CN109650402A - The method that hydrothermal synthesis method prepares nano-sheet FER molecular sieve - Google Patents
The method that hydrothermal synthesis method prepares nano-sheet FER molecular sieve Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 18
- 239000002135 nanosheet Substances 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
- 230000008025 crystallization Effects 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 58
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 239000011734 sodium Substances 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 238000009415 formwork Methods 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000005446 dissolved organic matter Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- LLSKXGRDUPMXLC-UHFFFAOYSA-N 1-phenylpiperidine Chemical class C1CCCCN1C1=CC=CC=C1 LLSKXGRDUPMXLC-UHFFFAOYSA-N 0.000 claims 1
- 239000000499 gel Substances 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 42
- 238000003756 stirring Methods 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000012824 chemical production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 20
- 239000004810 polytetrafluoroethylene Substances 0.000 description 20
- 229910021536 Zeolite Inorganic materials 0.000 description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 17
- 239000010457 zeolite Substances 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 10
- BFAKENXZKHGIGE-UHFFFAOYSA-N bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene Chemical compound FC1=C(C(=C(C(=C1F)I)F)F)N=NC1=C(C(=C(C(=C1F)F)I)F)F BFAKENXZKHGIGE-UHFFFAOYSA-N 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- C—CHEMISTRY; METALLURGY
- 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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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
-
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明涉及分子筛制备方法，旨在提供一种水热合成法制备纳米片状FER分子筛的方法。该方法包括：将水与铝源混合均匀后，加入氢氧化N,N‑二乙基‑顺‑2,6‑二甲基哌啶溶液和NaOH固体，在搅拌下加入硅源，继续搅拌混合溶液直到形成凝胶状；转至反应釜中，在110～150℃下动态晶化反应36～96h；对反应产物抽滤、烘干，即得到FER分子筛原粉。本发明利用水热单模板法合成的厚度为7nm左右的FER分子筛，极大降低了FER分子筛的厚度，并且合成方便、节能。与现有技术相比，整个生产过程中仅使用一种有机模板剂，得到的产品保持了良好的结晶度和纯度，具有良好的催化反应活性。因而本发明在实际化工生产领域具有重要意义。
The invention relates to a method for preparing molecular sieves, and aims to provide a method for preparing nano-sheet FER molecular sieves by a hydrothermal synthesis method. The method includes: after mixing water and aluminum source uniformly, adding N,N-diethyl-cis-2,6-dimethylpiperidine hydroxide solution and NaOH solid, adding silicon source under stirring, and continuing to stir and mix The solution is until gel-like; transferred to the reaction kettle, and the dynamic crystallization reaction is carried out at 110-150 ℃ for 36-96 hours; the reaction product is filtered and dried to obtain the original powder of FER molecular sieve. The invention utilizes the hydrothermal single template method to synthesize the FER molecular sieve with a thickness of about 7 nm, which greatly reduces the thickness of the FER molecular sieve, and is convenient to synthesize and save energy. Compared with the prior art, only one organic template agent is used in the whole production process, the obtained product maintains good crystallinity and purity, and has good catalytic reaction activity. Therefore, the present invention has great significance in the field of actual chemical production.
Description
Technical field
The invention belongs to molecular sieve preparation method, in particular to the hydrothermal synthesis method side for preparing nano-sheet FER molecular sieve
Method.
Background technique
Molecular sieve is widely used in catalysis, ion exchange, suction because it has spacious structure and big surface area
It is attached with separate equal fields.
Plank et a1 goes out FER molecular sieve (USP46016245) as templated synthesis with pyrrolidines for the first time.FER molecular sieve is
With a kind of zeolite comprising ten-ring and the two-dimentional microcellular structure in octatomic ring duct.For ten-ring along [001] direction, duct is big
Small is 0.42nm × 0.54nm；For octatomic ring along [010] direction, duct size is 0.35nm × 0.48nm.FER molecular sieve has well
Thermal stability and hydrothermal stability, be widely used in catalyzed alkene isomerization reaction, dimethyl ether carbonylation reaction etc., because
This causes the great interest of vast researcher to study this molecular sieve analog.
But meanwhile the cellular structure of FER molecular sieve also limits the activity that reaction molecular more closely touches FER molecular sieve
Site, and be easy to cause carbon distribution in catalysis reaction.The length of reduction diffusion path is a solution to the above problem.
By layers apart, Bonilla et al. introducing is mesoporous all to be solved this problem in that Corma et al..But these methods destroy micropore,
Reduce the shape selectivity of catalyst.Recently, Corma et al. double-template method (piperidines and N- methyl-N- hexadecane phenylpiperidines
Bromide) obtain the FER molecular sieve of sheet of the thickness between 10-20 nanometers.However, double-template method is more complicated.
Therefore, it is very necessary for finding easier, efficient, inexpensive method synthesis nano-sheet FER molecular sieve.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide a kind of hydrothermal synthesis method preparation
The method of nano-sheet FER molecular sieve.
In order to solve the technical problem, solution of the invention is:
A kind of method that hydrothermal synthesis method prepares nano-sheet FER molecular sieve is provided, comprising the following steps:
After mixing by water and silicon source, hydroxide N, N- diethyl-cis- 2,6- lupetidine solution (ROH) is added
With NaOH solid, silicon source is added under stiring, continues to be stirred solution until forming gel；It goes in reaction kettle, 110
Dynamic crystallization reacts 36~96h at~150 DEG C；Reaction product is filtered, is dried to get FER molecular sieve original powder is arrived；
The additive amount for controlling each reaction raw materials makes the molar ratio range SiO of following components in reaction system2: 0.02~
0.06Al2O3: 0.20~0.35Na2O: 0.05~0.15ROH: 50H2O。
In the present invention, source of aluminium is aluminum sulfate, aluminium hydroxide or sodium metaaluminate.
In the present invention, the silicon source is the solid silicone that dioxide-containing silica is 100% or white carbon black or solid content
40% silica solution.
In the present invention, the water is deionized water.
In the present invention, the hydroxide N, N- diethyl-cis- 2,6- lupetidine solution is obtained by following methods preparation
:
Cis- 2,6- lupetidine is dissolved in methanol, iodoethane and saleratus is then added；It is stirred back at 50 DEG C
After stream reaction 4 days, rotary evaporation removes solvent and extra iodoethane；With chloroform dissolved organic matter, it is filtered to remove solid；Rotation
After chloroform is evaporated off, ethyl alcohol and Diethyl ether recrystallization are successively used, N, N- diethyl-cis- 2,6- lupetidine salt compounded of iodine powder are obtained；
Powder is soluble in water, with hydrogen-oxygen type cation resin exchange, obtain organic formwork agent hydroxide N, N- diethyl-cis- 2,6-
Lupetidine solution.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention utilizes the FER molecular sieve with a thickness of 7nm or so of hydro-thermal list Template synthesis, greatly reduces FER
The thickness of molecular sieve, and synthesize convenience, energy conservation.
2, a kind of organic formwork agent compared with prior art, is used only in entire production process, obtained product maintains
Good crystallinity and purity have good catalytic reaction activity.Thus the present invention has weight in practical chemical production field
Want meaning.
Detailed description of the invention
Fig. 1: the XRD spectra for the 7nm thickness F ER zeolite product that hydro-thermal method synthesizes in embodiment 1.
Fig. 2: the stereoscan photograph for the 7nm thickness F ER zeolite product that hydro-thermal method synthesizes in embodiment 1..
Fig. 3: the transmission electron microscope photo for the 7nm thickness F ER zeolite product that hydro-thermal method synthesizes in embodiment 1.
Fig. 4: the XRD spectra for the 50nm thickness F ER zeolite product that in embodiment 2 prepared by hydro-thermal method.
Fig. 5: the stereoscan photograph for the 50nm thickness F ER zeolite product that in embodiment 2 prepared by hydro-thermal method.
Fig. 6: the transmission electron microscope photo for the 50nm thickness F ER zeolite product that in embodiment 2 prepared by hydro-thermal method.
Specific embodiment
In following embodiment, the dioxide-containing silica in solid silicone or white carbon black is 100%, the solid content of silica solution
40%.
Organic formwork agent used is hydroxide N, and N- diethyl-cis- 2,6- lupetidine solution can pass through following methods
It prepares: cis- 2,6- lupetidine is dissolved in methanol, iodoethane and saleratus is then added；It is stirred at 50 DEG C
After back flow reaction 4 days, rotary evaporation removes solvent and extra iodoethane；With chloroform dissolved organic matter, it is filtered to remove solid；
After revolving removes chloroform, ethyl alcohol and Diethyl ether recrystallization are successively used, N, N- diethyl-cis- 2,6- lupetidine salt compounded of iodine powder are obtained
End；Powder is soluble in water, with hydrogen-oxygen type cation resin exchange, organic formwork agent hydroxide N, N- diethyl-cis- 2 are obtained,
6- lupetidine solution.The preparation category prior art of ROH, reference can be made to document (M.Dusselier, J.E.Schmidt,
R.Moulton, B.Haymore, M.Hellums and M.E.Davis, Chem.Mater., 2015,27,2695), specific to make
The standby parameter present invention repeats no more.
Embodiment 1: hydro-thermal method synthesizes nano-sheet FER molecular sieve
Firstly, by 13.5gH2O is uniformly mixed with 0.16g sodium metaaluminate, then 1g hydroxide N, N- diethyl are added thereto
Cis- 2, the 6- lupetidine aqueous solution (2.3mol/L) of base-is uniformly mixed, and 0.20gNaOH is added, is added under stiring later
2.5g silica solution continues stirring after solution becomes uniformly (being in gel), polytetrafluoroethylene (PTFE) stainless steel is added in reaction raw materials
In reaction kettle, 140 DEG C of dynamic crystallization 48h, that is, complete crystallizations, product is filtered, and obtains product after drying.
The molar ratio relationship of each component is as follows in reaction system:
SiO2:0.04Al2O3:0.20Na2O:0.15ROH:50H2O
(contains Na in sodium metaaluminate, be added with the Na in sodium hydroxide and be only final NaO2Amount, below similarly)
It is FER zeolite molecular sieve through its structure of X-ray diffraction analysis, and thickness can be seen that by stereoscan photograph
For 7nm, product morphology is uniform.Attached drawing 1 is the XRD spectra of the product of hydro-thermal method synthesis.Attached drawing 2 is the product of hydro-thermal method synthesis
Stereoscan photograph (SEM).
Embodiment 2: FER molecular sieve is synthesized under conditions of less template
Firstly, by 13.5gH2O is uniformly mixed with 0.16g sodium metaaluminate, then 0.33g hydroxide N, N- bis- is added thereto
Cis- 2, the 6- lupetidine aqueous solution (2.3mol/L) of ethyl-is uniformly mixed, and 0.41gNaOH is added, is added under stiring later
2.5g silica solution continues stirring after solution becomes uniformly (being in gel), polytetrafluoroethylene (PTFE) stainless steel is added in reaction raw materials
In reaction kettle, 140 DEG C of dynamic crystallization 48h, that is, complete crystallizations, product is filtered, and obtains product after drying.
The molar ratio relationship of each component is as follows in reaction system:
SiO2:0.04Al2O3:0.35Na2O:0.05ROH:50H2O
It is FER zeolite molecular sieve through its structure of X-ray diffraction analysis, and thickness can be seen that by stereoscan photograph
For 50nm, product morphology is uniform.Attached drawing 3 is the XRD spectra of the product of hydro-thermal method synthesis.Attached drawing 4 is the product of hydro-thermal method synthesis
Stereoscan photograph (SEM).
Embodiment 3: FER molecular sieve is synthesized under conditions of the higher silica alumina ratio that feeds intake
Firstly, by 13.5gH2O is uniformly mixed with 0.08g sodium metaaluminate, then 0.67g hydroxide N, N- bis- is added thereto
Cis- 2, the 6- lupetidine aqueous solution (2.3mol/L) of ethyl-is uniformly mixed, and 0.38gNaOH is added, is added under stiring later
2.5g silica solution continues stirring after solution becomes uniformly (being in gel), polytetrafluoroethylene (PTFE) stainless steel is added in reaction raw materials
In reaction kettle, 140 DEG C of dynamic crystallization 48h, that is, complete crystallizations, product is filtered, and obtains product after drying.
The molar ratio relationship of each component is as follows in reaction system:
SiO2:0.02Al2O3:0.30Na2O:0.10ROH:50H2O
Obtained product is through X-ray diffraction analysis consisting of FER zeolite molecular sieve.
Embodiment 4: FER molecular sieve is synthesized under conditions of the lower silica alumina ratio that feeds intake
Firstly, by 13.5gH2O is uniformly mixed with 0.24g sodium metaaluminate, then 0.67g hydroxide N, N- bis- is added thereto
Cis- 2, the 6- lupetidine aqueous solution (2.3mol/L) of ethyl-is uniformly mixed, and 0.30gNaOH is added, is added under stiring later
2.5g silica solution continues stirring after solution becomes uniformly (being in gel), polytetrafluoroethylene (PTFE) stainless steel is added in reaction raw materials
In reaction kettle, 140 DEG C of dynamic crystallization 48h, that is, complete crystallizations, product is filtered, and obtains product after drying.
The molar ratio relationship of each component is as follows in reaction system:
SiO2:0.06Al2O3:0.30Na2O:0.10ROH:50H2O
Obtained product is through X-ray diffraction analysis consisting of FER zeolite molecular sieve.
Embodiment 5: FER molecular sieve is synthesized under conditions of lower temperature
Firstly, by 13.5gH2O is uniformly mixed with 0.16g sodium metaaluminate, then 0.67g hydroxide N, N- bis- is added thereto
Cis- 2, the 6- lupetidine aqueous solution (2.3mol/L) of ethyl-is uniformly mixed, and 0.34gNaOH is added, is added under stiring later
2.5g silica solution continues stirring after solution becomes uniformly (being in gel), polytetrafluoroethylene (PTFE) stainless steel is added in reaction raw materials
In reaction kettle, 110 DEG C of dynamic crystallization 96h, that is, complete crystallizations, product is filtered, and obtains product after drying.
The molar ratio relationship of each component is as follows in reaction system:
SiO2:0.04Al2O3:0.30Na2O:0.10ROH:50H2O
Obtained product is through X-ray diffraction analysis consisting of FER zeolite molecular sieve.
Embodiment 6: FER molecular sieve is synthesized under conditions of higher temperature
Firstly, by 13.5gH2O is uniformly mixed with 0.16g sodium metaaluminate, then 0.67g hydroxide N, N- bis- is added thereto
Cis- 2, the 6- lupetidine aqueous solution (2.3mol/L) of ethyl-is uniformly mixed, and 0.27gNaOH is added, is added under stiring later
2.5g silica solution continues stirring after solution becomes uniformly (being in gel), polytetrafluoroethylene (PTFE) stainless steel is added in reaction raw materials
In reaction kettle, 150 DEG C of dynamic crystallization 36h, that is, complete crystallizations, product is filtered, and obtains product after drying.
The molar ratio relationship of each component is as follows in reaction system:
SiO2:0.04Al2O3:0.25Na2O:0.10ROH:50H2O
Obtained product is through X-ray diffraction analysis consisting of FER zeolite molecular sieve.
Embodiment 7: solid silicone be silicon source under conditions of synthesize FER molecular sieve
Firstly, by 15.0gH2O is uniformly mixed with 0.16g sodium metaaluminate, then 0.67g hydroxide N, N- bis- is added thereto
Cis- 2, the 6- lupetidine aqueous solution (2.3mol/L) of ethyl-is uniformly mixed, and 0.27gNaOH is added, is added under stiring later
1g solid silicone continues stirring after solution becomes uniformly (being in gel), polytetrafluoroethylene (PTFE) stainless steel is added in reaction raw materials
In reaction kettle, 140 DEG C of dynamic crystallization 48h, that is, complete crystallizations, product is filtered, and obtains product after drying.
The molar ratio relationship of each component is as follows in reaction system:
SiO2:0.04Al2O3:0.20Na2O:0.15ROH:50H2O
Obtained product is through X-ray diffraction analysis consisting of FER zeolite molecular sieve.
Embodiment 8: white carbon black be silicon source under conditions of synthesize FER molecular sieve
Firstly, by 15.0gH2O is uniformly mixed with 0.16g sodium metaaluminate, then 0.67g hydroxide N, N- bis- is added thereto
Cis- 2, the 6- lupetidine aqueous solution (2.3mol/L) of ethyl-is uniformly mixed, and 0.27gNaOH is added, is added under stiring later
1g white carbon black continues stirring after solution becomes uniformly (being in gel), it is anti-that polytetrafluoroethylene (PTFE) stainless steel is added in reaction raw materials
It answers in kettle, 140 DEG C of dynamic crystallization 48h, that is, complete crystallizations, product filters, and obtains product after drying.
The molar ratio relationship of each component is as follows in reaction system:
SiO2:0.04Al2O3:0.20Na2O:0.15ROH:50H2O
Obtained product is through X-ray diffraction analysis consisting of FER zeolite molecular sieve.
Embodiment 9: aluminium hydroxide be silicon source under conditions of synthesize FER molecular sieve
Firstly, by 13.5gH2O is uniformly mixed with 0.052g aluminium hydroxide, then 0.67g hydroxide N, N- bis- is added thereto
Cis- 2, the 6- lupetidine aqueous solution (2.3mol/L) of ethyl-is uniformly mixed, and 0.28gNaOH is added, is added under stiring later
2.5g silica solution continues stirring after solution becomes uniformly (being in gel), polytetrafluoroethylene (PTFE) stainless steel is added in reaction raw materials
In reaction kettle, 140 DEG C of dynamic crystallization 48h, that is, complete crystallizations, product is filtered, and obtains product after drying.
The molar ratio relationship of each component is as follows in reaction system:
SiO2:0.04Al2O3:0.20Na2O:0.10ROH:50H2O
Obtained product is through X-ray diffraction analysis consisting of FER zeolite molecular sieve.
Embodiment 10: aluminum sulfate be silicon source under conditions of synthesize FER molecular sieve
Firstly, by 13.5gH2O is uniformly mixed with 0.114g aluminum sulfate, then 0.67g hydroxide N, N- diethyl are added thereto
Cis- 2, the 6- lupetidine aqueous solution (2.3mol/L) of base-is uniformly mixed, and 0.28gNaOH is added, is added under stiring later
2.5g silica solution continues stirring after solution becomes uniformly (being in gel), polytetrafluoroethylene (PTFE) stainless steel is added in reaction raw materials
In reaction kettle, 140 DEG C of dynamic crystallization 48h, that is, complete crystallizations, product is filtered, and obtains product after drying.
The molar ratio relationship of each component is as follows in reaction system:
SiO2:0.04Al2O3:0.20Na2O:0.10ROH:50H2O
Obtained product is through X-ray diffraction analysis consisting of FER zeolite molecular sieve.
The above is only several case study on implementation of the invention, not does limitation in any form to the present invention,
Although the present invention is disclosed as above with preferable case study on implementation, however, it is not intended to limit the invention, any skill for being familiar with this profession
Art personnel, without departing from the scope of the present invention, when the structure and technology contents using the disclosure above make it is a little
Change or be modified to the equivalence enforcement case of equivalent variations.But anything that does not depart from the technical scheme of the invention, foundation
Technical spirit of the invention still belongs to the present invention to any simple modification, equivalent change and modification made by the above case study on implementation
In technical proposal scope.
Claims (5)
1. a kind of method that hydrothermal synthesis method prepares nano-sheet FER molecular sieve, which comprises the following steps:
After mixing by water and silicon source, hydroxide N is added, N- diethyl-cis- 2,6- lupetidine solution and NaOH are solid
Silicon source is added in body under stiring, continues to be stirred solution until in gel；It goes in reaction kettle, at 110~150 DEG C
Dynamic crystallization reacts 36~96h；Reaction product is filtered, is dried to get FER molecular sieve original powder is arrived；
The additive amount for controlling each reaction raw materials makes the molar ratio range SiO of following components in reaction system2: 0.02~
0.06Al2O3: 0.20~0.35Na2O: 0.05~0.15ROH: 50H2O。
2. the method according to claim 1, wherein source of aluminium is aluminum sulfate, aluminium hydroxide or sodium metaaluminate.
3. the method according to claim 1, wherein the silicon source is the solid that dioxide-containing silica is 100%
The silica solution of silica gel or white carbon black or solid content 40%.
4. the method according to claim 1, wherein the water is deionized water.
5. according to claim 1 to method described in 4 any one, which is characterized in that the hydroxide N, N- diethyl-
Cis- lupetidine solution is prepared by following methods:
Cis- 2,6- lupetidine is dissolved in methanol, iodoethane and saleratus is then added；It is stirred at reflux at 50 DEG C anti-
After answering 4 days, rotary evaporation removes solvent and extra iodoethane；With chloroform dissolved organic matter, it is filtered to remove solid；Revolving is removed
After removing chloroform, ethyl alcohol and Diethyl ether recrystallization are successively used, N, N- diethyl-cis- 2,6- lupetidine salt compounded of iodine powder are obtained；By powder
End is soluble in water, with hydrogen-oxygen type cation resin exchange, obtains organic formwork agent hydroxide N, N- diethyl-cis- 2,6- diformazan
Phenylpiperidines solution.
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