CN108569705A - A kind of high silica alumina ratio NaY type molecular sieve and preparation method thereof - Google Patents
A kind of high silica alumina ratio NaY type molecular sieve and preparation method thereof Download PDFInfo
- Publication number
- CN108569705A CN108569705A CN201710151678.3A CN201710151678A CN108569705A CN 108569705 A CN108569705 A CN 108569705A CN 201710151678 A CN201710151678 A CN 201710151678A CN 108569705 A CN108569705 A CN 108569705A
- Authority
- CN
- China
- Prior art keywords
- sio
- molecular sieve
- silica alumina
- alumina ratio
- silicon source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 246
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 101
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 80
- 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 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000010703 silicon Substances 0.000 claims abstract description 42
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000002425 crystallisation Methods 0.000 claims abstract description 33
- 230000008025 crystallization Effects 0.000 claims abstract description 33
- 230000003068 static effect Effects 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000000499 gel Substances 0.000 claims description 45
- 229910001868 water Inorganic materials 0.000 claims description 38
- 239000000741 silica gel Substances 0.000 claims description 33
- 229910002027 silica gel Inorganic materials 0.000 claims description 33
- 229910052593 corundum Inorganic materials 0.000 claims description 30
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 30
- 229910052681 coesite Inorganic materials 0.000 claims description 28
- 229910052906 cristobalite Inorganic materials 0.000 claims description 28
- 229910052682 stishovite Inorganic materials 0.000 claims description 28
- 229910052905 tridymite Inorganic materials 0.000 claims description 28
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 25
- 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 21
- 229910052708 sodium Inorganic materials 0.000 claims description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 19
- 235000019353 potassium silicate Nutrition 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 12
- -1 aminopropyl Chemical group 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 4
- 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 4
- 239000004202 carbamide Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010457 zeolite Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 229910002796 Si–Al Inorganic materials 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 33
- 239000000047 product Substances 0.000 description 29
- 239000000203 mixture Substances 0.000 description 21
- 238000002156 mixing Methods 0.000 description 14
- 239000003643 water by type Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000004005 microsphere Substances 0.000 description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 7
- 238000005580 one pot reaction Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229950011008 tetrachloroethylene Drugs 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 235000013312 flour Nutrition 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical class CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 3
- 229910018540 Si C Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000019994 cava Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- GLISZRPOUBOZDL-UHFFFAOYSA-N 3-bromopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCBr GLISZRPOUBOZDL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920006335 epoxy glue Polymers 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 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
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J2029/081—Increasing the silica/alumina ratio; Desalumination
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of high silica alumina ratio NaY type molecular sieves and preparation method thereof.It includes the following steps：It according to certain molar ratio, is aged after silicon source, silicon source, alkali source, organosilan and deionized water are mixed, directed agents is made；According to certain molar ratio, deionized water, organosilan and directed agents are sequentially added into silicon source and silicon source, are mixed, and reaction gel is made；Reaction gel made from step (2) is subjected to static crystallization, is then filtered, washed, dries, high silica alumina ratio NaY type zeolite product is made.This method cost is relatively low, simple for process, crystallization time is short, yield and silicon source utilization rate are high, can be with synthesizing Si-Al ratio for 5.5 6.5, and crystallite dimension is the NaY molecular sieve of 200 500nm.
Description
Technical field
The present invention relates to a kind of high silica alumina ratio NaY type molecular sieves and preparation method thereof, belong to Zeolite synthesis technical field.
Background technology
Y type molecular sieve as catalyst activity constituent element or catalyst carrier be widely used in catalytic cracking, be hydrocracked with
It is current most widely used molecular screen material and during the oil-refining chemical of isomerization.Industrial production NaY molecular sieve at present
Conventional method be using the directing agent method proposed in US3639099 and US3671191.The NaY molecular sieve of this method synthesis
Framework si-al ratio (SiO2/Al2O3Molar ratio) generally 5.0 or so.
The performance that the framework silicon-aluminum of Y type molecular sieve compares FCC catalyst has a great impact.Improve the bone of Y type molecular sieve
Frame silica alumina ratio rationally reduces Al center densities and improves the relative intensity in acid site, and helping improves cracking lives with hydrogen migration
The ratio between property, hence it is evident that the burnt generation of catalysis is reduced, product distribution is improved.In addition, the framework si-al ratio of Y type molecular sieve is improved, it can be with
The hydrothermal stability and acid-resistant stability for significantly improving molecular sieve, during FCC under harsh reaction and aging condition still
It can keep higher cracking activity and selectivity, and then the product distribution that cracking reaction will be directly affected；It can bear FCC mistakes
Harsh reaction-regeneration condition in journey also directly affects catalyst production and catalysis to extend the service life of catalyst
The distribution of cracking unit product and economic benefit.
The method for preparing high silica alumina ratio Y type molecular sieve mainly has two kinds of post-modification method and direct synthesis technique：
Post-modification method is first to synthesize common NaY molecular sieve, then carries out dealumination complement silicon using various chemically or physically methods
I.e. " secondary synthesis " improves silica alumina ratio.Wherein include mainly：(1) hydrothermal synthesis method includes mainly：High temperature hydro-thermal method
(US3449370), high temperature gas-phase reaction method (US4701313, US4297335, US4297335, US4438178).This method is special
Point is the USY that can prepare silica alumina ratio 6-20, and most prominent advantage is that its process is simple and practicable.But in the process with non-skeleton
The generation of aluminium occurs zeolite portion lattice and caves in phenomenon, influences the catalytic performance of zeolite.(2) chemical dealuminization method includes mainly：
Organic complexing agent facture (US4093560), ammonium fluosilicate liquid phase reactor method (catalysis journal, 1993,14 (4)：300-306).
This method feature is can to prepare the Y type molecular sieve of silica alumina ratio 6-15, but can introduce other atoms, with zeolite portion lattice
It caves in phenomenon.Molecular sieve sial made from post treatment method is relatively high, but that there are preparation processes is complicated, molecular sieve crystallinity loss compared with
Greatly, the shortcomings of lattice easily collapses, yield is low, of high cost, environmental pollution is serious.
Direct synthesis technique refers to directly preparing high silica alumina ratio Y type molecular sieve without post-processing, single sintering.It is wherein main
Including：
(1) template agent method is used.Include mainly：Organic template agent method such as quaternary ammonium salt, quaternary ammonium base or crown ether-like
(US55490881、US5116590、US4965059、US4931267、US4714601、EP 0887310、CN1145278、
CN1226875), the inorganic template agent method (US4333859, US4309313) such as cesium salt, caesium alkali.This method feature is synthetic zeolite
Silica alumina ratio between 6-24, product property stablize, have higher hydrothermal stability, higher surface acid strength, but synthesize
Time is longer, and cost increases, and is unfavorable for industrial production.
(2) template agent method is not used.It is only through proportioning, crystallization condition and the directed agents and crystal seed for adjusting reactant
Dosage realizes synthesis, and feature is the silica alumina ratio of synthetic zeolite between 5.6-7.5.
CN1621348 and CN1621349 discloses the method for preparing high silica alumina ratio NaY molecular sieve, i.e., is reacted in high alkalinity
Gel mixture crystallization for a period of time after, being separately added into acidic materials reduces its basicity；Or addition silicon-containing material, it is solidifying to increase reaction
Glue feeds intake silica alumina ratio, to obtain compared with high silica alumina ratio NaY molecular sieve, but its one-pot yield, silicon source utilization rate is relatively low, and technique is multiple
It is miscellaneous.
CN101767799 discloses the method for preparing high silicon aluminium ratio small crystal NaY molecular sieve, i.e., stirs at a lower temperature
It mixes aging and prepares directed agents, matched by modulation directed agents and reaction gel, to obtain compared with high silicon aluminium ratio small crystal NaY molecule
Sieve.But it is relatively low that there are single-autoclave yield rates, the lower defect of silicon source utilization rate, while cooling device increases synthesis cost, economy effect
Benefit reduces.
CN101254929 discloses the method for preparing high silica alumina ratio NaY molecular sieve, i.e., by high alkalinity silica-alumina gel crystallization one
It after the section time, is added in low alkalinity silica-alumina gel, continues crystallization, to obtain compared with high silica alumina ratio NaY molecular sieve.But the method
Complex process, one-pot yield is relatively low, and pollutant discharge amount is larger.
It is asked therefore it provides a kind of preparation method of high silica alumina ratio NaY type molecular sieve becomes this field technology urgently to be resolved hurrily
Topic.
Invention content
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of preparations of high silica alumina ratio NaY type molecular sieve
Method, this method cost is relatively low, simple for process, crystallization time is short, yield and silicon source utilization rate are high, can be with synthesizing Si-Al ratio
5.5-6.5, crystallite dimension are the NaY molecular sieve of 200-500nm.
In order to achieve the above objectives, the present invention provides a kind of preparation method of high silica alumina ratio NaY type molecular sieve, this method with
Organosilan is as the direct synthesizing high-silicon aluminium ratio NaY type molecular sieves of accelerating agent comprising following steps：
Step 1, according to Na2O:Al2O3:SiO2:H2O=(15-20):1:(10-30):The molar ratio of (240-450),
It is aged after silicon source, silicon source, alkali source, organosilan and deionized water are mixed, directed agents is made；Wherein, by having
The SiO that machine silane introduces2Amount accounts for SiO in directed agents2The 0-20wt% of total amount；
Step 2, according to Na2O:Al2O3:SiO2:H2O=(2-6):1:(5.5-10.5):(50-150's) always feeds intake mole
Than under conditions of 15-60 DEG C, deionized water, organosilan and directed agents being sequentially added into silicon source and silicon source, mixing is stirred
It mixes, reaction gel is made；Wherein, the Al introduced by directed agents2O3Amount account for Al in reaction gel2O3The 5-20wt% of total amount,
The SiO introduced by organosilan2Amount accounts for SiO in reaction gel2The 0-20wt% of total amount；
Step 3, reaction gel made from step (2) is subjected to static crystallization, is then filtered, washed, dries, obtains high silicon
Aluminium ratio NaY type molecular sieves；
Wherein, the SiO introduced by organosilan in step (1)2Amount accounts for SiO in directed agents2Lead in total amount, with step (2)
Cross the SiO of organosilan introducing2Amount accounts for SiO in reaction gel2Total amount is 0wt% when the two difference.
In the art, it is generally recognized that silica alumina ratio is high silica alumina ratio 5.0 or more, and according to technology provided by the invention
The silica alumina ratio for the molecular sieve that scheme obtains can reach 5.5-6.5, be consequently belonging to the high Si-Al molecular sieve of this field identification.
Present invention research is found：Addition organosilicon can effectively improve the silicon of product as accelerating agent in the reaction system
Aluminium ratio, and further study show that polarity, the length of branch of silane can influence its function and effect, wherein branch
The influence of length becomes apparent：The shorter organosilicon product of branch is more apparent to the function and effect for improving silica alumina ratio.In addition,
Addition organosilicon can effectively shorten crystallization time.
When the prior art directly prepares high silicon Y molecular sieve, SiO in synthesized gel rubber molar ratio2:Al2O3Usually (10-
25):1, i.e. silica alumina ratio is usually (10-25), even higher, and the silica alumina ratio for the product being finally prepared usually only 6.5
Left and right, even lower, so the utilization rate of silicon source wants much lower, and utilization rate is generally all less than 60%.And the present invention provides
Technical solution when preparing reaction gel, SiO in molar ratio2:Al2O3For (5.5-10.5):1, i.e. silica alumina ratio is
(5.5-10.5), and the silica alumina ratio for the product being finally prepared has reached 5.5-6.5, the utilization rate of silicon source reached 60% with
On.
In the above-mentioned methods, the SiO introduced by organosilan in step (1)2Amount accounts for SiO in directed agents2Total amount, with step
Suddenly the SiO introduced by organosilicon in (2)2Amount accounts for SiO in reaction gel2Total amount is 0wt% when the two difference, is primarily referred to as：
Under the premise of ensureing that reaction system introduces organosilan, in directed agents and reaction gel, organosilan adds when can be different
Add, if such as organosilan is added in directed agents, then the organosilan in reaction gel can select to add；If opposite
Organosilan is added in reaction gel, then the organosilan in directed agents can then select to add.
In the above-mentioned methods, it is preferable that in step (1), the temperature being aged is 10-40 DEG C, more preferably 20-30
℃；The time of the ageing is 12 hours or more, more preferably 12-192 hours.
In technical solution provided by the invention, the water in molar ratio described in step (1) and step (2) comes from
Water in deionized water and silicon source.
In the above-mentioned methods, it is preferable that in step (1), the molar ratio is Na2O:Al2O3:SiO2:H2O=
(15-20):1:(10-25):(240-450)。
In the above-mentioned methods, it is preferable that in step (2), total molar ratio is Na2O:Al2O3:SiO2:H2O=
(2.5-3.5):1:(7-10):(85-95)。
In the above-mentioned methods, it is preferable that in step (3), when carrying out static crystallization, controlling crystallizing temperature is 90-110
DEG C, crystallization time is 18-72 hours.The present invention provides technical solution by the way of static crystallization, and which is amplified in industry
Only need to control room temperature when production to the heating rate of crystallization temperature, controllability is stronger.
In the above-mentioned methods, it is preferable that in step (1), the silicon source includes the waterglass and Ludox one kind of liquid
Or several combination；Source of aluminium includes sodium metaaluminate and/or aluminum sulfate；The alkali source includes sodium hydroxide.
In the above-mentioned methods, it is preferable that in step (2), the silicon source includes c-type silica gel (also referred to as gross porosity microballoon
Silica gel), the combination of white carbon, water quenching sodium metasilicate, one or more of Ludox and waterglass；Source of aluminium includes meta-aluminic acid
Sodium and/or aluminum sulfate；The alkali source includes sodium hydroxide.
In the above-mentioned methods, it is preferable that in step (1) and step (2), the organosilan includes having formula 1 to formula 3
The combination of one or more of the compound of shown structure
R-Si(OCH3)3Formula 1
R-Si(OC2H5)3Formula 2
In above formula, R1、R2Include saturated hydrocarbyl, vinyl, aminopropyl, halogen propyl and the urea third that carbon number is 1-10 with R
Any one in base；Wherein, R1And R2For identical group or different groups.
In technical solution provided by the invention, the organosilan includes alkyl trimethoxysilane, aminopropyl front three
Oxysilane, r-chloropropyl trimethoxyl silane, bromopropyl trimethoxy silane, iodine propyl trimethoxy silicane, vinyl front three
Oxysilane, urea propyl trimethoxy silicane, alkyl triethoxysilane, aminopropyl triethoxysilane, three ethoxy of chloropropyl
Base silane, vinyltriethoxysilane, urea propyl-triethoxysilicane, dialkyldimethoxysilane, dialkyl group diethoxy
The combination of one or more of base silane；Wherein, the carbon number of the alkyl is 1-10.
In technical solution provided by the invention, the waterglass, water quenching sodium metasilicate, Ludox, c-type silica gel (are also known as it
For gross porosity microsphere silica gel) all can be conventional commercial reagent, be not particularly limited.Such as waterglass can be Beijing Red Star chemical industry
The waterglass of factory's production, without being limited thereto, SiO in waterglass2Content can be 28.08wt%, Na2The content of O can be
8.83wt%；Ludox can be the Ludox of Qingdao Marine Chemical Co., Ltd.'s production, without being limited thereto, SiO in Ludox2's
Content can be 40.00wt%, Na2The content of O can be 0.40wt%；C-type silica gel be also referred to as gross porosity microsphere silica gel (Gu
State), belong to one kind of silica gel, can be conventional commercial product, be not particularly limited, such as can be Kong Rong >=0.78cm3/
The Ludox product of g.The organosilan can also be this field conventional commercial reagent, such as can be commercially available chloropropyl three
Ethoxysilane, mass percentage content can be 98.00%；It can also be the alkyl in commercially available alkyl triethoxysilane
Triethoxysilane, mass percentage content can be 98%, without being limited thereto.
The present invention is the study found that when adding above-mentioned organosilan into system, since a coordinate bond of silane is Si-
C keys, bond energy are higher, it is not easy to be broken.When depolymerization, condensation occur in directed agents system for sial species, the presence of Si-C keys
The coordination campaign for affecting sial atom makes the small nucleus framework si-al ratio formed in directed agents system change.Due to
The potential energy of silica aluminium key is less than silica silicon key, therefore the presence of Si-C keys makes small nucleus in directed agents system be intended to Silicon-rich knot
The silica alumina ratio of structure, synthesis of molecular sieve has raised trend.May be as promotion crystallization because being added in reaction gel system
Machine silane while silicon-carbon bonds influence silicon, aluminium atom coordination, plays certain promotion to nucleation and crystal growth process and makees
With shortening crystallization time.The mechanism that this shortening crystallization time improves silica alumina ratio still waits for further studying.
The present invention also provides a kind of high silica alumina ratio NaY type molecular sieve being prepared by the above method, the high silica alumina ratios
NaY type molecular sieves have following excellent properties：
1) silica alumina ratio has reached 5.5-6.5；
2) crystallite dimension is 200-500nm；
3) relative crystallinity of molecular sieve is higher than 90%.
Beneficial effects of the present invention：
1) technical solution provided by the invention introduces organosilan accelerating agent into system, shortens crystallization time so that
There is the crystallization time of NaY molecular sieve diffraction maximum by shortening to 18h for 24 hours, improves the silica alumina ratio of sintetics, improve product
Heat and hydrothermal stability, improve its catalytic activity；
2) technical solution provided by the invention using organosilan as accelerating agent synthesizing high-silicon aluminium than NaY molecular sieve, finally
The relative crystallinity for the molecular sieve being prepared is higher than 90%, and silica alumina ratio 5.5-6.5, crystallite dimension is in 200-500nm；
3) technical solution provided by the invention has raw material availability height, the yield height (one-pot of single preparation process simultaneously
Yield can reach 20-30%, and the silicon source utilization rate of single preparation process reaches 60-80%, than traditional hydrothermal crystallization method
Yield improves 15-20 percentage points), the features such as crystallization time is short, and utilization rate of equipment and installations is high, and blowdown is few；
4) compared with prior art, technical solution provided by the invention has high income, and product silica alumina ratio is high, crystallization time
Short advantage.
Description of the drawings
Fig. 1 is the XRD spectra for the high silica alumina ratio NaY type molecular sieve that embodiment 9 provides；
Fig. 2 is the XRD spectra for the NaY type molecular sieves that comparative example 1 provides；
Target XRD diagram in the NaY type molecular sieve silica flours that Fig. 3 provides for embodiment 9 and comparative example 1；
Fig. 4 is the SEM electron microscopes for the high silica alumina ratio NaY type molecular sieve that embodiment 9 provides；
Fig. 5 is the SEM electron microscopes for the NaY type molecular sieves that comparative example 1 provides.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
In following embodiment, the relative crystallinity and silica alumina ratio of NaY molecular sieve are all made of Japanese SIMADU Lab XRD-
6000 type X-ray diffractometers are tested.Experiment condition is：CuKa is radiated, Ni filtering, continuous scanning, tube voltage 40kv, tube current
For 30mA, step width 0.02.Using (311), (511,333), (440), (642), (822,660), (555,751), (664) crystal face
The sum of diffraction peak areas, according to the following formula Y types phase zeolite relative crystallinity Xi
Xi=Xr (∑ Ai/ ∑ Ar)
In formula, Xr is the crystallinity 93% of standard specimen, and ∑ Ai is the sum of eight peak areas of sample to be tested, and ∑ Ar is standard specimen
The sum of eight peak areas.
The assay method of silica alumina ratio according to SH/T0339-92 standard methods (referring to《Standard of chemical industry collects》, middle national standard
Quasi- publishing house, version in 2000).The silica alumina ratio of y-type zeolite is calculated using (555) diffraction maximum：Take 2 θ of angle of diffraction calculated value of silica flour
Si=28.443 °, to correct the position of sample to be tested diffraction maximum：
2 θ (school)=2 θ (survey)-(- 2 θ Si of 2 θ Si (survey))
Then lattice constant a is calculated：
In formula：A- lattice constants/
1 radiation wavelengths of λ-Cu-K α
(h2+k2+l2The interference index quadratic sum of)-diffracted ray.
Under this experiment condition, (θ (school)) a=6.671/sin.
According to Breck-Flanigen formula：
Si/Al=(25.858-a)/(a-24.191)
Calculate y-type zeolite silica alumina ratio.
Embodiment 1
Present embodiments provide a kind of preparation method of high silica alumina ratio NaY type molecular sieve comprising following steps：
It weighs 11.34g sodium hydrate solids to be dissolved in 56.09g deionized waters, after being cooled to room temperature, sodium metaaluminate is added
3.12g(Al2O3Content be 45wt%, Na2The content of O is 41wt%), high alkalinity sodium aluminate solution, stirring is made
Lower dropwise addition 55.8g waterglass (SiO2Content be 28.08wt%, Na2The content of O is 8.81wt%), it is uniformly mixed, and stirring
It mixes and is aged the obtained directed agents of 12h under state.Constitutive molar ratio in the directed agents is Na2O:Al2O3:SiO2:H2O=17:1:18:
369。
10.70gC types silica gel (being called gross porosity microsphere silica gel) is weighed to be placed in beaker, then weigh 6.00g sodium metaaluminates in
In beaker, after being uniformly mixed with c-type silica gel, 25g deionized waters are added, after mixing, 1.97g methyl trimethoxy oxygen are added
Base silane is uniformly mixed, and above-mentioned directed agents 24.11g is added, and stirs evenly to form white " milky " gel state, and reaction is solidifying
Glue mixture gross mass is 67.78g, constitutive molar ratio Na2O:Al2O3:SiO2:H2O=2.91:1:7.64:81.30.
Reaction gel mixture is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of static crystallization 20h,
Then it is dried to obtain NaY molecular sieve product by filtration washing.
The quality for the NaY molecular sieve product that the present embodiment is prepared is 15.78g, and the silicon source of one-pot NaY molecular sieve utilizes
Rate is 75.93%.It is 100% that XRD, which tests relative crystallinity, silica alumina ratio 5.80.
Embodiment 2
Present embodiments provide a kind of preparation method of high silica alumina ratio NaY type molecular sieve.Wherein：
The preparation of directed agents is with various raw material sources with embodiment 1.
It weighs 9.94gC type silica gel to be placed in beaker, then weighs 6.00g sodium metaaluminates in beaker, stirred with c-type silica gel
It mixes after mixing, 25g deionized waters and 5g Ludox (SiO in Ludox is added2Content be 40.00wt%, Na2O's contains
Amount can be 0.40wt%) after mixing, 3.94g dimethyl diethoxysilanes are added, are uniformly mixed, are added above-mentioned
Directed agents 23.82g, stirs evenly to form uniform white " milky " gel state, and the gross mass of reaction gel mixture is
73.70g, constitutive molar ratio Na2O:Al2O3:SiO2:H2O=2.90:1:8.33:86.67.
Reaction gel mixture is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, 100 DEG C of static crystallizations for 24 hours,
Then it is dried to obtain NaY molecular sieve product by filtration washing.
The quality for the NaY molecular sieve product that the present embodiment is prepared is 15.94g, and the silicon source of one-pot NaY molecular sieve utilizes
Rate is 67.35%.It is 98% that XRD, which tests relative crystallinity, silica alumina ratio 5.61.
Embodiment 3
Present embodiments provide a kind of preparation method of high silica alumina ratio NaY type molecular sieve.Wherein：
The preparation of directed agents is with various raw material sources with embodiment 1.
It weighs 7.62gC types silica gel (gross porosity microsphere silica gel) to be placed in beaker, sequentially adds 25g deionized waters, 5.89g chlorine
Propyl trimethoxy silicane is uniformly mixed, and above-mentioned directed agents 14.94g is added, then weighs 3.00g sodium metaaluminates and 2g
Aluminum sulfate is dissolved in above-mentioned epoxy glue, stirs evenly to form uniform white " milky " gel state, reaction gel mixture it is total
Quality is 58.45g, constitutive molar ratio Na2O:Al2O3:SiO2:H2O=3.06:1:9.46:122.48.
Reaction gel mixture is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of static crystallization 48h,
Then it is dried to obtain NaY molecular sieve product by filtration washing.
The quality for the NaY molecular sieve product that the present embodiment is prepared is 15.87g, and the silicon source of one-pot NaY molecular sieve utilizes
Rate is 64.70%.It is 92% that XRD, which tests relative crystallinity, silica alumina ratio 6.12.
Embodiment 4
Present embodiments provide a kind of preparation method of high silica alumina ratio NaY type molecular sieve.Wherein：
Various raw material sources are the same as embodiment 1.
It weighs 11.46g sodium hydrate solids to be dissolved in 60.16g water, after being cooled to room temperature, sodium metaaluminate 3.24g is added,
High alkalinity sodium aluminate solution is made, after stirring evenly, after 0.77g octyltri-ethoxysilanes are added dropwise, is added dropwise under stirring
54.90g waterglass is uniformly mixed, and maintains to be aged the obtained directed agents of 12h under stirring.Composition mole in the directed agents
Than for Na2O:Al2O3:SiO2:H2O=17:1:18:369.
10.55gC types silica gel (being called gross porosity microsphere silica gel) is weighed to be placed in beaker, then weigh 6.00g sodium metaaluminates in
In beaker, after being uniformly mixed with c-type silica gel, 25g deionized waters are added, after mixing, 1.97g methyl trimethoxy oxygen are added
Base silane is uniformly mixed, and above-mentioned directed agents 23.82g is added, and stirs evenly to form white " milky " gel state, and reaction is solidifying
Glue mixture gross mass is 67.34g, constitutive molar ratio Na2O:Al2O3:SiO2:H2O=3.89:1:7.55:80.98).
Static crystallization is carried out according to the method in embodiment 1, finally obtains NaY molecular sieve product 15.72g, the phase of product
It is 91% to crystallinity, silica alumina ratio 5.65.
Embodiment 5
Present embodiments provide a kind of preparation method of high silica alumina ratio NaY type molecular sieve.Wherein：
Various raw material sources are the same as embodiment 1.
It weighs 11.46g sodium hydrate solids to be dissolved in 60.16g water, after being cooled to room temperature, sodium metaaluminate 3.24g is added,
High alkalinity sodium aluminate solution is made, after stirring evenly, after 1.17g r-chloropropyl trimethoxyl silanes are added dropwise, is dripped under stirring
Add 54.90g waterglass, be uniformly mixed, and maintains to be aged the obtained directed agents of 12h under stirring.Composition in the directed agents rubs
You are than being Na2O:Al2O3:SiO2:H2O=17:1:18:369.
10.53gC types silica gel (being called gross porosity microsphere silica gel) is weighed to be placed in beaker, then weigh 6.00g sodium metaaluminates in
In beaker, after being uniformly mixed with c-type silica gel, 25g deionized waters are added, after mixing, 1.97g methyl trimethoxy oxygen are added
Base silane is uniformly mixed, and above-mentioned directed agents 25.81g is added, and stirs evenly to form white " milky " gel state, and reaction is solidifying
Glue mixture gross mass is 69.31g, constitutive molar ratio Na2O:Al2O3:SiO2:H2O=3.00:1:7.61:83.13.
Static crystallization is carried out according to the method in embodiment 1, finally obtains NaY molecular sieve product 15.86g, product is opposite
Crystallinity is 96%, silica alumina ratio 5.74.
Embodiment 6
Present embodiments provide a kind of preparation method of high silica alumina ratio NaY type molecular sieve.Wherein：
Various raw material sources are the same as embodiment 1.
It weighs 11.46g sodium hydrate solids to be dissolved in 60.16g water, after being cooled to room temperature, sodium metaaluminate 3.24g is added,
High alkalinity sodium aluminate solution is made, after stirring evenly, after 1.59g methyltriethoxysilane is added dropwise, is added dropwise under stirring
54.90g waterglass is uniformly mixed, and is aged 12h under stirring and directed agents are made.Constitutive molar ratio in the directed agents
For Na2O:Al2O3:SiO2:H2O=17:1:18:369.
10.53gC types silica gel (being called gross porosity microsphere silica gel) is weighed to be placed in beaker, then weigh 6.00g sodium metaaluminates in
In beaker, after being uniformly mixed with c-type silica gel, 20g deionized waters are added, 1.97g is added after mixing in 7g waterglass
Methyltrimethoxysilane is uniformly mixed, and above-mentioned directed agents 30.63g is added, stirs evenly to form white " milky " gel
State, reaction gel mixture gross mass are 76.13g, constitutive molar ratio Na2O:Al2O3:SiO2:H2O=3.25:1:8.87:
88.21。
Crystallization is carried out according to the method in embodiment 1, finally obtains high silica alumina ratio NaY type zeolite product 15.92g, is produced
Product relative crystallinity is 96%, silica alumina ratio 5.64.
Embodiment 7
Present embodiments provide a kind of preparation method of high silica alumina ratio NaY type molecular sieve.Wherein：
Various raw material sources are the same as embodiment 1.
It weighs 11.46g sodium hydrate solids to be dissolved in 60.16g water, after being cooled to room temperature, sodium metaaluminate 3.24g is added,
High alkalinity sodium aluminate solution is made, after stirring evenly, after 0.78g r-chloropropyl trimethoxyl silanes are added dropwise, is dripped under stirring
Add 54.90g waterglass, be uniformly mixed, and is aged 12h under stirring and directed agents are made.Composition mole in the directed agents
Than for Na2O:Al2O3:SiO2:H2O=17:1:18:369.
It weighs 12.97gC type silica gel to be placed in beaker, then weighs 6.00g sodium metaaluminates in beaker, stirred with c-type silica gel
It mixes after mixing, 25g deionized waters is added, after mixing, 1.96g methyltrimethoxysilane is added, is stirred
It is even, above-mentioned directed agents 25.41g is added, stirs evenly to form uniform white " milky " gel state, the total matter of reaction gel mixture
Amount is 69.38g, constitutive molar ratio Na2O:Al2O3:SiO2:H2O=2.98:1:8.96:82.70.
Reaction gel mixture is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, 100 DEG C of static crystallizations for 24 hours,
Then NaY molecular sieve product, quality 15.84g are dried to obtain by filtration washing.It is 90% that XRD, which tests relative crystallinity, silicon
Aluminium ratio is 6.11.
Embodiment 8
Present embodiments provide a kind of preparation method of high silica alumina ratio NaY type molecular sieve.Wherein：
Various raw material sources are the same as embodiment 1.
It weighs 11.46g sodium hydrate solids to be dissolved in 60.16g water, after being cooled to room temperature, sodium metaaluminate 3.22g is added,
High alkalinity sodium aluminate solution is made, after stirring evenly, after 1.21g methyltrimethoxysilane is added dropwise, continues to stir, be added dropwise
54.90g waterglass is uniformly mixed, and is aged 12h under stirring and directed agents are made.Constitutive molar ratio in the directed agents
For Na2O:Al2O3:SiO2:H2O=17:1:18:369.
12.64gC types silica gel (being also gross porosity microsphere silica gel) is weighed to be placed in beaker, then weigh 6.00g sodium metaaluminates in
In beaker, after being uniformly mixed with c-type silica gel, 35g deionized waters are added, after mixing, 1.96g methyl trimethoxy oxygen are added
Base silane is uniformly mixed, and above-mentioned directed agents 24.77g is added, and stirs evenly to form uniform white " milky " gel state,
Reaction gel mixture gross mass is 78.42g, constitutive molar ratio Na2O:Al2O3:SiO2:H2O=2.95:1:8.75:
101.05。
Reaction gel mixture is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, 100 DEG C of static crystallizations for 24 hours,
Then NaY molecular sieve product, quality 15.74g are dried to obtain by filtration washing.It is 96% that XRD, which tests relative crystallinity, silicon
Aluminium ratio is 6.47.
Embodiment 9
Present embodiments provide a kind of preparation method of high silica alumina ratio NaY type molecular sieve.Wherein：
Various raw material sources are the same as embodiment 1.
It weighs 11.35g sodium hydrate solids to be dissolved in 59.89g water, after being cooled to room temperature, sodium metaaluminate 3.24g is added,
High alkalinity sodium aluminate solution is made, after stirring evenly, after 1.57g dimethyl diethoxysilanes are added dropwise, continues to stir, be added dropwise
55.0g waterglass is uniformly mixed, and is aged 12h under stirring and directed agents are made.Constitutive molar ratio in the directed agents is
Na2O:Al2O3:SiO2:H2O=17:1:18:369.
It weighs 12.32gC type silica gel to be placed in beaker, then weighs 6.00g sodium metaaluminates in beaker, stirred with c-type silica gel
It mixes after mixing, 35g deionized waters is added, after mixing, 1.97g dimethyl diethoxysilanes are added, are stirred
Uniformly, above-mentioned directed agents 18.11g is added, stirs evenly to form uniform white " milky " gel state, reaction gel mixture is total
Quality is 71.42g, constitutive molar ratio Na2O:Al2O3:SiO2:H2O=2.58:1:8.32:94.14.
The mixture of reaction gel is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of static crystallizations
Then 48h is dried to obtain NaY molecular sieve product, quality 15.86g by filtration washing.XRD tests relative crystallinity
92%, silica alumina ratio 5.63.The product XRD spectra such as Fig. 1, SEM electron microscopes are as shown in Figure 4.
Comparative example 1
This comparative example provides a kind of preparation method for not adding organosilan synthesis NaY type molecular sieves.Wherein：
Various raw material sources are the same as embodiment 1.
It weighs 11.34g sodium hydrate solids to be dissolved in 59.99g water, after being cooled to room temperature, sodium metaaluminate 3.34g is added,
High alkalinity sodium aluminate solution is made, 54.8g waterglass is added dropwise under stirring, is uniformly mixed, and be aged under stirring
Directed agents are made in 12h.Constitutive molar ratio in the directed agents is Na2O:Al2O3:SiO2:H2O=17:1:18:369.
It weighs 12.15gC type silica gel to be placed in beaker, then weighs 6.00g sodium metaaluminates in beaker, stirred with c-type silica gel
It mixes after mixing, 25g deionized waters is added, above-mentioned directed agents 23.82g is added after mixing, stir evenly to be formed uniformly
White " milky " gel state, reaction gel mixture gross mass be 66.98g, constitutive molar ratio Na2O:Al2O3:SiO2:H2O
=2.89:1:8.45:80.98.
Reaction gel mixture is fitted into the stainless steel cauldron of liner tetrachloro-ethylene, in 100 DEG C of static crystallization 48h,
Then NaY molecular sieve product, quality 15.86g, the silicon source utilization rate of one-pot NaY molecular sieve are dried to obtain by filtration washing
It is 62.37%.It is 96% that XRD, which tests relative crystallinity, silica alumina ratio 5.27.The product XRD spectra such as Fig. 2, SEM electron microscopes are such as
Shown in Fig. 5.
Target XRD diagram in the NaY molecular sieve silica flour that embodiment 9 and comparative example 1 are prepared as shown in figure 3, wherein 28 °-
Peak between 29 ° is the characteristic peak of silica flour, and the peak between 31 ° -32 ° is the characteristic peak of sample.
Claims (10)
1. a kind of preparation method of high silica alumina ratio NaY type molecular sieve, this method directly synthesize height using organosilan as accelerating agent
Silica alumina ratio NaY type molecular sieve comprising following steps：
Step 1, according to Na2O:Al2O3:SiO2:H2O=(15-20):1:(10-30):The molar ratio of (240-450), by silicon
Source, silicon source, alkali source, organosilan and deionized water are aged after being mixed, and directed agents are made；Wherein, pass through organosilicon
The SiO that alkane introduces2Amount accounts for SiO in directed agents2The 0-20wt% of total amount；
Step 2, according to Na2O:Al2O3:SiO2:H2O=(2-6):1:(5.5-10.5):Total molar ratio of (50-150),
Under conditions of 15-60 DEG C, deionized water, organosilan and directed agents are sequentially added into silicon source and silicon source, are mixed, and are made
Reaction gel；Wherein, the Al introduced by directed agents2O3Amount account for Al in reaction gel2O3The 5-20wt% of total amount, by having
The SiO that machine silane introduces2Amount accounts for SiO in reaction gel2The 0-20wt% of total amount；
Step 3, reaction gel made from step (2) is subjected to static crystallization, is then filtered, washed, dries, obtains high silica alumina ratio
NaY type molecular sieves；
Wherein, the SiO introduced by organosilan in step (1)2Amount accounts for SiO in directed agents2By having in total amount, with step (2)
The SiO that machine silane introduces2Amount accounts for SiO in reaction gel2Total amount is 0wt% when the two difference.
2. according to the method described in claim 1, wherein, in step (1), the temperature of the ageing is 10-40 DEG C；It is described old
The time of change is 12 hours or more, preferably 12-192 hours.
3. method according to claim 1 or 2, wherein in step (1), the molar ratio is Na2O:Al2O3:
SiO2:H2O=(15-20):1:(10-25):(240-450)；
Preferably, in step (2), total molar ratio is Na2O:Al2O3:SiO2:H2O=(2.5-3.5):1:(7-
10):(85-95)。
4. according to the method described in claim 1, wherein, in step (3), when carrying out static crystallization, controlling crystallizing temperature is
90-110 DEG C, crystallization time is 18-72 hours.
5. according to the method described in claim 1, wherein, in step (1), the silicon source includes that waterglass and Ludox are a kind of
Or several combination；
In step (2), the silicon source includes one kind in c-type silica gel, white carbon, water quenching sodium metasilicate, Ludox and waterglass
Or several combination.
6. method according to claim 1 or 5, wherein in step (1) and step (2),
Source of aluminium includes sodium metaaluminate and/or aluminum sulfate；
The alkali source includes sodium hydroxide.
7. according to the method described in claim 1,5 or 6, wherein in step (1) and step (2), the organosilan includes
Combination with one or more of compound of structure shown in formula 1 to formula 3
R-Si(OCH3)3Formula 1
R-Si(OC2H5)3Formula 2
In above formula, R1、R2Include in saturated hydrocarbyl, vinyl, aminopropyl, halogen propyl and the urea propyl that carbon number is 1-10 with R
Any one；Wherein, R1And R2For identical group or different groups.
8. according to the method described in claim 7, wherein, the halogen propyl includes chloropropyl, bromopropyl or iodine propyl.
9. a kind of high silica alumina ratio NaY type molecular sieve being prepared by claim 1-8 any one of them methods, the high sial
Silica alumina ratio than NaY type molecular sieves is 5.5-6.5.
10. high silica alumina ratio NaY type molecular sieve according to claim 9, wherein the crystallite dimension of the molecular sieve is 200-
500nm；
Preferably, the relative crystallinity of the molecular sieve is more than 90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710151678.3A CN108569705B (en) | 2017-03-14 | 2017-03-14 | NaY type molecular sieve with high silicon-aluminum ratio and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710151678.3A CN108569705B (en) | 2017-03-14 | 2017-03-14 | NaY type molecular sieve with high silicon-aluminum ratio and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108569705A true CN108569705A (en) | 2018-09-25 |
| CN108569705B CN108569705B (en) | 2021-02-05 |
Family
ID=63575720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710151678.3A Active CN108569705B (en) | 2017-03-14 | 2017-03-14 | NaY type molecular sieve with high silicon-aluminum ratio and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108569705B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114074947A (en) * | 2020-08-14 | 2022-02-22 | 中国石油大学(北京) | Nanosheet Y molecular sieve aggregate and preparation method and application thereof |
| CN114684831A (en) * | 2020-12-31 | 2022-07-01 | 中海油天津化工研究设计院有限公司 | High-silica-alumina-ratio Y molecular sieve with high relative crystallinity and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007331982A (en) * | 2006-06-15 | 2007-12-27 | Saitama Univ | Method for manufacturing hydrophobic zeolite |
| CN103172082A (en) * | 2013-04-25 | 2013-06-26 | 哈尔滨工业大学 | Preparation method of mesoporous-containing Y-shaped molecular sieve |
| CN103896303A (en) * | 2012-12-25 | 2014-07-02 | 大连理工大学 | Method for directly synthesizing high silica-alumina ratio ultrafine NaY molecular sieve |
| CN104692412A (en) * | 2013-12-06 | 2015-06-10 | 中国石油大学(北京) | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve |
| CN104843738A (en) * | 2015-04-02 | 2015-08-19 | 北京工业大学 | Synthesization method for small-grained Y molecular sieve with controllable grain size |
-
2017
- 2017-03-14 CN CN201710151678.3A patent/CN108569705B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007331982A (en) * | 2006-06-15 | 2007-12-27 | Saitama Univ | Method for manufacturing hydrophobic zeolite |
| CN103896303A (en) * | 2012-12-25 | 2014-07-02 | 大连理工大学 | Method for directly synthesizing high silica-alumina ratio ultrafine NaY molecular sieve |
| CN103172082A (en) * | 2013-04-25 | 2013-06-26 | 哈尔滨工业大学 | Preparation method of mesoporous-containing Y-shaped molecular sieve |
| CN104692412A (en) * | 2013-12-06 | 2015-06-10 | 中国石油大学(北京) | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve |
| CN104843738A (en) * | 2015-04-02 | 2015-08-19 | 北京工业大学 | Synthesization method for small-grained Y molecular sieve with controllable grain size |
Non-Patent Citations (1)
| Title |
|---|
| 钟炳等: "《新世纪的催化科学与技术：第十届全国催化学术会议论文集》", 30 September 2000, 山西科学技术出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114074947A (en) * | 2020-08-14 | 2022-02-22 | 中国石油大学(北京) | Nanosheet Y molecular sieve aggregate and preparation method and application thereof |
| CN114684831A (en) * | 2020-12-31 | 2022-07-01 | 中海油天津化工研究设计院有限公司 | High-silica-alumina-ratio Y molecular sieve with high relative crystallinity and preparation method thereof |
| CN114684831B (en) * | 2020-12-31 | 2024-02-09 | 中海油天津化工研究设计院有限公司 | High silicon-aluminum ratio Y molecular sieve with high relative crystallinity and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108569705B (en) | 2021-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103803579B (en) | Core-shell structured ZSM-5 composite molecular sieve and preparation method thereof | |
| US7494951B2 (en) | Process for the manufacture of catalysts used for producing para-xylene by toluene shape selective alkylation | |
| CN100404418C (en) | Preparation method of high silicon aluminium ratio small crystal NaY molecular sieve | |
| CN101767799A (en) | Method for synthesizing high-silicon small grain NaY molecular sieve | |
| CN104876238A (en) | Method for assisted synthesis of molecular sieve by means of ultraviolet radiation | |
| CN103803576B (en) | A kind of low silica-alumina ratio ZSM-48 molecular sieve and preparation method thereof | |
| CN106348312A (en) | Inorganic synthesis method for regulating morphology of ZSM-5 molecular sieve | |
| CN108569705A (en) | A kind of high silica alumina ratio NaY type molecular sieve and preparation method thereof | |
| CN106582805A (en) | Method for preparing SAPO-11/MOR composite molecular sieve with preset MOR crystal seeds | |
| CN109626394A (en) | A method of SAPO-35 molecular sieve is prepared by template of N- methyl piperidine | |
| CN114749205B (en) | Preparation method of catalyst for preparing low-carbon olefin by directly cracking crude oil | |
| CN104891527A (en) | Method for synthesizing mordenite | |
| CN1785807A (en) | High silicon aluminium ratio small crystal NaY molecular sieve | |
| CN106276944A (en) | A kind of HTS and synthetic method thereof and application and a kind of method for hydroxylation of phenol | |
| CN105293519A (en) | Synthesis method of ZSM-5/Y composite molecular sieve without using template | |
| CN104591207B (en) | Small-grain NaY-type molecular sieve and preparation method thereof | |
| CN106946268B (en) | A kind of MOR/ZSM-35 composite molecular screen and its synthetic method | |
| CN101190795A (en) | Method for preparing NaY molecular screen by solid-phase conversion | |
| CN106745053A (en) | Microwave synthesizes the method for high selectivity preparing propylene from methanol molecular sieve of Nano zeolite | |
| CN103964466B (en) | 5 molecular sieves of a kind of ZSM and preparation method thereof | |
| CN106276966A (en) | The alkali metal-free system synthetic method of the ZSM-5 molecular sieve that a kind of intracrystalline is phosphorous | |
| CN105776242A (en) | Synthesis method of ZSM-50 molecular sieve | |
| CN104649294B (en) | Method for improving relative crystallinity of synthetic NaY zeolite | |
| CN103964467B (en) | A kind of preparation method of ZSM-5 molecular sieve | |
| CN1124979C (en) | SI-Zn-Al molecular sieve and its synthesizing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |