel are in direct contact.Crystallization process uses the mode of heating of this field routine, for example,
Oil bath heating, baking oven heating and microwave heating.
Crystallization terminates, and obtained mold compound is without filtration washing.Crystallization product maintains the identical shape of formed gel
Shape and size, are made of completely molecular sieve, and framework of molecular sieve structure is the AFO structure that International Zeolite Association confirms.Crystallization product
Do powder x-ray diffraction after crushing, diffraction maximum position and relatively strong and weak as follows：
| Position（Degree） | It is relatively strong and weak |
| 6.85±0.2 | By force |
| 9.72±0.2 | By force |
| 13.72±0.2 | By force |
| 18.26±0.2 | It is medium |
| 20.64±0.2 | It is weak |
| 21.26±0.2 | By force |
| 22.20±0.2 | By force |
| 22.91±0.2 | It is medium |
| 25.84±0.2 | It is medium |
| 29.46±0.2 | It is medium |
To help to understand the present invention, " preforming " term defined below.The term of this definition has relevant art
The normally understood meaning of those of ordinary skill.
Unless otherwise stated, " preforming " refers to the gel used in synthesis of molecular sieve in advance herein, by compressing, squeezing
The process or step of the formed gel with definite shape, size and mechanical strength are processed into the methods of going out, rotate, spraying.
In conclusion the present invention provides a kind of the preforming of hetero atom Metal-aluminophosphate Molecular Siever with AFO structure
Synthetic method has the following advantages that：
The shape and size that molecular sieve prepared by this method specifically uses are selected to determine, be met according to actual service conditions requirement
The requirement of differential responses device.Gel carries out the pretreatment of certain forms before forming operation in this method, improves its plasticity,
To ensure the convenient operation of forming process.Gel can be suitably aged or in no more than 110 °C Temperature Treatments, remove gel
The water of a middle part, obtains the solid of plasticity, then processing and forming.Formed gel is carried out crystallization by this method, after i.e.
Plastic product, without filtration washing；This method directly obtains molded molecular sieve, avoids the mistake of conventional molecular sieve production process
Filter washing step, waste liquid discharging amount is low, environmental-friendly.Crystallization product maintains the identical shape and size of formed gel, forming
Body is made of completely molecular sieve, and framework of molecular sieve structure is the AFO structure that International Zeolite Association confirms.This method uses a step system
Molded molecular sieve simplifies catalyst or adsorbent preparation process, formed body are made of completely molecular sieve, improve unit bodies
The content of molecular sieve, can improve its catalytic activity and adsorption capacity in product catalyst or adsorbent.
Description of the drawings
Fig. 1 is the XRD diagram of sample in the embodiment of the present invention 1.
Fig. 2 is cylinder bar shaped AFO type hetero atom Metal-aluminophosphate Molecular Sievers prepared by the pre-shaping method of the embodiment of the present invention 1
Photo in kind.
Fig. 3 is clover bar shaped AFO type hetero atom metal tripolyphosphate aluminium molecules prepared by the pre-shaping method of the embodiment of the present invention 2
The photo in kind of sieve.
Specific embodiment
The present invention is described in detail, but the method for the present invention is without being limited thereto below by example, it is impossible to which the present invention is protected
Range be construed as limiting.
1 embodiment of the present invention 1 ~ 8 of table and synthesis condition.
Embodiment 1
By 17.35g boehmites (78.6wt% Al2O3) be placed in 250ml beakers, add in 95.39g deionized waters, room temperature
Under the conditions of stir 30 minutes, add in the phosphoric acid of 33.90g a concentration of 85wt%, after being stirred at room temperature 3 hours, add in 1.72g magnesium acetates
Stirring 30 minutes adds in the hydrofluoric acid of a concentration of 40wt% of 1.34g, after continuing stirring 30 minutes, adds in 11.10g 2- methyl miaows
Azoles after stirring 30 minutes, adds in 28.09g 1- ethyl -3- methy limidazolium ionic liquids, said mixture is stirred to equal
It is even to be handled under the conditions of 90 °C, and it is extruded into cylinder bar shaped.Forming cylinder bar shaped gel is packed into and is served as a contrast with polytetrafluoroethylkettle kettle
Crystallizing kettle in, in 200 °C of lower crystallization 3 days.
Crystallizing kettle is cooled to room temperature after crystallization, obtains molded molecular sieve.By molded molecular sieve grind into powder, warp
XRD spectra is analyzed, which is MgAPO-41, as shown in Figure 1, Fig. 2 is the photo in kind of the present embodiment molded molecular sieve.
Embodiment 2
By 17.35g boehmites (78.6wt% Al2O3) be placed in 250ml beakers, add in 129.23g deionized waters, room temperature
Under the conditions of stir 30 minutes, add in the phosphoric acid of 53.08g a concentration of 85wt% and ammonium dihydrogen phosphate that 6.152g purity is 99%, room
After temperature stirring 3 hours, add in 0.025g magnesium chlorides and stir 30 minutes, add in the hydrofluoric acid of a concentration of 40wt% of 0.14g, continue to stir
After mixing 30 minutes, 31.71g pyridines and 32.92g 2-methylimidazoles (2-mim) are added in, after stirring 30 minutes, adds in 0.31g N-
Said mixture is stirred until homogeneous and is handled under the conditions of 100 °C, and is extruded into clover by butyl-pyridinium acetate ionic liquid
Bar shaped.Clover bar shaped gel will be molded to be fitted into the crystallizing kettle served as a contrast with polytetrafluoroethylkettle kettle, in 220 °C of lower crystallization 7 days.
Crystallizing kettle is cooled to room temperature after crystallization, obtains molded molecular sieve.By molded molecular sieve grind into powder, warp
XRD spectra is analyzed, which is MgAPO-41.Fig. 3 is the present embodiment MgAPO-41 molecular sieve material object photos.
Embodiment 3
By 17.35g boehmites (78.6wt% Al2O3) be placed in 250ml beakers, add in 44.23g deionized waters, room temperature
Under the conditions of stir 30 minutes, add in the phosphoric acid of 12.33g a concentration of 85wt%, after being stirred at room temperature 3 hours, add in 34.27g magnesium nitrates
Stirring 30 minutes, the hydrofluoric acid and 1.00g purity for adding in a concentration of 40wt% of 12.03g are 99% ammonium fluoride, continue 30 points of stirring
Zhong Hou adds in 1.34g 1- methyl piperidines, after stirring 30 minutes, adds in 45.31g 1- butyl -3- methyl imidazolium tetrafluoroborates
Ionic liquid and 38.31g 1- ethyl -3- methy limidazolium ionic liquids, said mixture is stirred until homogeneous in 75 °C of items
It is handled under part, and is rolled into spherical shape.Spherical gel will be molded to be fitted into the crystallizing kettle with polytetrafluoroethylkettle kettle lining, under 220 °C
Crystallization 30 minutes.
Crystallizing kettle is cooled to room temperature after crystallization, obtains molded molecular sieve.By molded molecular sieve grind into powder, warp
XRD spectra is analyzed, which is MgAPO-41.
Embodiment 4
By 17.35g boehmites (78.6wt% Al2O3) be placed in 250ml beakers, add in 32.03g deionized waters, room temperature
Under the conditions of stir 30 minutes, add in the phosphoric acid of 12.33g a concentration of 85wt%, after being stirred at room temperature 3 hours, add in 0.06g magnesium acetates
Stirring 30 minutes adds in the hydrofluoric acid of a concentration of 40wt% of 13.37g, after continuing stirring 30 minutes, adds in 2-methylimidazole, stirring
After 30 minutes, 0.22g etamon chloride ionic liquids are added in, said mixture is stirred until homogeneous under the conditions of 75 °C
Reason, and it is extruded into honeycombed.Formed honeycomb shape gel piece is fitted into the crystallizing kettle with polytetrafluoroethylkettle kettle lining, at 220 °C
Lower crystallization 30min.
Crystallizing kettle is cooled to room temperature after crystallization, obtains molded molecular sieve.By molded molecular sieve grind into powder, warp
XRD spectra is analyzed, which is MgAPO-41.
Embodiment 5
By 14.74g boehmites (78.6wt% Al2O3) and 4.09g purity be 99% aluminium isopropoxide be placed in 250ml beakers
In, 103.37g deionized waters are added in, are stirred 30 minutes under room temperature, add in the phosphoric acid of a concentration of 85wt% of 12.33g, room temperature
After stirring 3 hours, add in 0.06g magnesium acetates and stir 30 minutes, add in the hydrofluoric acid of a concentration of 40wt% of 0.14g, continue stirring 30
After minute, 1.10g 2-methylimidazoles are added in, after stirring 30 minutes, add in 0.14g nitric acid second ammonium ion liquid, it will be above-mentioned mixed
Conjunction object is stirred until homogeneous to be handled, and be prepared into spheric granules using oil-drop method under the conditions of 80 °C.Formed gel is packed into
In crystallizing kettle with polytetrafluoroethylkettle kettle lining, in 110 °C of lower crystallization 7 days.
Crystallizing kettle is cooled to room temperature after crystallization, obtains molded molecular sieve.By molded molecular sieve grind into powder, warp
XRD spectra is analyzed, which is MgAPO-41.
Embodiment 6
By 17.35g boehmites (78.6wt% Al2O3) be placed in 250ml beakers, add in 95.39g deionized waters, room temperature
Under the conditions of stir 30 minutes, add in the phosphoric acid of 33.90g a concentration of 85wt%, after being stirred at room temperature 3 hours, add in 1.47g zinc acetates
Stirring 30 minutes adds in the hydrofluoric acid of a concentration of 40wt% of 1.34g, after continuing stirring 30 minutes, adds in 11.10g 2- methyl miaows
Azoles after stirring 30 minutes, adds in 28.09g 1- ethyl -3- methy limidazolium ionic liquids, is stirred until homogeneous and in 90 °C
Under the conditions of handle, and be extruded into clover bar shaped.Clover bar shaped gel will be molded and be packed into the crystalline substance with polytetrafluoroethylkettle kettle lining
Change in kettle, in 210 °C of lower crystallization 3 days.
Crystallizing kettle is cooled to room temperature after crystallization, obtains molded molecular sieve.By molded molecular sieve grind into powder, warp
XRD spectra is analyzed, which is ZnAPO-41.
Embodiment 7
By 17.35g boehmites (78.6wt% Al2O3) be placed in 250ml beakers, add in 95.39g deionized waters, room temperature
Under the conditions of stir 30 minutes, add in the phosphoric acid of 33.90g a concentration of 85wt%, after being stirred at room temperature 3 hours, add in 2.00g cobalt acetates
Stirring 30 minutes adds in the hydrofluoric acid of a concentration of 40wt% of 1.34g, after continuing stirring 30 minutes, adds in 11.10g 2- methyl miaows
Azoles, stirring 30 minutes after, add in 28.09g 1- ethyl -3- methy limidazolium ionic liquids, by said mixture stir to
It is uniformly handled under the conditions of 90 °C, and is extruded into cylinder bar shaped.Forming cylinder bar shaped gel is packed into polytetrafluoroethylkettle kettle
In the crystallizing kettle of lining, in 210 °C of lower crystallization 3 days.
Crystallizing kettle is cooled to room temperature after crystallization, obtains molded molecular sieve.By molded molecular sieve grind into powder, warp
XRD spectra is analyzed, which is CoAPO-41.
Embodiment 8
By 17.35g boehmites (78.6wt% Al2O3) be placed in 250ml beakers, add in 95.39g deionized waters, room temperature
Under the conditions of stir 30 minutes, add in the phosphoric acid of 33.90g a concentration of 85wt%, after being stirred at room temperature 3 hours, add in 1.97g manganese acetates
Stirring 30 minutes adds in the hydrofluoric acid of a concentration of 40wt% of 1.34g, after continuing stirring 30 minutes, adds in 11.10g 2- methyl miaows
Azoles, stirring 30 minutes after, add in 28.09g 1- ethyl -3- methy limidazolium ionic liquids, by said mixture stir to
It is uniformly handled under the conditions of 90 °C, and is extruded into cylinder bar shaped.Forming cylinder bar shaped gel is packed into polytetrafluoroethylkettle kettle
In the crystallizing kettle of lining, in 210 °C of lower crystallization 3 days.
Crystallizing kettle is cooled to room temperature after crystallization, obtains molded molecular sieve.By molded molecular sieve grind into powder, warp
XRD spectra is analyzed, which is MnAPO-41.
Table 2 is the XRD diffraction maximums position of 1 ~ 8 sample of the embodiment of the present invention and relatively strong and weak.
As seen from the above table, the AFO type hetero atoms of pure phase can be prepared in the Reaction conditions range stated in this method
Metal-aluminophosphate Molecular Siever.
Claims (8)
1. a kind of preforming synthetic method of the hetero atom Metal-aluminophosphate Molecular Siever with AFO structure, which is characterized in that including
Following steps：
(1) silicon source, phosphorus source, source metal, Fluorine source, organic amine, ionic liquid and water are uniformly mixed to obtain gel, in gel
Al2O3:P2O5:MeO:F-:Organic amine:Ionic liquid:H2The molar ratio of O is 1:0.2~5: 0.002~6:0.01~9:0.01~10:
0.005~5:2~100；
(2) gel made from step (1) is subjected to pretreatment post-processing into the formed gel with required shape, pretreatment uses
Gel is aged or gel is in no more than 110 °C Temperature Treatments；
(3) formed gel made from step (2) is placed in closed container, in the d of 100 ~ 260 °C of lower 10 min of crystallization ~ 10, obtained
To the molded molecular sieve with AFO topological structures；
The Me of the MeO is magnesium, cobalt, zinc, manganese or nickel；Anion in the ionic liquid is、、、、、One or more of, cation is alkyl-substituted imidazol ion, alkyl-substituted pyridine from
Son, quaternary ammonium alkyl salt ionOne or more of, wherein R is the alkyl of C1-C16；The organic amine
For one or more of 2-methylimidazole, pyridine, 1- methyl piperidines.
2. a kind of preforming synthesis of hetero atom Metal-aluminophosphate Molecular Siever with AFO structure according to claim 1
Method, it is characterised in that：Al in the gel2O3:P2O5: MeO:F-:Organic amine:Ionic liquid:H2The molar ratio of O is 1:
0.4~2.0 : 0.002~1: 0.02~2.0 : 0.1~6.0 : 0.01~3.0 : 25~60。
3. a kind of preforming synthesis of hetero atom Metal-aluminophosphate Molecular Siever with AFO structure according to claim 1
Method, it is characterised in that：The source metal for magnesium acetate, magnesium chloride, magnesium nitrate, cobalt acetate, cobalt carbonate, cobaltous sulfate, zinc acetate,
One or more of zinc chloride, zinc nitrate, manganese acetate, manganese chloride, manganese sulfate, nickel acetate, nickel nitrate, nickel oxide.
4. a kind of preforming synthesis of hetero atom Metal-aluminophosphate Molecular Siever with AFO structure according to claim 1
Method, it is characterised in that：Source of aluminium is boehmite, activated alumina, aluminium hydroxide, in aluminium isopropoxide, aluminum sulfate or
The one or more of aluminum nitrate.
5. a kind of preforming synthesis of hetero atom Metal-aluminophosphate Molecular Siever with AFO structure according to claim 1
Method, it is characterised in that：Phosphorus source is phosphoric acid, monoammonium phosphate, ammonium dihydrogen phosphate, one or both of triammonium phosphate with
On.
6. a kind of preforming synthesis of hetero atom Metal-aluminophosphate Molecular Siever with AFO structure according to claim 1
Method, it is characterised in that：The Fluorine source is one or more of hydrofluoric acid, ammonium fluoride, sodium fluoride.
7. a kind of preforming synthesis of hetero atom Metal-aluminophosphate Molecular Siever with AFO structure according to claim 1
Method, it is characterised in that：The crystallization temperature of the crystallization process is 110 ~ 220 °C, and crystallization time is the d of 30 min ~ 7.
8. a kind of preforming synthesis of hetero atom Metal-aluminophosphate Molecular Siever with AFO structure according to claim 1
Method, it is characterised in that：The shape of the formed gel is spherical shape, bar shaped, cylinder, honeycombed, bunge bedstraw herb shape, clover
Shape, external tooth wheel shape, non-porous external tooth wheel shape, it is quincunx, porous it is quincunx, seven apertures in the human head is spherical, non-porous spherical, seven muscle wheel shapes, four holes
Shape or four leaf butterfly shapes.
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