CN108862309A - A kind of NaY molecular sieve aggregation and preparation method thereof with nano-micro structure - Google Patents
A kind of NaY molecular sieve aggregation and preparation method thereof with nano-micro structure Download PDFInfo
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- CN108862309A CN108862309A CN201710328690.7A CN201710328690A CN108862309A CN 108862309 A CN108862309 A CN 108862309A CN 201710328690 A CN201710328690 A CN 201710328690A CN 108862309 A CN108862309 A CN 108862309A
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- Prior art keywords
- molecular sieve
- directed agents
- quaternary ammonium
- ammonium salt
- reaction gel
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 122
- 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 121
- 238000004220 aggregation Methods 0.000 title claims abstract description 71
- 230000002776 aggregation Effects 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 63
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 34
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002425 crystallisation Methods 0.000 claims abstract description 26
- 230000008025 crystallization Effects 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 238000013459 approach Methods 0.000 claims abstract description 4
- 239000000499 gel Substances 0.000 claims description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000010703 silicon Substances 0.000 claims description 51
- 229910052710 silicon Inorganic materials 0.000 claims description 51
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000000741 silica gel Substances 0.000 claims description 46
- 229910002027 silica gel Inorganic materials 0.000 claims description 46
- 229910001868 water Inorganic materials 0.000 claims description 40
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 claims description 30
- 229960004029 silicic acid Drugs 0.000 claims description 30
- 230000015572 biosynthetic process Effects 0.000 claims description 27
- 238000003786 synthesis reaction Methods 0.000 claims description 26
- 239000011734 sodium Substances 0.000 claims description 22
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 235000019353 potassium silicate Nutrition 0.000 claims description 19
- 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 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 229960001866 silicon dioxide Drugs 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 11
- -1 Silicon quaternary ammonium salt Chemical class 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 9
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [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 5
- 125000001453 quaternary ammonium group Chemical class 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 3
- 230000000694 effects Effects 0.000 description 27
- 239000000243 solution Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 18
- 239000002994 raw material Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 11
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 10
- 239000004005 microsphere Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 229950011008 tetrachloroethylene Drugs 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 238000003483 aging Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000005580 one pot reaction Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- NVIIYWDYGCZVCT-UHFFFAOYSA-N O.[Na].[Si](O)(O)(O)O Chemical compound O.[Na].[Si](O)(O)(O)O NVIIYWDYGCZVCT-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 210000003850 cellular structure Anatomy 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- WWBITQUCWSFVNB-UHFFFAOYSA-N 3-silylpropan-1-amine Chemical compound NCCC[SiH3] WWBITQUCWSFVNB-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241001522296 Erithacus rubecula Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229920006335 epoxy glue Polymers 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-O hydron;octadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCC[NH3+] REYJJPSVUYRZGE-UHFFFAOYSA-O 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 229940094989 trimethylsilane Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
- 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
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/205—Faujasite type, e.g. type X or Y using at least one organic template directing agent; Hexagonal faujasite; Intergrowth products of cubic and hexagonal faujasite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
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- 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
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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
- C01P2004/50—Agglomerated particles
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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
- C01P2004/51—Particles with a specific particle size distribution
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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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
The present invention provides a kind of NaY molecular sieve aggregation and preparation method thereof with nano-micro structure.This approach includes the following steps：Synthesize directed agents；Reaction gel is prepared using the directed agents；Crystallization is carried out to the reaction gel, obtains the NaY molecular sieve aggregation with nano-micro structure；Wherein, organosilicon quaternary ammonium salt is introduced during synthesizing directed agents and/or preparation reaction gel.The series of advantages such as technical solution simple process provided by the invention, cost is relatively low, and finally obtained product has that crystal phase is complete, high silica alumina ratio, high-specific surface area, is rich in mesoporous-microcellular structure, and crystallite dimension is controllable.
Description
Technical field
The present invention relates to a kind of NaY molecular sieve aggregation and preparation method thereof with nano-micro structure, belongs to system with molecular sieve for preparing
Standby technical field.
Background technique
Y type molecular sieve due to its special three-dimensional open-framework, high-temperature stability and good catalytic activity industrially
It is used widely.The end of the fifties, MILTON R.M. and BRECK D.W. (US3130007) successfully synthesize Y type molecular sieve.Y
Type molecular sieve replaces X-type zeolite to become the main of catalyst with its high stability, high activity, anti-metallic contamination and anti-caking power
Active component.The beginning of the seventies, GRACE company of the U.S. (US 3639099, US 3671191) synthesize NaY molecule with directing agent method
Sieve, raw material, instead of expensive silica solution, simplify technique with waterglass, shorten the production cycle, thus make NaY molecular sieve rapidly and
It is widely used in petroleum catalytic cracking field.
The conventional method of industrial production NaY molecular sieve is to do raw material using waterglass to prepare epoxy glue at present, is carried out brilliant
Change the synthesis for completing Y type molecular sieve.Since waterglass system raw material itself contains a large amount of water, wherein the quality of silica is divided
Number only has 19-28%, and its synthetic system viscosity can not improve greatly the solid content of system, cause this method solid content low,
So the one-pot yield for preparing Y type molecular sieve during each reaction is low lower than 10-12%, silicon source utilization rate, silicon source stream is caused
It loses seriously, causes damages so generating a large amount of siliceous lye to environment.It is reported that big Alternative is to preparing Y type molecular sieve
Mother liquor carries out multiple reuse, compensates for a large amount of silicon source in above-mentioned technique to a certain extent and is lost, but this virtually brings Y
The complexity of type preparation of molecular sieve and product property it is uncontrollable.
The study on the synthesis of Y type molecular sieve mainly focuses on expansion in terms of following two：
Firstly, considering from angle of enhancing product performance.NaY type molecular sieve is with high stability and good catalytic activity in work
It is used widely in industry.The Y type molecular sieve of other forms is obtained by ion exchange or other method of modifying, such as KY, NH4Y、
USY, REY, both HY and REUSY etc. are well used in fields such as petroleum refinings.As catalyst active component or
Person's carrier, sodium ions content, framework si-al ratio, molecular sieve cell parameter, molecule in the crystallite dimension and molecular sieve of molecular sieve
Cellular structure influences it and shows in the catalyst in sieve.For example, the molecular sieve of high silica alumina ratio can be improved the bone of modified molecular screen
Frame sial, hydrothermal stability with higher and crystallinity reservation degree；Small crystal grain molecular sieve can be improved catalytic selectivity, drop
Low coke formation increases diesel yield, improves quality of gasoline；Grade porous molecular sieve has the cellular structure of height connection, can
Improve reaction rate, selectivity, lower deactivation rate and new adsorption capacity.
Secondly, the synthesis technology of NaY molecular sieve is being continuously improved how from the point of view of efficient, economical, environmentally friendly
Single-autoclave yield rate, silicon source utilization rate are being improved, the Y molecular sieve that high-quality is synthesized under conditions of reduction pollutant emission, which becomes, to be ground
One of striving direction for the person of studying carefully.
Therefore, exploitation efficiently synthesizes system and technique, and preparation has good crystallinity, high silica alumina ratio, controlled grain size
And the high-performance Y type molecular sieve of grade pore structure has become a hot topic of research.
1967 by McDaniel (Society of Chemical Industry, London.1968:Et al. 186) mention
Hydrothermal dealumination method out, is developed so far, and has 50 years history.This method be to zeolite skeleton super stabilizing during, lead to
Zeolite framework dealumination is crossed by mesoporous introducing zeolite skeleton, to obtain high silica alumina ratio and rich in mesoporous molecular sieve.
Nineteen eighty-three, Breck D.W. and Skeels G.W (US4503023) have been invented with ammonium fluosilicate liquid phase dealumination complement silicon
The method of modified zeolite of Y-type.1980, Beyer et al. was reported under gaseous environment for the first time with silicon tetrachloride same order elements zeolite
In skeleton aluminium atom (Studies in Surface Science and Catalysis.Elsevier, 1980:203-
210).Under suitable condition, the product framework si-al ratio obtained increases, structural integrity, but generates transgranular mesoporous less.
Other reported chemical dealuminization methods mainly have EDTA that dealuminzation (Catalysis Letters.1993,19 (2-3) is complexed:
159-165.) and (the Journal of Catalysis.2011,279 (1) such as citric acid dealuminzation:27-35).
2010, (Chemical Communications, 2010.46 (41) such as Chal.Robin:P.7840.) containing
In the solution for having TMAOH and CTAB, after HY is handled, total pore volume is by 0.4cm3g-1Increase to 0.6cm3g-1, micro pore volume by
0.19cm originally3g-1Halve, mesopore volume increases to 0.51cm3g-1.Then, author[80]Point out that this method can also be applied
In the molecular sieve of lower sial atomic ratio (2.5-3.0), molecular sieve is pre-processed with diluted acid solution.
2010, (Microporous and Mesoporous Materials, 2010.127 (3) such as Yi Huang:
P.167-175. it) is synthesized in hydrothermal system by three step temperature controls (being stirred at room temperature for 24 hours, 38 DEG C are aged for 24 hours, 60 crystallization 48h) small
The grade hole Y type molecular sieve (190-600nm) of crystal grain (20-80nm) accumulation, the size of crystal grain is controlled by adjusting water content.
2013, and researcher (Microporous and Mesoporous Materials.2013,170:243-
250) it is that mesoporous directed agents carry out molecular sieve recrystallization synthesis with cationicsurfactants, successfully draws in molecular sieve
Enter biggish pore structure.The method of this recrystallization is to handle molecular sieve crystal in the alkaline solution there are surfactant.
This method shows that can generate uniform mesoporous be distributed in inside molecular sieve crystal is with Y type molecular sieve in previous studies
Model, and the primary morphology of molecular sieve can be retained.
2011, CN102689910A was used as co-template using trimethyl silane is polymer-modified, using collosol and gel
Method synthesizes in hydrothermal system and obtains the Y type molecular sieve of Jie's micropore.Help the molecular weight of template it can close with modulation by changing
At the mesoporous aperture size generated in the process to molecular sieve.
2013, CN103214003A utilized amphiphilic organosilan N, N- dimethyl-N-[3- (trimethoxy) propyl] chlorine
Change octadecyl ammonium (TPOAC) as the synthesis for being oriented to mesoporous Y molecular sieve in mesoporous one step hydrothermal system of template.
2013, CN103043680A provided the complete of Zeolite synthesis with natural kaolin mineral and natural diatomaceous earth mineral
Portion's silicon source and silicon source, and the matrix as molecular sieve growth, form NaY molecular sieve/natural mine of multilevel structure through in-situ crystallization
Object composite material, but the product that the molecular sieve obtained in this way is mixed with matrix.
2014, the Y molecular sieve for the containing mesopore that CN104891523A is synthesized using organic formwork agent was further mesoporous with this
The synthetic system of Y molecular sieve is added as crystal seed for Y molecular sieve, and directed agents are used in combination in the synthesis process, prepare mesoporous point
Son sieve.The preparation system has used a small amount of organic formwork agent, synthesising mesoporous Y molecular sieve indirectly in this way.
In conclusion synthesis Jie's micro-structure Y molecular sieve is to use waterglass for raw material at present, pass through in hydrothermal system
Modified synthesis gel is prepared, and there are template materials are big, product yield is low, Mother liquid the problems such as.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of NaY molecular sieves with nano-micro structure to gather
Collective and preparation method thereof.Technical solution simple process provided by the invention, cost is relatively low, and finally obtained product has crystal phase
Completely, high silica alumina ratio, high-specific surface area, rich in mesoporous-microcellular structure, the series of advantages such as crystallite dimension is controllable.
In order to achieve the above objectives, the preparation side of the present invention provides a kind of NaY molecular sieve aggregation with nano-micro structure
Method, this approach includes the following steps：
Synthesize directed agents；
Reaction gel is prepared using the directed agents；
Crystallization is carried out to the reaction gel, obtains the NaY molecular sieve aggregation with nano-micro structure；Wherein,
Organosilicon quaternary ammonium salt is introduced during synthesizing directed agents and/or preparation reaction gel.
Technical solution provided by the invention introduces organosilicon quaternary ammonium salt in directed agents and/or reaction gel can obtain height
The directed agents of regularity and/or high regularity hydrated silica gel.
Technical solution provided by the invention is using organosilicon quaternary ammonium salt to the directed agents or reaction gel of synthesis Y molecular sieve
Silylating reagent is carried out, synthesis has the NaY molecular sieve ordered aggregation of nano-micro structure in highly concentrated system, on the one hand improves
One-pot yield and one-pot utilization rate, on the other hand improve the performance of product, and the product being finally prepared has nanocrystal
And its constitute grade hole the characteristics of, the aggregation being formed simultaneously understands the problem of the nanocrystalline separation engineering of molecular sieve
Certainly.
In the above-mentioned methods, it is preferable that synthesis directed agents include following procedure：According to Na2O:Al2O3:SiO2:H2O:
QASiCs=(15-25):1:(8-30):(250-450):The molar ratio of (0-10) by silicon source, water, alkali source, silicon source and has
Machine silicon quaternary ammonium salt is uniformly mixed, and directed agents are made in ageing；Wherein, the organosilicon quaternary ammonium salt is indicated with QASiCs；More preferably
Ground, when synthesizing directed agents, molar ratio Na2O:Al2O3:SiO2:H2O:QASiCs=(15-25):1:(8-30):(250-
450):(0-5).When synthesizing directed agents, (external adding water includes for water in silicon source of water in molar ratio and external adding water
Deionized water).
In the above-mentioned methods, it is preferable that during synthesis directed agents, by silicon source, water, alkali source, silicon source and organosilicone quaternary ammonium
It includes following procedure that salt, which is uniformly mixed,：Silicon source is mixed into pretreatment with alkali source；Then water, silicon source and organosilicon season are added thereto
Ammonium salt is uniformly mixed.
In the above-mentioned methods, it is preferable that silicon source used in during synthesis directed agents includes that waterglass and/or silicon are molten
Glue.
In the above-mentioned methods, it is preferable that synthesis directed agents during used in silicon source include sodium metaaluminate, aluminum sulfate and
One or more of combinations of aluminum nitrate.
In the above-mentioned methods, it is preferable that the alkali source being applicable in during synthesis directed agents includes sodium hydroxide.
In the above-mentioned methods, it is preferable that water used in during synthesis directed agents is deionized water.
In the above-mentioned methods, during synthesizing directed agents, the ageing can use existing ageing operational means, preferably
The degree on ground, the ageing temperature is 0-40 DEG C, more preferably 10-30 DEG C；The time of the ageing is 5-100h, more preferably 15-
60h。
In the above-mentioned methods, it is preferable that preparing reaction gel using the directed agents includes following procedure：
According to Na2O:Al2O3:SiO2:H2O:QASiCs=(2-6):1:(5.5-10.5):(50-150):(0-5.0's) is total
Silicon source, water, silicon source, directed agents and organosilicon quaternary ammonium salt are uniformly mixed by molar ratio, and reaction gel is made；Wherein, described
Organosilicon quaternary ammonium salt is indicated with QASiCs.It is understood that mole when preparation reaction gel, in total molar ratio
Number refers to the total mole number that synthesis directed agents+preparation reaction gel all feeds intake.
In the above-mentioned methods, it is preferable that total molar ratio is Na when using directed agents preparation reaction gel2O:
Al2O3:SiO2:H2O:QASiCs=(2.5-4):1:(7-9):(85-120):(0-2.0).
In the above-mentioned methods, it is preferable that preparation reaction gel during used in silicon source include waterglass, c-type silica gel,
One or more of combinations of sodium metasilicate and white carbon black；It is highly preferred that the silicon source is solid.
In the above-mentioned methods, it is preferable that silicon source used in during preparation reaction gel includes sodium metaaluminate, aluminum sulfate
With combination one or more of in aluminum nitrate.
In the above-mentioned methods, it is preferable that water used in during preparation reaction gel is deionized water.
In the above-mentioned methods, it is preferable that during preparation reaction gel, by silicon source, water, silicon source, directed agents and organosilicon
Quaternary ammonium salt includes following procedure when being uniformly mixed：Silicon source is added to the water and is pre-processed, hydrated silica gel is prepared；To institute
It states and silicon source, directed agents and organosilicon quaternary ammonium salt is added in hydrated silica gel；It is pre-processed it is highly preferred that silicon source is added to the water
When, the pretreated temperature is 0-60 DEG C, and the pretreated time is 2-4h.
In the above-mentioned methods, it is preferable that when preparation reaction gel, pass through the H of addition water introducing2The weight of O accounts for described anti-
Answer the 30-80% of gel total weight, more preferably 30-50%.
In the above-mentioned methods, it is preferable that when preparation reaction gel, pass through the Al of addition directed agents introducing2O3Weight account for institute
State Al in reaction gel2O3The 5-20% of total weight.
In the above-mentioned methods, it is preferable that when preparation reaction gel, pass through the SiO of addition organosilicon quaternary ammonium salt introducing2Weight
Amount accounts for SiO in the reaction gel2The 0.1-15% of total weight, more preferably 0.1-10%.
In the above-mentioned methods, it is preferable that synthesis directed agents and/or the organosilicone quaternary ammonium for preparing introducing during reaction gel
Salt includes N, N- Dimethyl-N-dodecyl aminopropyl alkoxy silane quaternary ammonium salt, N, N- dimethyl-N-tetradecyl base aminopropyl
Alkoxy silane quaternary ammonium salt and N, one or more of N- dimethyl-N-hexadecyl base aminopropyl alkoxy silane quaternary ammonium salt
Combination.
In the above-mentioned methods, it is preferable that synthesis directed agents and/or the organosilicone quaternary ammonium for preparing introducing during reaction gel
Salt includes the combination of one or more of compound with structure described in formula 1
[(CnH2n+1O)3SiC3H6N(CH3)2-CxH2x+1] X formula 1
In formula 1, n is 1 or 2；X is=12,14 or 16；X is Cl, Br or I.
In the above-mentioned methods, the crystallization operation side of this field routine can be used when carrying out crystallization to the reaction gel
Method, it is preferable that carrying out crystallization to the reaction gel includes following procedure：By the reaction gel at 90-110 DEG C crystallization
20-120h；It after crystallization, is filtered, washed, dries；It is highly preferred that the time of the crystallization is 24-72h.
In a preferred embodiment, the preparation method of the NaY molecular sieve aggregation with nano-micro structure includes
Following steps：
According to Na2O:Al2O3:SiO2:H2O:QASiCs=(15-25):1:(8-30):(250-450):(0-10's) feeds intake
Silicon source, water, alkali source, silicon source and organosilicon quaternary ammonium salt are uniformly mixed by molar ratio, and directed agents are made in ageing；Wherein, described to have
Machine silicon quaternary ammonium salt is indicated with QASiCs；
According to Na2O:Al2O3:SiO2:H2O:QASiCs=(2-6):1:(5.5-10.5):(50-150):(0-5.0's) is total
Silicon source is added to the water and pre-processes so that hydrated silica gel is prepared by molar ratio, successively adds into the hydrated silica gel
Enter silicon source, directed agents and organosilicon quaternary ammonium salt, be uniformly mixed, reaction gel is made；Wherein, the organosilicon quaternary ammonium salt with
QASiCs is indicated；
The reaction gel is subjected to crystallization, obtains the NaY molecular sieve aggregation with nano-micro structure；Wherein,
When preparing directed agents and reaction gel, the organosilicon quaternary ammonium salt of introducing is not 0 simultaneously.
The present invention also provides a kind of NaY molecular sieve aggregation prepared by the above method with nano-micro structure,
The NaY molecular sieve aggregation has micropore and mesoporous feature.The overall dimensions of the NaY molecular sieve aggregation are 1-5 μm, excellent
Be selected as 2-4 μm, the NaY molecular sieve aggregation is formed by receiving the brilliant orderly aggregation of micron, wherein receive micron crystalline substance size it is excellent
It is selected as 5-100nm, more preferably 10-100nm.
In above-mentioned NaY molecular sieve aggregation, it is preferable that the silica alumina ratio of the NaY molecular sieve aggregation is 4.0-
6.0；Kong Rongwei 0.3-0.6cm3/g；External surface area is 50-180m2/ g, more preferably 80-140m2/g；BET specific surface area is
650-750m2/ g, more preferably 680-750m2/g。
In above-mentioned NaY molecular sieve aggregation, it is preferable that the relative crystallinity of the NaY molecular sieve aggregation is 95%-
100%.
In the technical solution provided by the present invention, waterglass can for example use SiO using conventional reagent is sold2Contain
Amount is 28.08wt%, Na2O content is the commercial water glass product of 8.83wt%；Silica solution can use commercially available conventional reagent,
SiO can for example be used2Content is 40.00wt%, Na2O content is 0.40wt%, and average-size is that the commercially available silicon of 10-20nm is molten
Glue product；C-type silica gel (also referred to as silochrom) can use commercially available conventional products, for example Kong Rong >=0.78cm3The city of/g
Sell c-type silica gel；In addition, white carbon black can also use commercially available conventional chemical reagent.
In the technical solution provided by the present invention, organosilan quaternary ammonium salt can synthesize in accordance with the following methods：By silane and
Tertiary amine is according to (1:1)-(1:3) ratio mixing reacts 24-60h, organosilicone quaternary ammonium is prepared under conditions of 40-80 DEG C
Salt；Wherein, silane and tertiary amine can be the conventional reagent of this field, be not particularly limited, and can for example use three second of chloropropyl
The commercially available chloropropyl triethoxysilane that oxysilane content is 98.00%, dodecyl tertiary amine content are commercially available the ten of 97%
Dialkyl group tertiary amine.
Beneficial effects of the present invention：
1) technical solution provided by the invention is using organosilan quaternary ammonium salt to the directed agents of synthesis Y molecular sieve and/or anti-
Gel is answered to be modified and be modified, synthesis has the NaY molecular sieve aggregation ordered aggregation of nano-micro structure in highly concentrated system,
On the one hand one-pot yield and one-pot utilization rate are improved, on the other hand improves the performance of product, finally synthesizes obtained production
Product have the characteristics that little crystal grain and grade hole, and the aggregation being formed simultaneously obtains the problem of the nanocrystalline separation engineering of molecular sieve
Solution has been arrived, has provided new thinking and direction for the synthesis and application of nanocrystalline Y molecular sieve；
2) technical solution provided by the invention introduces organosilicon quaternary ammonium salt in directed agents and/or reaction gel and can obtain
The directed agents of high regularity and/or high regularity hydrated silica gel, finally obtained product complete, high silica alumina ratio with crystal phase are high
Specific surface area, rich in mesoporous-microcellular structure, the series of advantages such as crystallite dimension is controllable；
3) technical solution simple process provided by the invention, cost is relatively low, containing mesopore-micropore of uniform size can be synthesized
NaY molecular sieve aggregation, the silica alumina ratio of the NaY molecular sieve aggregation are 4.0-6.0, crystallite dimension 5-100nm, Y molecular sieve
The size of aggregate particle is 1-5 μm, Kong Rongwei 0.3-0.6cm3/g；And the external surface area of the NaY molecular sieve aggregation and
Total pore volume is improved largely compared with the molecular sieve that hydrothermal system synthesizes and (can be improved 50% or more), NaY molecular sieve aggregation
The crystallite dimension of body is in 100nm hereinafter, these features can significantly improve the utilization of product catalytic perfomance and molecular sieve
Rate；；
4) compared with prior art, technical solution provided by the invention can pass through modification on the basis of modified gel
Directed agents introduce less template, thus the crystallite dimension and cellular structure of more efficient regulation sintetics；In addition, and originally
The technical solution provided is invented when preparing reaction gel, using solid silicon source, the yield of product, energy-saving ring can be greatly improved
It protects.
Detailed description of the invention
Fig. 1 is the XRD spectrum of the NaY molecular sieve aggregation that embodiment 1 provides and the NaY molecular sieve that comparative example 1 provides；
Fig. 2 is the SEM photograph for the NaY molecular sieve aggregation that embodiment 1 provides；
Fig. 3 is the SEM picture for the NaY molecular sieve aggregation that comparative example 1 provides；
Fig. 4 is the N of the NaY molecular sieve aggregation that embodiment 1 provides and the NaY molecular sieve that comparative example 1 provides2Absorption-is de-
Attached curve.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
Present embodiments provide a kind of preparation method of NaY molecular sieve aggregation with nano-micro structure comprising following
Step：
1) 57.81g waterglass (SiO in waterglass is weighed2Content be 28.08wt%, Na2The content of O is 8.83wt%)
It is placed in a beaker, then weighs 8.81g sodium hydrate solid (Beijing Century Red Star Chemical Co., Ltd. analyzes pure) and be placed in beaker
In, the two is mixed evenly, and is stirred 2 hours in (27 DEG C) of room temperature, high activity hydration sodium silicate solution is prepared；
Sequentially add 54.11g deionized water, 3.12g sodium metaaluminate (Tianjin saliva section chemical institute, Al2O3Content
For 45wt%, Na2The content of O is 41wt%), it is uniformly mixed, 3g N, N- dimethyl-N-hexadecyl is added in system
Base γ-aminopropylsilane quaternary ammonium salt [(CnH2n+1O)3SiC3H6N(CH3)2-CxH2x+1] X, wherein n=1；X=16；X=Cl), in room
Directed agents are prepared in 36 hours in (27 DEG C) ageings of temperature.
Table 1
| Embodiment 1 | Comparative example 1 | |
| Silicon source in directed agents | Waterglass | Waterglass |
| Silicon source in reaction gel | Solid silicone | Solid silicone |
| Specific surface area/(m2/g) | 683.00 | 689.20 |
| External surface area/(m2/g) | 122.80 | 26.80 |
| Mesoporous Kong Rong/(cm3/g) | 0.16 | 0.06 |
| Silica alumina ratio | 5.6 | 5.30 |
| Crystallite dimension/nm | 20-100 | 200-800 |
| Whole pattern/size | Aggregation (1-4 μm) | -- |
2) it weighs 42.54gC type silica gel (also known as gross porosity microsphere silica gel) to be added in 90g deionized water, at 20 DEG C of constant temperature
Lower stirring 3 hours, is prepared the hydrated silica gel of high activity, then weighs 21.00g sodium metaaluminate in the hydrated silica gel of high activity
In, after mixing evenly, above-mentioned directed agents 83.38g is added, stirs evenly obtained reaction gel.
3) above-mentioned reaction gel is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of static crystallization 48h,
Then it is filtered, washed, dries, obtain NaY molecular sieve aggregation product.
The BET specific surface area of NaY molecular sieve aggregation product provided in this embodiment is 683m2/ g, silica alumina ratio 5.6,
Crystallite dimension is 20-100nm, and aggregate size is 1-4 μm, Kong Rongwei 0.46cm3/g。
Physical and chemical performance and the preparation process analysis of NaY molecular sieve aggregation provided in this embodiment are shown in Table 1, the product
XRD spectra as shown in Figure 1, Electronic Speculum spectrogram as shown in Fig. 2, N2Adsorption/desorption curve is as shown in Figure 4.
Embodiment 2
Present embodiments provide a kind of preparation method of NaY molecular sieve aggregation with nano-micro structure comprising following
Step：
1) preparation method of directed agents and raw material sources are the same as embodiment 1.
2) it weighs 32.54gC type silica gel (also referred to as gross porosity microsphere silica gel) to be added in 50g deionized water, add
53.19g waterglass stirs 3 hours at 20 DEG C of constant temperature, the hydrated silica gel of high activity is prepared, it is inclined then to weigh 15.00g
(development in science and technology Co., Ltd, Al are recovered in Tianjin to the aluminum sulfate of sodium aluminate and 17.64g2SO4·18H2The content of O is 99%) molten
In the hydrated silica gel of high activity, after mixing evenly, above-mentioned directed agents 83.38g is added, stirs evenly obtained reaction gel.
3) above-mentioned reaction gel is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of static crystallization 48h,
Then it is filtered, washed, dries, obtain NaY molecular sieve aggregation product.
The BET specific surface area of NaY molecular sieve aggregation product provided in this embodiment is 662m2/ g, silica alumina ratio 5.3,
Crystallite dimension is 20-100nm, and aggregate size is 1-4 μm, Kong Rongwei 0.39cm3/g。
Embodiment 3
Present embodiments provide a kind of preparation method of NaY molecular sieve aggregation with nano-micro structure comprising following
Step：
1) directed agents preparation method and raw material sources are the same as embodiment 1.
2) it weighs 40.54g gross porosity microsphere silica gel to be added in 86g deionized water, be stirred 3 hours at 20 DEG C of constant temperature, made
It is standby to obtain the hydrated silica gel of high activity, 20.00g sodium metaaluminate is then weighed in the hydrated silica gel of high activity, after mixing evenly,
Above-mentioned directed agents 83.38g is added, stirs evenly obtained reaction gel.
3) above-mentioned reaction gel is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of static crystallization 96h,
Then it is filtered, washed, dries, obtain NaY molecular sieve aggregation product.
The specific surface area of NaY molecular sieve aggregation product provided in this embodiment is 693m2/ g, silica alumina ratio 5.6, crystal grain
Having a size of 60-100nm, aggregate size is 1-4 μm, Kong Rongwei 0.53cm3/g。
Embodiment 4
Present embodiments provide a kind of preparation method of NaY molecular sieve aggregation with nano-micro structure comprising following
Step：
1) various raw material sources are the same as embodiment 1
It weighs 55.80g waterglass to be placed in a beaker, then weighs 9.66g sodium hydrate solid and be placed in a beaker, the two is mixed
Conjunction stirs evenly, and stirs 1 hour in (20 DEG C) of room temperature, and the silicic acid hydrate sodium solution of high activity is prepared；It sequentially adds
47.39g deionized water, 2.82g sodium metaaluminate, is uniformly mixed, and directed agents are prepared after being aged 120 hours in 15 DEG C.
2) it weighs 20.31g gross porosity microsphere silica gel to be added in ionized water, stirs 3 hours, be prepared at 40 DEG C of constant temperature
Then the hydrated silica gel of high activity weighs 10.00g sodium metaaluminate in the hydrated silica gel of high activity, after mixing evenly, in addition
Directed agents 37.65g is stated, is stirred evenly, 3.5g N, N- dimethyl-N-hexadecyl base γ-aminopropylsilane are then added in system
Quaternary ammonium salt ([(CnH2n+1O)3SiC3H6N(CH3)2-CxH2x+1] X, wherein n=1；X=16；X=Cl), reaction gel is made.
3) reaction gel is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of static crystallization 72h, then
It is filtered, washed, dries, obtain NaY molecular sieve aggregation product.
The BET specific surface area of NaY molecular sieve aggregation provided in this embodiment is 683m2/ g, silica alumina ratio 5.24, crystal grain
Having a size of 20-100nm, aggregate size is 1-3 μm, Kong Rongwei 0.42cm3/g。
Embodiment 5
Present embodiments provide a kind of preparation method of NaY molecular sieve aggregation with nano-micro structure comprising following
Step：
1) directed agents preparation method and raw material sources are the same as embodiment 4.
2) it weighs 20.31g gross porosity microsphere silica gel to be added in ionized water, stirs 3 hours, be prepared at 20 DEG C of constant temperature
Then the hydrated silica gel of high activity weighs 10.00g sodium metaaluminate in the hydrated silica gel of high activity, after mixing evenly, in addition
Directed agents 37.65g is stated, is stirred evenly, 4.5g N, N- dimethyl-N-hexadecyl base γ-aminopropylsilane are then added in system
Quaternary ammonium salt ([(CnH2n+1O)3SiC3H6N(CH3)2-CxH2x+1] X, wherein n=1；X=16；X=Br), reaction gel is made.
3) reaction gel is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of static crystallization 72h, then
It is filtered, washed, dries, obtain NaY molecular sieve aggregation product.
The BET specific surface area of NaY molecular sieve aggregation provided in this embodiment is 703m2/ g, silica alumina ratio 5.34, crystal grain
Having a size of 20-100nm, aggregate size is 1-3 μm, Kong Rongwei 0.40cm3/g。
Embodiment 6
Present embodiments provide a kind of preparation method of NaY molecular sieve aggregation with nano-micro structure comprising following
Step：
1) preparation method of directed agents and raw material sources are the same as embodiment 4.
2) it weighs 20.31g gross porosity microsphere silica gel to be added in ionized water, stirs 3 hours, be prepared at 20 DEG C of constant temperature
Then the hydrated silica gel of high activity weighs 10.00g sodium metaaluminate in the hydrated silica gel of high activity, after mixing evenly, in addition
Directed agents 37.65g is stated, is stirred evenly, 4.0g N, N- Dimethyl-N-dodecyl γ-aminopropylsilane are then added in system
Quaternary ammonium salt ([(CnH2n+1O)3SiC3H6N(CH3)2-CxH2x+1] X, wherein n=1；X=12；X=Cl), reaction gel is made.
3) reaction gel is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of static crystallization 72h, then
It is filtered, washed, dries, obtain NaY molecular sieve aggregation product.
The specific surface area of NaY molecular sieve aggregation provided in this embodiment is 675m2/ g, silica alumina ratio 5.21, crystal grain ruler
Very little is 20-100nm, and aggregate size is 1-2 μm, Kong Rongwei 0.41cm3/g。
Embodiment 7
Present embodiments provide a kind of preparation method of NaY molecular sieve aggregation with nano-micro structure comprising following
Step：
The source of various raw materials is the same as embodiment 1.
1) it weighs 74.40g waterglass to be placed in a beaker, then weighs 11.21g sodium hydrate solid and be placed in the beaker, it will
The two is mixed evenly, and stirs 4 hours in 18 DEG C, and the silicic acid hydrate sodium solution of high activity is prepared；It sequentially adds
62.95g deionized water, 5.27g sodium metaaluminate, 3.40g N, N- dimethyl-N-tetradecyl base γ-aminopropylsilane quaternary ammonium salt
([(CnH2n+1O)3SiC3H6N(CH3)2-CxH2x+1] X, wherein n=1；X=14；X=Cl), it is uniformly mixed, it is old in 24 DEG C
Change 72 hours and directed agents are prepared.
2) it weighs 22.28g gross porosity microsphere silica gel to be add to deionized water, stirs 3 hours, be prepared at 30 DEG C of constant temperature
To the hydrated silica gel of high activity, 11.00g sodium metaaluminate is then weighed in the hydrated silica gel of high activity, after mixing evenly, is added
Above-mentioned directed agents 43.68g, stirs evenly obtained reaction gel.
3) reaction gel is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of crystallization 60h, then filter,
Washing, drying, obtain NaY molecular sieve aggregation product.
The specific surface area of NaY molecular sieve aggregation provided in this embodiment is 645m2/ g, silica alumina ratio 5.47, crystal grain
Having a size of 60-100nm, aggregate size is 3-5 μm, Kong Rongwei 0.40cm3/g。
Embodiment 8
Various raw material sources are the same as embodiment 1.
1) it weighs 55.80g waterglass to be placed in a beaker, then weighs 9.66g sodium hydrate solid in the beaker, by the two
It is mixed evenly, and is stirred 4 hours in 15 DEG C, the silicic acid hydrate sodium solution of high activity is prepared；It sequentially adds
36.24g deionized water, 1.97g sodium metaaluminate, is uniformly mixed, and the guiding that high activity is made for 120 hours is aged in 15 DEG C
Agent.
2) it weighs 30.39g gross porosity microsphere silica gel to be add to deionized water, be stirred 3.5 hours at 30 DEG C of constant temperature, prepared
The hydrated silica gel of high activity is obtained, 15.00g sodium metaaluminate is then weighed in the hydrated silica gel of high activity, after mixing evenly, adds
Enter above-mentioned directed agents 59.56g, stir evenly, 1.5g N, N- dimethyl-N-tetradecyl base aminopropyl are then added in system
Silane quaternary ammonium salt ([(CnH2n+1O)3SiC3H6N(CH3)2-CxH2x+1] X, wherein n=2；X=14；X=Cl), it is solidifying that reaction is made
Glue；The gross mass of reaction gel is 179.33g.
3) reaction gel is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of crystallization 48h, then filter,
It washs, be dried to obtain NaY molecular sieve aggregation product.
The BET specific surface area of NaY molecular sieve aggregation provided in this embodiment is 676.51m2/ g, silica alumina ratio 5.41,
Crystallite dimension is 20-100nm, and aggregate size is 1-4 μm, Kong Rongwei 0.40cm3/g。
Embodiment 9
Present embodiments provide a kind of preparation method of NaY molecular sieve aggregation with nano-micro structure comprising following
Step：
1) preparation method of directed agents and raw material sources are the same as embodiment 1.
2) it weighs 42.54g gross porosity microsphere silica gel to be added in 90g deionized water, be stirred 3 hours at 20 DEG C of constant temperature, made
It is standby to obtain the hydrated silica gel of high activity, 21.00g sodium metaaluminate is then weighed in the hydrated silica gel of high activity, after mixing evenly,
Above-mentioned directed agents 83.38g is added, stirs evenly obtained reaction gel.
3) reaction gel is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of static crystallization 96h, then
It is filtered, washed, dries, obtain NaY molecular sieve aggregation product.
The specific surface area of NaY molecular sieve aggregation provided in this embodiment is 698m2/ g, silica alumina ratio 5.4, the ruler of crystal grain
Very little is 20-100nm, and the size of aggregation is 1-4 μm, Kong Rongwei 0.43cm3/g。
Comparative example 1
This comparative example provides a kind of synthetic method of NaY molecular sieve comprising following steps：
This comparative example illustrates solid referring to the class in Publication No. CN104692412A (application No. is 201310656066.1)
Phase method synthesizes NaY molecular sieve, and the preparation of directed agents and various raw material sources are the same as embodiment 1.
1) it weighs 57.81g waterglass to be placed in a beaker, then weighs 8.81g sodium hydrate solid and be placed in a beaker, by the two
It is mixed evenly, and is stirred 2 hours in (27 DEG C) of room temperature, the silicic acid hydrate sodium solution of high activity is prepared；Successively add again
Enter 54.11g deionized water, 3.12g sodium metaaluminate is uniformly mixed, and is aged 36 hours in (27 DEG C) of room temperature and guiding is prepared
Agent.
2) it weighs 5.00g sodium hydrate solid to be dissolved in 45g deionized water, stirring dissolves it sufficiently, and alkali is prepared
Property solution, then weigh 42.54g gross porosity microsphere silica gel and be added in alkaline solution, it stirs 3 hours, is prepared at 20 DEG C of constant temperature
To the hydrated silica gel of high activity, 21.00g sodium metaaluminate is then weighed in the hydrated silica gel of high activity, after mixing evenly, is added
Above-mentioned directed agents 83.38g, stirs evenly obtained reaction gel, and the gross mass of reaction gel is 249.9g.
3) reaction gel is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of static crystallization 48h, then
It is filtered, washed, is dried to obtain NaY molecular sieve product.
The specific surface area of the NaY molecular sieve aggregation of this comparative example synthesis is 689.20m2/ g, silica alumina ratio 5.30, crystal grain
Having a size of 200-800nm.
Physical and chemical performance and the preparation process analysis for the NaY molecular sieve aggregation that this comparative example provides are shown in Table 1, product XRD
Spectrogram is as shown in Figure 1, electron microscope is as shown in Figure 3.
Claims (10)
1. a kind of preparation method of the NaY molecular sieve aggregation with nano-micro structure, this approach includes the following steps：
Synthesize directed agents；
Reaction gel is prepared using the directed agents；
Crystallization is carried out to the reaction gel, obtains the NaY molecular sieve aggregation with nano-micro structure；Wherein,
Organosilicon quaternary ammonium salt is introduced during synthesizing directed agents and/or preparation reaction gel.
2. according to the method described in claim 1, wherein, synthesis directed agents include following procedure：
According to Na2O:Al2O3:SiO2:H2O:QASiCs=(15-25):1:(8-30):(250-450):(0-10's) feeds intake mole
Than silicon source, water, alkali source, silicon source and organosilicon quaternary ammonium salt are uniformly mixed, are aged, directed agents are made；Wherein, the organosilicon
Quaternary ammonium salt is indicated with QASiCs；
Preferably, the silicon source includes waterglass and/or silica solution；
Source of aluminium includes one or more of combinations of sodium metaaluminate, aluminum sulfate and aluminum nitrate；
The alkali source includes sodium hydroxide；
The water is deionized water.
3. method according to claim 1 or 2, wherein preparing reaction gel using the directed agents includes following procedure：
According to Na2O:Al2O3:SiO2:H2O:QASiCs=(2-6):1:(5.5-10.5):(50-150):(0-5.0's) always feeds intake
Silicon source, water, silicon source, directed agents and organosilicon quaternary ammonium salt are uniformly mixed by molar ratio, and reaction gel is made；Wherein, described organic
Silicon quaternary ammonium salt is indicated with QASiCs；
Preferably, the silicon source includes one or more of combinations of waterglass, c-type silica gel, sodium metasilicate and white carbon black；
Source of aluminium includes combination one or more of in sodium metaaluminate, aluminum sulfate and aluminum nitrate；
The water is deionized water；
It is further preferred that total molar ratio is Na when preparing reaction gel using the directed agents2O:Al2O3:SiO2:H2O:
QASiCs=(2.5-4):1:(7-9):(85-120):(0-2.0).
4. method according to claim 1-3, wherein in synthesis directed agents and/or preparation reaction gel process
The organosilicon quaternary ammonium salt of middle introducing includes the combination of one or more of compound with structure described in formula 1
[(CnH2n+1O)3SiC3H6N(CH3)2-CxH2x+1] X formula 1
In formula 1, n is 1 or 2；X is=12,14 or 16；X is Cl, Br or I.
5. according to the method described in claim 3, wherein, during preparing reaction gel, by silicon source, water, silicon source, directed agents,
And organosilicon quaternary ammonium salt be uniformly mixed when include following procedure：
Silicon source is added to the water and is pre-processed, hydrated silica gel is prepared；
Silicon source, directed agents and organosilicon quaternary ammonium salt is added, into the hydrated silica gel reaction gel is made；
Preferably, the pretreated temperature is 0-60 DEG C, and the pretreated time is 2-4h.
6. method according to claim 1-3, wherein when preparation reaction gel,
The H introduced by addition water2The weight of O accounts for the 30-80% of the reaction gel total weight；
Preferably, the Al introduced by addition directed agents2O3Weight account for Al in the reaction gel2O3The 5-20% of total weight；
It is highly preferred that the SiO introduced by addition organosilicon quaternary ammonium salt2Weight account for SiO in the reaction gel2Total weight
0.1-15%.
7. method according to claim 1-4, wherein carrying out crystallization to the reaction gel includes following mistake
Journey：
By the reaction gel at 90-110 DEG C crystallization 20-120h；
It after crystallization, is filtered, washed, dries.
8. according to the method described in claim 1, wherein, this approach includes the following steps：
According to Na2O:Al2O3:SiO2:H2O:QASiCs=(15-25):1:(8-30):(250-450):(0-10's) feeds intake mole
Than silicon source, water, alkali source, silicon source and organosilicon quaternary ammonium salt are uniformly mixed, are aged, directed agents are made；Wherein, the organosilicon
Quaternary ammonium salt is indicated with QASiCs；
According to Na2O:Al2O3:SiO2:H2O:QASiCs=(2-6):1:(5.5-10.5):(50-150):(0-5.0's) always feeds intake
Silicon source is added to the water and pre-processes so that hydrated silica gel is prepared, sequentially adds aluminium into the hydrated silica gel by molar ratio
Source, directed agents and organosilicon quaternary ammonium salt are uniformly mixed, and reaction gel is made；Wherein, the organosilicon quaternary ammonium salt is with QASiCs table
Show；
The reaction gel is subjected to crystallization, obtains the NaY molecular sieve aggregation with nano-micro structure；Wherein,
When preparing directed agents and reaction gel, the organosilicon quaternary ammonium salt of introducing is not 0 simultaneously.
9. a kind of NaY molecular sieve aggregation with nano-micro structure is by the described in any item method preparations of claim 1-8
It obtains, the overall dimensions of the NaY molecular sieve aggregation are 1-5 μm, wherein the ruler of crystal grain in the NaY molecular sieve aggregation
Very little is 5-100nm.
10. NaY molecular sieve aggregation according to claim 9, wherein the Kong Rongwei of the NaY molecular sieve aggregation
0.3-0.6cm3/g；
The BET specific surface area of the NaY molecular sieve aggregation is 650-750m2/g。
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