CN114684831B - High silicon-aluminum ratio Y molecular sieve with high relative crystallinity and preparation method thereof - Google Patents
High silicon-aluminum ratio Y molecular sieve with high relative crystallinity and preparation method thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 144
- 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 144
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052796 boron Inorganic materials 0.000 claims abstract description 65
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 238000002425 crystallisation Methods 0.000 claims abstract description 34
- 230000008025 crystallization Effects 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 11
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims description 67
- 229910052708 sodium Inorganic materials 0.000 claims description 59
- 238000003756 stirring Methods 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 28
- 238000006467 substitution reaction Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000499 gel Substances 0.000 claims description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 235000019353 potassium silicate Nutrition 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- -1 ammonium fluoroborate Chemical compound 0.000 claims description 11
- 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
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010926 purge Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000004411 aluminium 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
- 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
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 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
- 239000000463 material Substances 0.000 abstract description 3
- 230000003068 static effect Effects 0.000 abstract description 2
- 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 description 57
- 239000012071 phase Substances 0.000 description 26
- 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
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910003902 SiCl 4 Inorganic materials 0.000 description 6
- 239000013078 crystal 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
- 238000005303 weighing Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910021536 Zeolite Inorganic materials 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
- 239000010457 zeolite Substances 0.000 description 5
- 238000010306 acid treatment Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000011068 loading method Methods 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
- 230000001502 supplementing effect Effects 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 238000007664 blowing 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
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000002431 foraging effect Effects 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
- 229910052744 lithium Inorganic materials 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- 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 high silicon-aluminum ratio Y molecular sieve with high relative crystallinity and a preparation method thereof. The method comprises the following steps: mixing silicon source, guiding agent, aluminum source and fluoborate into gel with the mole ratio of gel material being 0.5-10 Na 2 O:1Al 2 O 3 :5～40SiO 2 :80～800H 2 0.01 to 0.5 part of O fluoborate; carrying out static crystallization on the prepared mixed gel for 6-72 hours at the temperature of 90-150 ℃ to obtain a boron-containing heteroatom Y molecular sieve; and (3) introducing dry gas saturated by the 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 Y molecular sieve with high relative crystallinity and high silicon-aluminum ratio. The high silicon-aluminum ratio Y molecular sieve provided by the invention has the advantages of relative crystallinity of more than 90%, silicon-aluminum ratio of more than 10, simple preparation process, low production cost and industrial application prospect.
Description
Technical Field
The invention belongs to the field of molecular sieve materials and preparation thereof, and particularly relates to a high silicon-aluminum ratio Y molecular sieve with high relative crystallinity and a preparation method thereof.
Background
The Y molecular sieve has excellent pore canal structure and proper surface acidity, and has wide application in the fields of adsorption, separation, catalysis and the like. The Y molecular sieve framework consists of silicon oxygen tetrahedra and aluminum oxygen tetrahedra, and has a silicon-aluminum ratio (SiO 2 /Al 2 O 3 ) 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, and the framework structure of the molecular sieve is not easily damaged in the catalytic reaction process and the regeneration process, so that the Y molecular sieve has better catalytic stability and regeneration performance.
The high silica-alumina ratio Y molecular sieve 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 modulating the feed ratio, adding a template agent and modulating the process steps.
In the preparation of the high silica-alumina ratio Y molecular sieve by modulating the raw material proportion, a representative method is compared: patent CN104118885B discloses a method for synthesizing NaY zeolite with high silicon-aluminum ratio, which can synthesize NaY zeolite with high silicon-aluminum ratio in a shorter crystallization time by modulating raw material proportion and preparation process conditions under the condition of not using a template agent.
In the preparation of a high silica to alumina ratio Y molecular sieve by adding a template agent, a representative method is compared: patent CN104692413B discloses a method for preparing a NaY molecular sieve with high silicon-aluminum ratio and a product thereof, wherein the method uses a short-chain alkyl imidazole ionic liquid which is not easy to volatilize as a template agent, and the obtained high silicon Y molecular sieve has high crystallinity and the silicon-aluminum ratio is more than 6; patent CN100390059C discloses a synthesis method of faujasite with high silicon-aluminum ratio, which adopts a proper template agent, and adopts a hydrothermal crystallization method to directly synthesize the faujasite with high silicon-aluminum ratio under the condition of less sodium consumption, and has the characteristics of short crystallization time and less alkali consumption.
In the preparation of a high silica to alumina ratio Y molecular sieve by the modulation process steps, a representative method is compared: patent CN101254929B discloses a preparation method of a NaY molecular sieve with high silicon-aluminum 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 high silicon-aluminum ratio; the patent CN100404418C and the patent CN100443407C adopt a first step of dynamic crystallization and a second step of static crystallization to obtain the small-grain NaY molecular sieve with high silicon-aluminum ratio and the relative crystallinity of more than 80 percent; patent CN103896303B discloses a method for directly synthesizing an ultrafine NaY molecular sieve with high silicon-aluminum ratio, which adopts dynamic crystallization under the condition of no template agent and additive, and undergoes at least three sections of temperature programming control crystallization processes, wherein the average grain size of the obtained NaY molecular sieve is between 100 and 500nm, and the skeleton silicon-aluminum ratio is higher than 6.5.
In the post-treatment modification method, the high silica-alumina ratio Y molecular sieve can be obtained through acid treatment modification, hydrothermal roasting treatment and gas-solid phase modification.
The Y molecular sieve with high silicon-aluminum ratio can be obtained through acid treatment modification or hydrothermal roasting treatment, but the framework structure of the molecular sieve is easily damaged, the relative crystallinity is obviously reduced, and the stability and the acidity of the Y molecular sieve are greatly influenced. Shen Baojian et al in patent CN103539151B disclose a preparation method of a Y-type zeolite with a high silica-alumina ratio and rich secondary pores, which comprises the steps of synthesizing a Fe-Y molecular sieve, and then performing ammonium exchange and hydrothermal roasting twice respectively, wherein the obtained Y-type zeolite has a higher silica-alumina ratio and a richer secondary pore.
In the preparation of the high silica-alumina ratio Y molecular sieve by gas-solid phase modification, a representative method is compared: the patent CN102553630B adopts an in-situ crystallization method to prepare NaY/matrix, and adopts a gas phase method to perform ultra-stabilization treatment to prepare the small-grain Y-type zeolite catalytic cracking catalyst with high silicon-aluminum ratio, 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 obtained by direct synthesis through adjusting the feed ratio is smaller than 6.0, and the silicon-aluminum ratio of the molecular sieve still needs to be improved by subsequent modification treatment; the template agent is prepared into the Y molecular sieve, although the silicon-aluminum ratio can reach more than 6.0, the used template agent has high price and increased production cost, and in addition, the removal of the template agent can influence the relative crystallinity of the molecular sieve and cause pollution to the environment; the process condition for preparing the high-silicon Y molecular sieve by using a fractional crystallization method or a dynamic crystallization method is harsh, the production process is relatively complex, and the single kettle yield is low. The preparation of the high-silicon Y molecular sieve by acid treatment or hydrothermal roasting treatment is a method commonly applied in the industry at present, but the repeated exchange, the hydrothermal roasting and the acid treatment are needed, the process steps are complex, the production cost is high, the framework structure of the molecular sieve is easily damaged 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.
From the analysis of the technical methods of industrial production and literature reporting, it can be seen that: the existing technical method for preparing the Y molecular sieve with high silicon-aluminum ratio has the defects of high production cost, complex process, low yield, low relative crystallinity of the obtained molecular sieve and insufficient silicon-aluminum ratio of the molecular sieve.
Disclosure of Invention
Based on the problems of high production cost, low relative crystallinity of the molecular sieve and insufficient silicon-aluminum ratio of the molecular sieve in the prior art, the invention provides the preparation method of the Y molecular sieve with high silicon-aluminum ratio, which has the advantages of simple preparation process, low production cost, industrial application prospect and high relative crystallinity.
The preparation method comprises the steps of firstly obtaining a boron-containing heteroatom Y molecular sieve by a hydrothermal synthesis method, then carrying out gas-phase boron-removing and silicon-supplementing and aluminum-removing and silicon-supplementing on the boron-containing heteroatom Y molecular sieve, namely replacing heteroatom boron and part of aluminum in the molecular sieve by silicon, and finally obtaining the Y molecular sieve with high silicon-aluminum ratio, wherein the Y molecular sieve has higher relative crystallinity, and the preparation method specifically adopts the following technical scheme:
a preparation method of a high silicon-aluminum ratio Y molecular sieve with high relative crystallinity comprises the following process steps:
(1) Preparing a guiding agent: mixing silicon source, aluminium source, alkali and water according to (3-45) Na 2 O:1Al 2 O 3 :(5～80)SiO 2 :(100～800)H 2 Mixing the O at the molar ratio of 5-60 ℃, standing and aging for 2-72 hours at the temperature of 5-60 ℃ after stirring completely to obtain the catalyst;
(2) Synthesizing a 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: (0.5-10) Na 2 O:1Al 2 O 3 :(5～40)SiO 2 :(80～800)H 2 O (0.01-0.5) fluoborate, and stirring vigorously for 0.5-3 hours; heating the gel to 90-120 ℃, crystallizing for 8-100 hours, filtering, washing and drying the product after crystallization to obtain a 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%; the temperature of the dried boron-containing heteroatom Y molecular sieve is reduced to 80-600 ℃; under the drying condition, introducing a drying 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 the reaction temperature of 120-800 ℃; after the reaction is finished, stopping introducing dry gas saturated by the gas phase isomorphous substituent, purging for 0.5 to 12 hours by using the dry gas, and cooling to room temperature to obtain the Y molecular sieve with high silicon-aluminum ratio and high relative crystallinity.
According to the preparation method of 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 fluoroborate is one or more of ammonium fluoroborate, lithium fluoroborate, sodium fluoroborate and potassium fluoroborate.
The molar ratio of each component in the guiding agent is preferably (5-20) Na 2 O:1Al 2 O 3 :(10～50)SiO 2 :(200～500)H 2 O, the aging temperature is preferably 15-50 ℃, and the aging time is preferably 12-48 hours.
The said containsThe molar ratio of the components in the synthetic gel of the boron heteroatom Y molecular sieve is preferably: (0.5-7) Na 2 O:1Al 2 O 3 :(5～32)SiO 2 :(150～500)H 2 O (0.05-0.3) fluoborate, the gelatinization 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 heteroatom Y molecular sieve after drying is preferably lower than 1wt.%, and the temperature is preferably reduced to 120-400 ℃.
The gas phase isomorphous substituent 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 purging time by dry gas is preferably 1-6 hours after the reaction is finished; wherein the drying gas is preferably one or more of drying air, drying helium, drying nitrogen and drying argon.
The preparation method provided by the invention uses silane as the same crystal substituent for gas phase boron removal, dealumination and silicon supplementation of the boron-containing heteroatom Y molecular sieve. Compared with the existing gas-phase dealumination silicon supplementing method, the preparation method provided by the invention is used for gas-phase removal and silicon supplementing of heteroatom boron introduced in synthesis. The heteroatom molecular sieve skeleton prepared by the invention contains boron, aluminum and silicon, and the electronegativity of the boron and the aluminum is obviously different, and in addition, the bond length of a B-O (0.147 nm) covalent bond formed by the skeleton boron and oxygen is different from the bond length of an Al-O (0.175 nm) covalent bond formed by the skeleton aluminum and oxygen. Therefore, framework boron is weaker in the heteroatom molecular sieve than framework aluminum, and is easier to remove from the framework. In the gas phase isomorphous substitution process of the boron-containing heteroatom molecular sieve, silane is preferentially isomorphous substituted with framework boron with poor stability, and then isomorphous substituted with framework aluminum is carried out, namely boron and part of aluminum in the framework of the Y molecular sieve are removed from the framework in the gas phase isomorphous substitution process to form vacancies, and meanwhile silicon in the gas phase isomorphous substituent enters into the vacancies of the molecular sieve, so that the substitution of silicon for the framework boron and aluminum is realized on the basis of preserving the crystal phase structure of the Y molecular sieve. The positions of boron and part of aluminum in the Y molecular sieve after the same crystal 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 substituent is substituted with framework boron and framework aluminum, and the framework structure of the molecular sieve is kept complete, so that the molecular sieve has relatively high relative crystallinity.
The preparation method combines the synthesis of the heteroatom Y molecular sieve containing boron with the gas phase isomorphous substitution technology, utilizes the instability of heteroatom boron in a molecular sieve framework, preferentially substitutes the heteroatom by the gas phase isomorphous substitution, namely realizes the substitution of silicon on 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, preserving 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 molecular sieve framework, 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 same crystal substitution process of the heteroatom molecular sieve.
Detailed Description
The present invention is further illustrated by the following comparative examples and examples, which are not intended to limit the scope of the invention.
In each example, XRD characterization of the synthesis product was performed to calculate the ratio of skeletal silica to alumina and relative crystallinity of each sample, wherein the ratio of skeletal silica to alumina (SiO 2 /Al 2 O 3 ) The crystal package parameter a of the molecular sieve is measured according to the RIPP145-90 standard method 0 Then according to the formula SiO 2 /Al 2 O 3 Molar ratio= (2.5935-a) 0 )/(a 0 -2.4212) x 2; the relative crystallinity was calculated using NaY molecular sieves at university of south open as standard.
Example 1
The sources of the raw materials are the same as in example 1.
Preparing a guiding agent: 15g of sodium metaaluminate (Al 2 O 3 The content is 41wt%, na 2 O content is 28.7%) is dissolved in 83g deionized water, 47g sodium hydroxide (purity 96%) is added under mechanical stirring, and stirring is continued to dissolve completely, thus obtaining high alkalinity sodium metaaluminate solution. The above-mentioned high-basicity sodium metaaluminate solution was added to 211g of water glass (SiO) under stirring 2 The content is 26.2wt percent, na 2 O content is 8.3%), stirring for 2 hr, and standing at 60deg.C for aging for 12 hr to obtain the final product.
Synthesis of boron-containing heteroatom Y molecular sieves: 7.9g of sodium metaaluminate is dissolved in 78g of deionized water at 80 ℃, 51g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so that a low-alkalinity sodium metaaluminate solution is obtained. Pouring the prepared guiding agent into 436g of water glass under stirring at a gelatinization temperature of 35 ℃, uniformly mixing, and then adding 205g of aluminum sulfate solution (Al 2 O 3 Content 90 g/L), the low alkalinity sodium metaaluminate solution obtained above and 65g sodium fluoroborate. And (3) continuously stirring for 2 hours, filling the obtained silica-alumina gel into a stainless steel crystallization kettle, heating to 95 ℃ for crystallization, sampling after 36 hours of crystallization, 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: weighing 10g of boron-containing heteroatom Y molecular sieve, drying at 600 ℃ for 12 hours, cooling to 350 ℃, and then introducing SiCl 4 Saturated dry nitrogen is heated to 550 ℃ and reacts for 2 hours, after the reaction is finished, the dry nitrogen is used for blowing for 2 hours, and the temperature is reduced to room temperature, so that the high silicon-aluminum ratio Y molecular sieve S1 with high relative crystallinity is obtained.
Example 2:
the sources of the raw materials are 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, thus obtaining high-alkalinity sodium metaaluminate solution. Under the stirring state, adding the high-alkalinity sodium metaaluminate solution into 240g of water glass, continuously 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 sieves: 6.8g of sodium metaaluminate is dissolved in 55g of deionized water at 80 ℃, 38g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so that a low-alkalinity sodium metaaluminate solution is obtained. Under the stirring state, the gelatinizing temperature is 25 ℃, the prepared guiding agent is poured into 425g of water glass, the mixture is uniformly mixed, and then 188g of aluminum sulfate solution, the low-alkalinity sodium metaaluminate solution and 72g of potassium fluoborate are added. And (3) continuously stirring for 1 hour, filling the obtained silica-alumina gel into a stainless steel crystallization kettle, heating to 90 ℃ for crystallization, sampling after 48 hours of crystallization, 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: weighing 10g of boron-containing heteroatom Y molecular sieve, drying at 550 ℃ for 12 hours, cooling to 350 ℃, and then introducing SiCl 4 Saturated dry nitrogen is heated to 580 ℃ for 2 hours of reaction, after the reaction is finished, the dry nitrogen is used for purging for 2 hours, and the temperature is reduced to room temperature, so that the high silicon-aluminum ratio Y molecular sieve S2 with high relative crystallinity is obtained.
Example 3:
the sources of the raw materials are the same as in example 1.
Preparing a guiding agent: 7.5g of sodium metaaluminate is dissolved in 88g of deionized water at 80 ℃, 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. Under the stirring state, adding the high-alkalinity sodium metaaluminate solution into 268g of water glass, continuously 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 sieves: 7.3g of sodium metaaluminate is dissolved in 78g of deionized water at 80 ℃, 48g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so that a low-alkalinity sodium metaaluminate solution is obtained. Under the stirring state, the gelling temperature is 50 ℃, the prepared guiding agent is poured into 452g of water glass, the mixture is uniformly mixed, and then 235g of aluminum sulfate solution, the low-alkalinity sodium metaaluminate solution and 45g of lithium fluoborate are added. And (3) continuously stirring for 1 hour, filling the obtained silica-alumina gel into a stainless steel crystallization kettle, heating to 110 ℃ for crystallization, sampling after 30 hours of crystallization, 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: weighing 10g of boron-containing heteroatom Y molecular sieve, drying at 500 ℃ for 12 hours, cooling to 400 ℃, and then introducing SiCl 4 Saturated dry nitrogen is heated to 500 ℃ for reaction for 4 hours, after the reaction is finished, the dry nitrogen is used for purging for 2 hours, and the temperature is reduced to room temperature, so that the high silicon-aluminum ratio Y molecular sieve S3 with high relative crystallinity is obtained.
Example 4:
the sources of the raw materials are the same as in example 1.
Preparing a guiding agent: 21g of sodium metaaluminate is dissolved in 25g of deionized water at 80 ℃, 26g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so that a high-alkalinity sodium metaaluminate solution is obtained. Under the stirring state, the high-alkalinity sodium metaaluminate solution is added into 188g of water glass, and after uniform mixing, stirring is continued for 2 hours, and then standing and aging are carried out for 60 hours at the temperature of 5 ℃ to prepare the guiding agent.
Synthesis of boron-containing heteroatom Y molecular sieves: 5.8g of sodium metaaluminate is dissolved in 56g of deionized water at 80 ℃, 40g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so that a low-alkalinity sodium metaaluminate solution is obtained. Under the stirring state, the gelling temperature is 40 ℃, the prepared guiding agent is poured into 404g of water glass, the mixture is uniformly mixed, and 195g of aluminum sulfate solution, the low-alkalinity sodium metaaluminate solution and 40g of ammonium fluoborate are added. And (3) stirring for 3 hours, loading the obtained silica-alumina gel into a stainless steel crystallization kettle, heating to 120 ℃ for crystallization, sampling after 24 hours of crystallization, 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: weighing 10g of boron-containing heteroatom Y molecular sieve, drying at 600 ℃ for 24 hours, cooling to 400 ℃, and then introducing SiCl 4 Saturated dry nitrogen is heated to 450 ℃ for reaction for 6 hours, after the reaction is finished, the dry nitrogen is used for purging for 2 hours, and the temperature is reduced to room temperature, so that the high silicon-aluminum ratio Y molecular sieve S4 with high relative crystallinity is obtained.
Example 5:
the sources of the raw materials are 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, thus obtaining high-alkalinity sodium metaaluminate solution. Under the stirring state, adding the high-alkalinity sodium metaaluminate solution into 52g of water glass, continuously stirring for 2 hours after uniformly mixing, and then standing and aging for 36 hours at 20 ℃ to prepare the guiding agent.
Synthesis of boron-containing heteroatom Y molecular sieves: 9.3g of sodium metaaluminate is dissolved in 60g of deionized water at 80 ℃, 18g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so that a low-alkalinity sodium metaaluminate solution is obtained. Under the stirring state, the gel forming temperature is 30 ℃, the prepared guiding agent is poured into 412g of water glass, the mixture is uniformly mixed, and then 216g of aluminum sulfate solution, the low-alkalinity sodium metaaluminate solution and 45g of sodium fluoborate are added. Stirring for 1.5 hr, loading the obtained silica-alumina gel into a stainless steel crystallizing kettle, heating to 95 deg.c for crystallization, sampling after 36 hr crystallization, filtering, washing and stoving at 110 deg.c to obtain boron-containing hetero atom Y molecular sieve.
Gas phase isomorphous substitution of boron-containing heteroatom Y molecular sieves: weighing 10g of boron-containing heteroatom Y molecular sieve, drying at 600 ℃ for 12 hours, cooling to 350 ℃, and then introducing SiCl 4 Saturated dry nitrogen is heated to 600 ℃ for reaction for 1 hour, after the reaction is finished, the dry nitrogen is used for purging for 2 hours, and the temperature is reduced to room temperature, so that the high silicon-aluminum ratio Y molecular sieve S5 with high relative crystallinity is obtained.
Example 6:
the sources of the raw materials are 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, thus obtaining high-alkalinity sodium metaaluminate solution. Under the stirring state, adding the high-alkalinity sodium metaaluminate solution into 204g of water glass, continuously stirring for 2 hours after uniformly mixing, and then standing and aging for 24 hours at 15 ℃ to prepare the guiding agent.
Synthesis of boron-containing heteroatom Y molecular sieves: 10.8g of sodium metaaluminate is dissolved in 72g of deionized water at 80 ℃, 36g of sodium hydroxide is added under mechanical stirring, and stirring is continued to completely dissolve the sodium metaaluminate, so that a low-alkalinity sodium metaaluminate solution is obtained. Under the stirring state, the gelatinizing temperature is 20 ℃, the prepared guiding agent is poured into 486g of water glass, and then, 235g of aluminum sulfate solution, the low-alkalinity sodium metaaluminate solution and 45g of sodium fluoborate are added. And (3) continuously stirring for 2 hours, filling the obtained silica-alumina gel into a stainless steel crystallization kettle, heating to 105 ℃ for crystallization, sampling after 48 hours of crystallization, 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: weighing 10g of boron-containing heteroatom Y molecular sieve, drying at 600 ℃ for 18 hours, cooling to 300 ℃, and then introducing SiCl 4 Saturated dry nitrogen is heated to 600 ℃ for reaction for 5 hours, after the reaction is finished, the dry nitrogen is used for purging for 2 hours, and the temperature is reduced to room temperature, so that the high silicon-aluminum ratio Y molecular sieve S6 with high relative crystallinity is obtained.
Comparative example:
the NaY molecular sieves were prepared by conventional methods and the sources of the various materials were the same 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, thus obtaining high-alkalinity sodium metaaluminate solution. Under the stirring state, adding the high-alkalinity sodium metaaluminate solution into 232g of water glass, continuously stirring for 2 hours after uniformly mixing, and then standing and aging for 20 hours at 25 ℃ to prepare the guiding agent.
Directly synthesizing the high silicon-aluminum 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, thus obtaining low-alkalinity sodium metaaluminate solution. Pouring the prepared guiding agent into 419g of water glass at the gelatinizing temperature of 20 ℃ under the stirring state, uniformly mixing, adding 156g of aluminum sulfate solution and the low-alkalinity sodium metaaluminate solution, stirring for 1 hour, putting the obtained silica-alumina 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 skeleton silica-alumina ratio and the relative crystallinity of the samples obtained in examples 1 to 6 and comparative examples.
TABLE 1
| Sample numbering | Silicon-aluminum ratio of skeleton | Relative crystallinity (%) |
| Sample S1 obtained in example 1 | 12.6 | 94.5 |
| Example 2 sample S2 | 15.3 | 92.3 |
| Sample S3 obtained in example 3 | 17.8 | 93.3 |
| Sample S4 obtained in example 4 | 16.9 | 92.5 |
| Sample S5 obtained in example 5 | 22.5 | 91.2 |
| Sample S6 obtained in example 6 | 20.4 | 91.4 |
| Comparative example 1 sample D1 | 5.57 | 91.3 |
Claims (8)
1. The preparation method of the Y molecular sieve with high silicon-aluminum ratio and high relative crystallinity is characterized by comprising the following steps:
a) Preparing a guiding agent: mixing silicon source, aluminium source, alkali and water according to (3-45) Na 2 O: 1Al 2 O 3 : （5～80）SiO 2 : （100～800）H 2 Mixing the O at the molar ratio of 5-60 ℃, standing and aging for 2-72 hours at the temperature of 5-60 ℃ after stirring completely to obtain the catalyst;
b) Synthesizing a 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: (0.5-10) Na 2 O: 1Al 2 O 3 : （5～40）SiO 2 :（80～800） H 2 O (0.01-0.5) fluoborate, and stirring vigorously for 0.5-3 hours; the saidHeating the gel to 90-120 ℃, crystallizing for 8-100 hours, filtering, washing and drying the product after crystallization is completed 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 water content 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 substituent into the dry boron-containing heteroatom Y molecular sieve, and reacting for 0.1-48 hours at the temperature of 120-800 ℃; after the reaction is finished, stopping introducing dry gas saturated by the gas phase isomorphous substituent, purging for 0.5-12 hours by using the dry gas, and cooling to room temperature to obtain the high silicon-aluminum ratio Y molecular sieve with high relative crystallinity;
wherein the gas phase isomorphous substituent is one or more of dichlorosilane, trichlorosilane and tetrachlorosilane.
2. The method for preparing a high silica-alumina ratio Y molecular sieve having a 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 fluoroborate is one or more of ammonium fluoroborate, lithium fluoroborate, sodium fluoroborate and potassium fluoroborate.
3. The method for producing a high silica-alumina ratio Y molecular sieve having a high relative crystallinity according to claim 1, wherein the molar ratio of each component in the directing agent is (5 to 20) Na 2 O: 1Al 2 O 3 : （10～50）SiO 2 : （200～500）H 2 O, the aging temperature is 15-50 ℃, and the aging time is 12-48 hours.
4. The method for preparing a high silica to alumina ratio Y molecular sieve having a high relative crystallinity according to claim 1, whereinThe molar ratio of each component in the synthetic gel of the boron-containing heteroatom Y molecular sieve is as follows: (0.5-7) Na 2 O: 1Al 2 O 3 : （5～32）SiO 2 : （150～500）H 2 O (0.05-0.3) fluoborate, the gelatinization 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 a high silica alumina ratio Y molecular sieve having a high relative crystallinity according to claim 1, wherein in the gas phase isomorphous substitution process of the boron-containing hetero atom Y molecular sieve, the drying temperature of the hetero atom Y molecular sieve is 200 to 650 ℃, the drying time is 0.5 to 24 hours, the water content of the dried hetero atom Y molecular sieve is less than 1wt.%, and the temperature is reduced to 120 to 400 ℃.
6. The method for preparing a high silica alumina ratio Y molecular sieve with high relative crystallinity according to claim 1, wherein the gas phase isomorphous substitution reaction temperature of the dried boron-containing hetero atom Y molecular sieve is 150-650 ℃, the reaction time is 0.5-12 hours, and the purging time with dry gas is 1-6 hours after the reaction is finished.
7. The method for preparing a high silica-alumina ratio Y molecular sieve having a high relative crystallinity according to claim 6, wherein the dry gas is one or more of dry air, dry helium, dry nitrogen and dry argon.
8. A high silica to alumina ratio Y molecular sieve of high relative crystallinity prepared by the method of any one of claims 1 to 7.
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