CN114684831A - High-silica-alumina-ratio Y molecular sieve with high relative crystallinity and preparation method thereof - Google Patents
High-silica-alumina-ratio Y molecular sieve with high relative crystallinity and preparation method thereof Download PDFInfo
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- CN114684831A CN114684831A CN202011637894.7A CN202011637894A CN114684831A CN 114684831 A CN114684831 A CN 114684831A CN 202011637894 A CN202011637894 A CN 202011637894A CN 114684831 A CN114684831 A CN 114684831A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 142
- 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 142
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052796 boron Inorganic materials 0.000 claims abstract description 66
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 239000010703 silicon Substances 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims description 63
- 229910052708 sodium Inorganic materials 0.000 claims description 62
- 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 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 46
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 41
- 238000002425 crystallisation Methods 0.000 claims description 34
- 230000008025 crystallization Effects 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- 238000006467 substitution reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000499 gel Substances 0.000 claims description 18
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 235000019353 potassium silicate Nutrition 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 10
- 230000032683 aging Effects 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 9
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 29
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000010907 mechanical stirring Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- -1 alkyl imidazole Chemical compound 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 238000010306 acid treatment Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910003910 SiCl4 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000009469 supplementation Effects 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
-
- 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
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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)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a Y molecular sieve with high silicon-aluminum ratio and high relative crystallinity and a preparation method thereof. The method comprises the following steps: mixing a silicon source, a guiding agent, an aluminum source and fluoborate to form a gel, wherein the molar ratio of gel materials is 0.5-10 Na2O:1Al2O3:5～40SiO2:80～800H2O is 0.01 to 0.5 of fluoroborate; statically crystallizing the prepared mixed gel at 90-150 ℃ for 6-72 hours to obtain a boron-containing heteroatom Y molecular sieve; and introducing dry gas saturated by a gas-phase isomorphous substituent into the dried boron-containing heteroatom Y molecular sieve, and reacting for 0.1-48 hours at 140-800 ℃ to obtain the high-silica-alumina-ratio Y molecular sieve with high relative crystallinity. The high-silicon-aluminum-ratio Y molecular sieve provided by the invention has the advantages that the relative crystallinity is more than 90%, the silicon-aluminum ratio is more than 10, the preparation process is simple, the production cost is low, and the industrial application prospect is realized.
Description
Technical Field
The invention belongs to the field of molecular sieve materials and preparation thereof, and particularly relates to a high-silica-alumina-ratio Y molecular sieve with high relative crystallinity and a preparation method thereof.
Background
The Y molecular sieve has excellent pore structure and proper surface acidity, and is widely applied to the fields of adsorption, separation, catalysis and the like. The framework of the Y molecular sieve is composed of silicon-oxygen tetrahedron and aluminum-oxygen tetrahedron, and the silicon-aluminum ratio (SiO) of the framework2/Al2O3) Affecting the thermal stability, hydrothermal stability and acidity of the Y molecular sieve. The Y molecular sieve with higher silicon-aluminum ratio has better thermal stability and hydrothermal stability, the framework structure of the molecular sieve is not easily damaged in the catalytic reaction process and the regeneration process, and better catalytic stability and regeneration performance are shown.
The Y molecular sieve with high silicon-aluminum ratio can be obtained by a direct synthesis method and a post-treatment modification method.
In the direct synthesis method, the high silica-alumina ratio Y molecular sieve can be obtained by the steps of adjusting the feeding proportion, adding the template agent and adjusting the process.
In the preparation of the Y molecular sieve with high silica-alumina ratio by adjusting the raw material ratio, the method is more representative: patent CN104118885B discloses a method for synthesizing NaY zeolite with high silica-alumina ratio, which can synthesize NaY zeolite with high silica-alumina ratio in a short crystallization time by adjusting the raw material ratio and the preparation process conditions without using a template agent.
In the preparation of the Y molecular sieve with high silica-alumina ratio by adding the template agent, the method is more representative: patent CN104692413B discloses a method for preparing NaY molecular sieve with high silica-alumina ratio and a product thereof, the method uses nonvolatilizable short-chain alkyl imidazole ionic liquid as a template agent, and the obtained high-silica Y molecular sieve has high crystallinity and the silica-alumina ratio is more than 6; patent CN100390059C discloses a method for synthesizing faujasite with high silica-alumina ratio, which adopts a suitable template agent and adopts a hydrothermal crystallization method to directly synthesize faujasite with high silica-alumina ratio under the condition of less sodium dosage, and the method has the characteristics of short crystallization time and less alkali dosage.
In the preparation of the Y molecular sieve with high silica-alumina ratio by modulation process steps, the method is more representative: patent CN101254929B discloses a preparation method of a NaY molecular sieve with a high silica-alumina ratio, which comprises the steps of firstly preparing high-alkalinity silica-alumina gel obtained by uniformly mixing a conventional guiding agent, a silicon source, an aluminum source and water, then heating and crystallizing the high-alkalinity silica-alumina gel for a period of time, adding low-alkalinity silica-alumina gel, uniformly stirring, and heating to crystallize to obtain the NaY molecular sieve with the high silica-alumina ratio; the patent CN100404418C and the patent CN100443407C adopt a first step of dynamic crystallization and a second step of static crystallization to obtain a high silica alumina ratio small crystal grain NaY molecular sieve with the relative crystallinity of more than 80 percent; the patent CN103896303B discloses a method for directly synthesizing a high-silica-alumina ratio superfine NaY molecular sieve, which adopts dynamic crystallization under the condition of no template agent and no additive, and undergoes at least three sections of temperature programming control crystallization processes, the average grain size of the obtained NaY molecular sieve is between 100 nm and 500nm, and the silica-alumina ratio of a framework is higher than 6.5.
In the post-treatment modification method, the Y molecular sieve with high silica-alumina ratio can be obtained through acid treatment modification, hydrothermal roasting treatment and gas-solid phase modification.
The Y molecular sieve with high silica-alumina ratio can be obtained by acid treatment modification or hydrothermal roasting treatment, but the framework structure of the molecular sieve is easy to damage, the relative crystallinity is obviously reduced, and the stability and the acidity of the Y molecular sieve are greatly influenced. Patent CN103539151B of Shenbao sword et al discloses a preparation method of Y-type zeolite with rich secondary pores and high silica-alumina ratio, which comprises the steps of firstly synthesizing Fe-Y molecular sieve, and then respectively carrying out ammonium exchange and hydrothermal roasting treatment twice, wherein the obtained Y-type zeolite has higher silica-alumina ratio and more rich secondary pores.
The method for obtaining the high-silica-alumina-ratio Y molecular sieve through gas-solid phase modification is representative: in patent CN102553630B, NaY/matrix is prepared by in-situ crystallization, and then the Y-type zeolite catalytic cracking catalyst with high silica-alumina ratio and small crystal grains is prepared by adopting gas phase ultra-stabilization treatment, and the catalyst has high activity and hydrothermal stability and good selectivity of target products.
At present, the research results show that: the silicon-aluminum ratio of the Y molecular sieve directly synthesized by adjusting the feeding ratio is less than 6.0, and the subsequent modification treatment is still needed to improve the silicon-aluminum ratio of the molecular sieve; although the silicon-aluminum ratio of the Y molecular sieve prepared by adopting the template method can reach more than 6.0, the used template is expensive, the production cost is increased, and in addition, the relative crystallinity of the molecular sieve is influenced by the removal of the template, and the environment is polluted; the process conditions for preparing the high-silicon Y molecular sieve by using the fractional crystallization method or the dynamic crystallization method are harsh, the production process is relatively complex, and the yield of a single kettle is low. The preparation of the high-silicon Y molecular sieve by adopting acid treatment or hydrothermal roasting treatment is a method generally applied in the industry at present, but multiple times of exchange, hydrothermal roasting and acid treatment are needed, the process steps are complex, the production cost is high, the framework structure of the molecular sieve is easy to damage in the modification process, the relative crystallinity is obviously reduced, and the stability of the molecular sieve is influenced. Meanwhile, non-framework aluminum generated in the post-treatment process can influence the surface acidity of the Y molecular sieve, so that the catalytic activity of the molecular sieve is influenced.
In conclusion, the analysis of the industrial production and the technical method reported in the literature shows that: the existing technical method for preparing the Y molecular sieve with the high silica-alumina ratio has the disadvantages of high production cost, complex process and low yield, and the obtained molecular sieve has low relative crystallinity and the silica-alumina ratio of the molecular sieve is not high enough.
Disclosure of Invention
Based on the problems of high production cost, low relative crystallinity of the molecular sieve and insufficient silica-alumina ratio of the molecular sieve in the prior art, the invention provides the preparation method of the Y molecular sieve with high silica-alumina ratio, which has simple preparation process, low production cost, industrial application prospect and high relative crystallinity.
The preparation method comprises the steps of firstly obtaining the boron-containing heteroatom Y molecular sieve by a hydrothermal synthesis method, then carrying out gas phase boron removal, silicon supplement and dealumination silicon supplement on the boron-containing heteroatom Y molecular sieve, namely substituting heteroatom boron and partial aluminum in the molecular sieve by silicon to finally obtain the Y molecular sieve with high silicon-aluminum ratio, wherein the Y molecular sieve has higher relative crystallinity, and the specific technical scheme is as follows:
a preparation method of a high-silica-alumina ratio Y molecular sieve with high relative crystallinity comprises the following process steps:
(1) preparing a guiding agent: mixing a silicon source, an aluminum source, alkali and water according to the proportion of (3-45) Na2O:1Al2O3:(5～80)SiO2:(100～800)H2Mixing the O with the molar ratio of 5-60 ℃, stirring completely, and then statically aging for 2-72 hours at 5-60 ℃ to obtain the product;
(2) synthesis of boron-containing heteroatom Y molecular sieve: mixing a silicon source with the guiding agent at 15-60 ℃, adding an aluminum source, and adding fluoborate to prepare gel, wherein the molar ratio of each component in the gel is as follows: (0.5-10) Na2O:1Al2O3:(5～40)SiO2:(80～800)H2O (0.01-0.5) vigorously stirring the fluoborate for 0.5-3 hours; heating the gel to 90-120 ℃, crystallizing for 8-100 hours, and filtering, washing and drying a product after crystallization is finished to obtain the boron-containing heteroatom Y molecular sieve;
(3) gas phase isomorphous substitution of boron containing heteroatom Y molecular sieves: treating the boron-containing heteroatom Y molecular sieve at 100-700 ℃ for 0.1-48 hours, wherein the water content of the dried boron-containing heteroatom Y molecular sieve is lower than 2 wt.%; cooling the dried boron-containing heteroatom Y molecular sieve to 80-600 ℃; under the drying condition, introducing a drying gas saturated by a gas-phase isomorphous substituting agent into the dried boron-containing heteroatom Y molecular sieve, and reacting at the temperature of 120-800 ℃ for 0.1-48 hours; and after the reaction is finished, stopping introducing the dry gas saturated by the gas-phase isomorphous substituting agent, purging for 0.5-12 hours by using the dry gas, and cooling to room temperature to obtain the high-silica-alumina-ratio Y molecular sieve with high relative crystallinity.
According to the preparation method provided by the invention, preferably, the silicon source is one or more of silica gel, silica sol, sodium silicate, white carbon black and water glass; the aluminum source is one or more of aluminum oxide, aluminum hydroxide, aluminum sulfate, sodium metaaluminate and aluminum sol; the alkali is sodium hydroxide; the fluoborate is one or more of ammonium fluoborate, lithium fluoborate, sodium fluoborate and potassium fluoborate.
The preferable molar ratio of each component in the guiding agent is (5-20) Na2O:1Al2O3:(10～50)SiO2:(200～500)H2And O, the aging temperature is preferably 15-50 ℃, and the aging time is preferably 12-48 hours.
The molar ratio of each component in the synthetic gel containing the boron heteroatom Y molecular sieve is preferably as follows: (0.5 to 7) Na2O:1Al2O3:(5～32)SiO2:(150～500)H2O (0.05-0.3) fluoborate, the gelling temperature is preferably 20-50 ℃, the stirring time is preferably 2-4 hours, the crystallization temperature is preferably 95-110 ℃, and the crystallization time is preferably 12-72 hours.
In the gas-phase isomorphous substitution process of the boron-containing heteroatom Y molecular sieve, the drying temperature of the heteroatom Y molecular sieve is preferably 200-650 ℃, the drying time is preferably 0.5-24 hours, the water content of the dried heteroatom Y molecular sieve is preferably lower than 1 wt.%, and the temperature is preferably reduced to 120-400 ℃.
The gas-phase isomorphous substituting agent is one or more of dichlorosilane, trichlorosilane and tetrachlorosilane.
The gas-phase isomorphous substitution reaction temperature of the dried boron-containing heteroatom Y molecular sieve is preferably 150-650 ℃, the reaction time is preferably 0.5-12 hours, and the time of purging with a dry gas after the reaction is finished is preferably 1-6 hours; wherein the drying gas is preferably one or more of drying air, drying helium gas, drying nitrogen gas and drying argon gas.
The preparation method provided by the invention utilizes silane as a gas-phase isomorphous substituent to carry out gas-phase boron removal, dealumination and silicon supplementation on the boron-containing heteroatom Y molecular sieve. Compared with the existing gas-phase dealuminization silicon supplement, the preparation method of the invention carries out gas-phase removal and silicon supplement on heteroatom boron introduced in the synthesis. The heteroatom molecular sieve prepared by the invention contains boron, aluminum and silicon, and the electronegativity of boron and aluminum is obviously different, and in addition, the bond length of a B-O (0.147nm) covalent bond formed by framework boron and oxygen is different from the bond length of an Al-O (0.175nm) covalent bond formed by framework aluminum and oxygen. Thus, framework boron is less stable in heteroatom molecular sieves than framework aluminum and is more easily removed from the framework. In the gas-phase isomorphous substitution process of the boron-containing heteroatom molecular sieve, silane is preferably isomorphous substituted with framework boron with poor stability, and then isomorphous substituted with framework aluminum, namely in the gas-phase isomorphous substitution process, boron and partial aluminum in a Y molecular sieve framework are removed from the framework to form vacancies, and meanwhile, silicon in a gas-phase isomorphous substitution agent enters the vacancies of the molecular sieve, so that the substitution of the framework boron and the aluminum by the silicon is realized on the basis of the preservation of a crystal phase structure of the Y molecular sieve. The positions of boron and partial aluminum in the Y molecular sieve after gas-phase isomorphous substitution are substituted by silicon, so that the silicon-aluminum ratio of the molecular sieve is obviously improved. In the gas-phase isomorphous substitution process, only the gas-phase substitution agent is substituted with framework boron and framework aluminum, the framework structure of the molecular sieve is kept complete, and the molecular sieve has relatively high relative crystallinity.
The preparation method provided by the invention combines the synthesis of the boron-containing heteroatom Y molecular sieve with a gas-phase isomorphous substitution technology, utilizes the instability of heteroatom boron in a molecular sieve framework, preferentially substitutes the heteroatom through gas-phase isomorphous substitution, namely, realizes the substitution of silicon for framework boron and aluminum on the basis of preserving the crystal phase structure of the Y molecular sieve, thereby greatly improving the framework silicon-aluminum ratio of the Y molecular sieve, reserving the complete molecular sieve framework structure and maintaining the high relative crystallinity of the molecular sieve.
Compared with the prior art, the invention has the innovation points and advantages that:
1. the technical method provided by the invention has small damage to the framework of the molecular sieve, and the prepared Y molecular sieve has high silicon-aluminum ratio and higher relative crystallinity.
2. The boron source used by the technical method provided by the invention is cheap and easy to obtain, and the production cost is reduced.
3. The technical method provided by the invention can improve the silicon-aluminum ratio of the Y molecular sieve on the basis of ensuring the relative crystallinity of the Y molecular sieve by changing the synthesis process and the gas-phase isomorphous substitution process of the heteroatom molecular sieve.
Detailed Description
The present invention is further illustrated by the following comparative examples and examples, but the scope of the invention which can be practiced is not limited thereby.
In each example, XRD characterization of the synthesized product was performed to calculate the framework silicon-aluminum ratio (SiO) and relative crystallinity of each sample2/Al2O3) The crystal packet parameter a of the molecular sieve is measured according to the RIPP145-90 standard method0Then according to the formula SiO2/Al2O3(2.5935-a) in a molar ratio0)/(a0-2.4212) × 2 calculation; the relative crystallinity is calculated by using NaY molecular sieve of southern Kai university as a standard sample.
Example 1
The sources of the raw materials were the same as in example 1.
Preparing a guiding agent: 15g of sodium metaaluminate (Al) are added at 80 DEG2O341 wt% of Na2O content of 28.7%) was dissolved in 83g of deionized water, 47g of sodium hydroxide (purity 96%) was added with mechanical stirring, and stirring was continued to completely dissolve the sodium hydroxide, thereby obtaining a high-basicity sodium metaaluminate solution. The above high-alkalinity sodium metaaluminate solution was added to 211g of water glass (SiO) under stirring226.2 wt% of Na2The O content is 8.3 percent), the mixture is evenly mixed and then is continuously stirred for 2 hours, and then the mixture is kept stand and aged for 12 hours at the temperature of 60 ℃ to prepare the guiding agent.
Synthesis of boron-containing heteroatom Y molecular sieve: at 80 ℃, 7.9g of sodium metaaluminate is dissolved in 78g of deionized water, 51g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so as to obtain a low-alkalinity sodium metaaluminate solution. Pouring the prepared guiding agent into 436g of water glass at the gelling temperature of 35 ℃ under the stirring state, uniformly mixing, and then adding 205g of aluminum sulfate solution (Al)2O3Content 90g/L), the low alkalinity sodium metaaluminate solution obtained above and 65g sodium fluoroborate. Relay (S)And (3) continuously stirring for 2 hours, then filling the obtained silicon-aluminum gel into a stainless steel crystallization kettle, heating to 95 ℃ for crystallization, sampling after crystallization for 36 hours, filtering, washing, and drying at 110 ℃ to obtain the boron-containing heteroatom Y molecular sieve.
Gas phase isomorphous substitution of boron containing heteroatom Y molecular sieves: 10g of boron-containing heteroatom Y molecular sieve are weighed, dried at 600 ℃ for 12 hours, cooled to 350 ℃ and then SiCl is introduced4And (3) heating saturated dry nitrogen to 550 ℃, reacting for 2 hours, purging with dry nitrogen for 2 hours after the reaction is finished, and cooling to room temperature to obtain the Y molecular sieve S1 with high silica-alumina ratio and high relative crystallinity.
Example 2:
the sources of the raw materials were the same as in example 1.
Preparing a guiding agent: at 80 ℃, 8.2g of sodium metaaluminate is dissolved in 77g of deionized water, 65g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so as to obtain a high-alkalinity sodium metaaluminate solution. Adding the high-alkalinity sodium metaaluminate solution into 240g of water glass under the stirring state, stirring for 2 hours after uniformly mixing, and then standing and aging for 48 hours at 25 ℃ to prepare the guiding agent.
Synthesis of boron-containing heteroatom Y molecular sieve: at 80 ℃, 6.8g of sodium metaaluminate is dissolved in 55g of deionized water, 38g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so as to obtain a low-alkalinity sodium metaaluminate solution. Pouring the prepared guiding agent into 425g of water glass at the gelling temperature of 25 ℃ under the stirring state, uniformly mixing, and then adding 188g of aluminum sulfate solution, the low-alkalinity sodium metaaluminate solution and 72g of potassium fluoborate. And (3) continuously stirring for 1 hour, filling the obtained silicon-aluminum gel into a stainless steel crystallization kettle, heating to 90 ℃ for crystallization, sampling after crystallization for 48 hours, filtering, washing, and drying at 110 ℃ to obtain the boron-containing heteroatom Y molecular sieve.
Gas phase isomorphous substitution of boron containing heteroatom Y molecular sieves: 10g of boron-containing heteroatom Y molecular sieve are weighed, dried at 550 ℃ for 12 hours, cooled to 350 ℃ and then SiCl is introduced4Saturated dry nitrogen, heating to 580 deg.C, reacting for 2 hours, after the reaction is finished,purging with dry nitrogen for 2 hours, and cooling to room temperature to obtain the high silica-alumina ratio Y molecular sieve S2 with high relative crystallinity.
Example 3:
the sources of the raw materials were the same as in example 1.
Preparing a guiding agent: at 80 ℃, 7.5g of sodium metaaluminate is dissolved in 88g of deionized water, 74g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so as to obtain a high-alkalinity sodium metaaluminate solution. Adding the high-alkalinity sodium metaaluminate solution into 268g of water glass under the stirring state, stirring for 2 hours after uniformly mixing, and then standing and aging for 24 hours at 45 ℃ to prepare the guiding agent.
Synthesis of boron-containing heteroatom Y molecular sieve: at 80 ℃, 7.3g of sodium metaaluminate is dissolved in 78g of deionized water, 48g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so as to obtain a low-alkalinity sodium metaaluminate solution. Pouring the prepared guiding agent into 452g of water glass at the gelling temperature of 50 ℃ under the stirring state, uniformly mixing, and then adding 235g of aluminum sulfate solution, the low-alkalinity sodium metaaluminate solution and 45g of lithium fluoroborate. And (3) continuously stirring for 1 hour, filling the obtained silicon-aluminum gel into a stainless steel crystallization kettle, heating to 110 ℃ for crystallization, sampling after crystallization for 30 hours, filtering, washing, and drying at 110 ℃ to obtain the boron-containing heteroatom Y molecular sieve.
Gas phase isomorphous substitution of boron containing heteroatom Y molecular sieves: 10g of boron-containing heteroatom Y molecular sieve are weighed, dried at 500 ℃ for 12 hours, cooled to 400 ℃ and then SiCl is introduced4And (3) heating saturated dry nitrogen to 500 ℃, reacting for 4 hours, purging with dry nitrogen for 2 hours after the reaction is finished, and cooling to room temperature to obtain the Y molecular sieve S3 with high silica-alumina ratio and high relative crystallinity.
Example 4:
the sources of the raw materials were the same as in example 1.
Preparing a guiding agent: at 80 ℃, 21g of sodium metaaluminate is dissolved in 25g of deionized water, 26g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so that the high-alkalinity sodium metaaluminate solution is obtained. Under the stirring state, the high-alkalinity sodium metaaluminate solution is added into 188g of water glass, the mixture is stirred for 2 hours after being mixed evenly, and then the mixture is kept stand and aged for 60 hours at the temperature of 5 ℃ to prepare the guiding agent.
Synthesis of boron-containing heteroatom Y molecular sieve: at 80 ℃, 5.8g of sodium metaaluminate is dissolved in 56g of deionized water, 40g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so as to obtain a low-alkalinity sodium metaaluminate solution. Pouring the prepared guiding agent into 404g of water glass at the gelling temperature of 40 ℃ under the stirring state, uniformly mixing, and then adding 195g of aluminum sulfate solution, the low-alkalinity sodium metaaluminate solution and 40g of ammonium fluoroborate. And continuously stirring for 3 hours, putting the obtained silicon-aluminum gel into a stainless steel crystallization kettle, heating to 120 ℃ for crystallization, sampling after crystallization is carried out for 24 hours, filtering, washing, and drying at 110 ℃ to obtain the boron-containing heteroatom Y molecular sieve.
Gas phase isomorphous substitution of boron containing heteroatom Y molecular sieves: 10g of boron-containing heteroatom Y molecular sieve are weighed, dried at 600 ℃ for 24 hours, cooled to 400 ℃ and then charged with SiCl4And (3) heating saturated dry nitrogen to 450 ℃, reacting for 6 hours, purging with dry nitrogen for 2 hours after the reaction is finished, and cooling to room temperature to obtain the Y molecular sieve S4 with high silica-alumina ratio and high relative crystallinity.
Example 5:
the sources of the raw materials were the same as in example 1.
Preparing a guiding agent: at 80 ℃, 15g of sodium metaaluminate is dissolved in 35g of deionized water, 52g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so that high-alkalinity sodium metaaluminate solution is obtained. And adding the high-alkalinity sodium metaaluminate solution into 52g of water glass under the stirring state, stirring for 2 hours after uniformly mixing, and standing and aging for 36 hours at the temperature of 20 ℃ to prepare the guiding agent.
Synthesis of boron-containing heteroatom Y molecular sieve: at 80 ℃, 9.3g of sodium metaaluminate is dissolved in 60g of deionized water, 18g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so as to obtain the low-alkalinity sodium metaaluminate solution. Pouring the prepared guiding agent into 412g of water glass at the gelling temperature of 30 ℃ under the stirring state, uniformly mixing, and then adding 216g of aluminum sulfate solution, the obtained low-alkalinity sodium metaaluminate solution and 45g of sodium fluoborate. And (3) continuously stirring for 1.5 hours, then filling the obtained silicon-aluminum gel into a stainless steel crystallization kettle, heating to 95 ℃ for crystallization, sampling after crystallization for 36 hours, filtering, washing, and drying at 110 ℃ to obtain the boron-containing heteroatom Y molecular sieve.
Gas phase isomorphous substitution of boron containing heteroatom Y molecular sieves: 10g of boron-containing heteroatom Y molecular sieve are weighed, dried at 600 ℃ for 12 hours, cooled to 350 ℃ and then SiCl is introduced4And (3) heating saturated dry nitrogen to 600 ℃, reacting for 1 hour, purging with dry nitrogen for 2 hours after the reaction is finished, and cooling to room temperature to obtain the Y molecular sieve S5 with high silica-alumina ratio and high relative crystallinity.
Example 6:
the sources of the raw materials were the same as in example 1.
Preparing a guiding agent: at 80 ℃, 8.8g of sodium metaaluminate is dissolved in 60g of deionized water, 42g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so as to obtain a high-alkalinity sodium metaaluminate solution. Under the stirring state, the high-alkalinity sodium metaaluminate solution is added into 204g of water glass, the stirring is continued for 2 hours after the uniform mixing, and then the standing and aging are carried out for 24 hours at the temperature of 15 ℃, thus obtaining the guiding agent.
Synthesis of boron-containing heteroatom Y molecular sieve: at 80 ℃, 10.8g of sodium metaaluminate is dissolved in 72g of deionized water, 36g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so as to obtain a low-alkalinity sodium metaaluminate solution. Pouring the prepared guiding agent into 486g of water glass under the stirring state at the gelling temperature of 20 ℃, uniformly mixing, and then adding 235g of aluminum sulfate solution, the obtained low-alkalinity sodium metaaluminate solution and 45g of sodium fluoborate. And (3) continuously stirring for 2 hours, filling the obtained silicon-aluminum gel into a stainless steel crystallization kettle, heating to 105 ℃ for crystallization, sampling after crystallization for 48 hours, filtering, washing, and drying at 110 ℃ to obtain the boron-containing heteroatom Y molecular sieve.
Gas phase isomorphous substitution of boron containing heteroatom Y molecular sieves: 10g of boron-containing heteroatom Y molecular sieve were weighed, dried at 600 ℃ for 18 hours,cooling to 300 ℃, and then introducing SiCl4And (3) heating saturated dry nitrogen to 600 ℃, reacting for 5 hours, purging with dry nitrogen for 2 hours after the reaction is finished, and cooling to room temperature to obtain the Y molecular sieve S6 with high silica-alumina ratio and high relative crystallinity.
Comparative example:
the NaY molecular sieve was prepared by conventional methods, with the same sources of raw materials as in example 1.
Preparing a guiding agent: at 80 ℃, 6.8g of sodium metaaluminate is dissolved in 55g of deionized water, 45g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so as to obtain a high-alkalinity sodium metaaluminate solution. Under the stirring state, the high-alkalinity sodium metaaluminate solution is added into 232g of water glass, the mixture is stirred for 2 hours after being mixed evenly, and then the mixture is kept stand and aged for 20 hours at the temperature of 25 ℃ to prepare the guiding agent.
Directly synthesizing the high-silica-alumina-ratio Y molecular sieve: at 80 ℃, 11.8g of sodium metaaluminate is dissolved in 80g of deionized water, 38g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so as to obtain a low-alkalinity sodium metaaluminate solution. Pouring the prepared guiding agent into 419g of water glass under the condition of stirring at the gelling temperature of 20 ℃, uniformly mixing, then adding 156g of aluminum sulfate solution and the obtained low-alkalinity sodium metaaluminate solution, stirring for 1 hour, then filling the obtained silicon-aluminum gel into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, heating to 100 ℃ for crystallization, crystallizing for 24 hours, filtering, washing, and drying at 110 ℃ to obtain a solid sample D.
Table 1 shows the results of the framework Si/Al ratio and the relative crystallinity of the samples obtained in examples 1 to 6 and comparative examples.
TABLE 1
| Sample numbering | Framework silicon to aluminum ratio | Relative crystallinity (%) |
| Sample S1 from example 1 | 12.6 | 94.5 |
| Example 2 sample S2 | 15.3 | 92.3 |
| Sample S3 obtained in example 3 | 17.8 | 93.3 |
| Example 4 sample S4 | 16.9 | 92.5 |
| Sample S5 obtained in example 5 | 22.5 | 91.2 |
| Sample S6 obtained in example 6 | 20.4 | 91.4 |
| Sample D1 from comparative example 1 | 5.57 | 91.3 |
Claims (9)
1. A preparation method of a Y molecular sieve with high silicon-aluminum ratio and high relative crystallinity is characterized by comprising the following steps:
a) guide devicePreparation of the agent: mixing a silicon source, an aluminum source, alkali and water according to the proportion of (3-45) Na2O:1Al2O3:(5～80)SiO2:(100～800)H2Mixing the O with the molar ratio of 5-60 ℃, stirring completely, and then statically aging for 2-72 hours at 5-60 ℃ to obtain the product;
b) synthesis of boron-containing heteroatom Y molecular sieve: mixing a silicon source with the guiding agent at 15-60 ℃, then adding an aluminum source, and adding fluoborate to prepare gel, wherein the molar ratio of each component in the gel is as follows: (0.5 to 10) Na2O:1Al2O3:(5～40)SiO2:(80～800)H2O (0.01-0.5) vigorously stirring the fluoborate for 0.5-3 hours; heating the gel to 90-120 ℃, crystallizing for 8-100 hours, and filtering, washing and drying a product after crystallization is finished to obtain the boron-containing heteroatom Y molecular sieve;
c) gas phase isomorphous substitution of boron containing heteroatom Y molecular sieves: treating the boron-containing heteroatom Y molecular sieve at 100-700 ℃ for 0.1-48 hours to obtain a dry boron-containing heteroatom Y molecular sieve with the water content of less than 2 wt.%; cooling the dried boron-containing heteroatom Y molecular sieve to 80-600 ℃; under a drying condition, introducing a drying gas saturated by a gas-phase isomorphous substituting agent into the dried boron-containing heteroatom Y molecular sieve, and reacting at the temperature of 120-800 ℃ for 0.1-48 hours; and after the reaction is finished, stopping introducing the dry gas saturated by the gas-phase isomorphous substituting agent, purging for 0.5-12 hours by using the dry gas, and cooling to room temperature to obtain the high-silica-alumina-ratio Y molecular sieve with high relative crystallinity.
2. The method for preparing the Y molecular sieve with high silica-alumina ratio and high relative crystallinity according to claim 1, wherein the silicon source is one or more of silica gel, silica sol, sodium silicate, white carbon black and water glass; the aluminum source is one or more of aluminum oxide, aluminum hydroxide, aluminum sulfate, sodium metaaluminate and aluminum sol; the alkali is sodium hydroxide; the fluoborate is one or more of ammonium fluoborate, lithium fluoborate, sodium fluoborate and potassium fluoborate.
3. The method for preparing the Y molecular sieve with high silicon-aluminum ratio and high relative crystallinity according to claim 1, wherein the molar ratio of each component in the guiding agent is (5-20) Na2O:1Al2O3:(10～50)SiO2:(200～500)H2And O, aging at the temperature of 15-50 ℃ for 12-48 hours.
4. The method of claim 1, wherein the molar ratio of each component in the synthetic gel of the boron-containing heteroatom Y molecular sieve is: (0.5 to 7) Na2O:1Al2O3:(5～32)SiO2:(150～500)H2O (0.05-0.3) fluoborate, the gelling temperature is 20-50 ℃, the stirring time is 2-4 hours, the crystallization temperature is 95-110 ℃, and the crystallization time is 12-72 hours.
5. The method for preparing the Y molecular sieve with high silica-alumina ratio and high relative crystallinity according to claim 1, wherein in the gas phase isomorphous substitution process of the boron-containing heteroatom Y molecular sieve, the drying temperature of the heteroatom Y molecular sieve is 200-650 ℃, the drying time is 0.5-24 hours, the water content of the dried heteroatom Y molecular sieve is less than 1 wt.%, and the temperature is reduced to 120-400 ℃.
6. The method of claim 1, wherein the gas phase isomorphous substituent is one or more of dichlorosilane, trichlorosilane, and tetrachlorosilane.
7. The method for preparing the Y molecular sieve with high silica-alumina ratio and high relative crystallinity according to claim 1, wherein the gas phase isomorphous substitution reaction temperature of the dried Y molecular sieve with boron and heteroatom is 150-650 ℃, the reaction time is 0.5-12 hours, and the time for purging with the drying gas after the reaction is finished is 1-6 hours.
8. The method of claim 7, wherein the dry gas is one or more of dry air, dry helium, dry nitrogen and dry argon.
9. A high silica-alumina ratio Y molecular sieve having a high relative crystallinity prepared by the method of any one of claims 1 to 8.
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