CN115594192B - NaY zeolite with high silicon-aluminum ratio and preparation method and application thereof - Google Patents
NaY zeolite with high silicon-aluminum ratio and preparation method and application thereof Download PDFInfo
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- CN115594192B CN115594192B CN202211316665.4A CN202211316665A CN115594192B CN 115594192 B CN115594192 B CN 115594192B CN 202211316665 A CN202211316665 A CN 202211316665A CN 115594192 B CN115594192 B CN 115594192B
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- 239000010457 zeolite Substances 0.000 title claims abstract description 166
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 164
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 164
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 59
- 239000003513 alkali Substances 0.000 claims abstract description 113
- 239000010703 silicon Substances 0.000 claims abstract description 93
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 93
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 92
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 92
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 84
- 230000032683 aging Effects 0.000 claims abstract description 62
- 239000013078 crystal Substances 0.000 claims abstract description 60
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 55
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 239000011734 sodium Substances 0.000 claims description 159
- 229910052708 sodium Inorganic materials 0.000 claims description 96
- 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 95
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 91
- 239000000499 gel Substances 0.000 claims description 77
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 68
- 235000019353 potassium silicate Nutrition 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 44
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 42
- 239000000377 silicon dioxide Substances 0.000 claims description 41
- 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 28
- 238000002425 crystallisation Methods 0.000 claims description 26
- 230000008025 crystallization Effects 0.000 claims description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 41
- 239000008367 deionised water Substances 0.000 description 29
- 229910021641 deionized water Inorganic materials 0.000 description 29
- 239000011541 reaction mixture Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 9
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 8
- -1 cesium ions Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
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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 belongs to the technical field of NaY zeolite materials, and discloses a high silica-alumina ratio NaY zeolite and a preparation method and application thereof, wherein the preparation method comprises the following steps: uniformly dispersing a silicon source A, an aluminum source A and sodium salt in the aqueous solution A, and aging to obtain a guiding agent A; uniformly dispersing a guiding agent A, a silicon source B, an aluminum source B and an alkali source A in an aqueous solution B, aging, and crystallizing at 85-100 ℃ to obtain zeolite gel seed crystals; uniformly dispersing a silicon source C and an aluminum source C in the aqueous solution C, and aging to obtain a guiding agent B; uniformly dispersing the guiding agent B, the silicon source D, the zeolite gel seed crystal, the alkali source B and the aluminum source D in the aqueous solution D, aging, and crystallizing at 85-100 ℃ to obtain the NaY zeolite with high silicon-aluminum ratio. The preparation method is simple, green and environment-friendly, the preparation period is short, the crystallinity of the prepared NaY zeolite with high silicon-aluminum ratio can reach more than 90 percent, the silicon-aluminum ratio is 5.5-7.0, and the preparation method is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of NaY zeolite materials, in particular to a high silica-alumina ratio NaY zeolite, a preparation method and application thereof.
Background
Y zeolite is widely used in petroleum refining and other fields because of its advantages of developed three-dimensional pore canal, adjustable acidity, good thermal and hydrothermal stability, etc. Crystallinity and silicon to aluminum ratio (SiO 2 /Al 2 O 3 ) Is one of the most dominant factors affecting the properties and function of Y zeolite. The higher crystallinity means that the Y zeolite has higher stability and more active centers, and the higher silicon-aluminum ratio means that the Y zeolite has higher stability, and also means that the Y zeolite has the advantages of low acid density, more strong acid centers, high catalytic cracking activity, good coke selectivity and the like.
NaY zeolite as super stable Y zeolite (USY molecular sieve) and SiCl 4 The properties of the main raw materials of the gas-phase ultrastable Y zeolite and the mesoporous Y zeolite directly influence the performance of the produced material, and further influence the performance of the catalyst.
At present, the NaY zeolite is mainly prepared by adopting a guiding agent method in the prior art, but the crystallinity of the NaY zeolite prepared by the method is about 83 percent, and the silicon aluminum (SiO) 2 /Al 2 O 3 ) The molar ratio is low, and is only about 5.0, so that the NaY zeolite prepared by the method cannot bear the complex and severe conditions of the post-modification process, has large crystallinity loss in the treatment process, and is difficult to meet the production requirement of the high-performance catalyst.
In order to solve the above technical problems, those skilled in the art have tried to improve the silica-alumina ratio and crystallinity of NaY zeolite, and have proposed two kinds of methods for synthesizing NaY zeolite with high silica-alumina ratio, namely a template-free method and a template method. Wherein, the template-free method is to add metal cesium ions into reactant gel to synthesize high silica-alumina ratio Y zeolite with silica-alumina ratio between 5.0 and 7.0, but the method needs to remove cesium ions by a method of ion exchange and roasting for multiple times. Compared with the template-free method, the template-free method has the advantages that the template is used for synthesizing the NaY zeolite with high silicon-aluminum ratio, and the NaY zeolite is easier to carry out ion exchange during the subsequent modification, so that the template-free method has been widely studied for synthesizing the NaY zeolite with high silicon-aluminum ratio. The template method is also divided into an organic template method and an organic template-free method. The organic template agent process is adopted to synthesize NaY zeolite, and the silicon-aluminum ratio of the NaY zeolite is up to 6.0-18.2. The choice of organic templating agent is primarily focused on organic ammonium and crown ethers. The addition of the organic template agent tends to prolong the crystallization time of the NaY zeolite with high silicon-aluminum ratio, and some of the zeolite needs to be crystallized for more than ten days or one month. In addition, the secondary use of the organic template is still a difficult problem, and the current treatment method generally removes the organic template by roasting, so that environmental pollution is caused, and energy consumption and production cost are increased. Therefore, the synthesis of NaY zeolite with high silica alumina ratio by the organic template-free method is favored by industry. For example, CN101767799a discloses a synthesis method of NaY zeolite with high silica-alumina ratio, which synthesizes a guiding agent by stirring for 24 hours at a relatively low temperature (0-10 ℃) and crystallizing a reactant gel at a low temperature (15-80 ℃), thus synthesizing NaY zeolite with silica-alumina ratio of 6.0 or higher. However, the crystallinity of the sample is lower than 90% due to poor dispersibility of the director in the gel, and the synthesis temperature of the director is low, which is not suitable for industrial application.
Therefore, the invention provides a high silica-alumina ratio NaY zeolite, and a preparation method and application thereof.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the NaY zeolite with high silicon-aluminum ratio, and the preparation method and the application thereof.
The invention relates to a high silicon-aluminum ratio NaY zeolite and a preparation method and application thereof, which are realized by the following technical scheme:
the first object of the invention is to provide a preparation method of NaY zeolite with high silicon-aluminum ratio, which comprises the following steps:
step 1, preparing zeolite gel seed crystal
According to (5.0X10) -2 -20) sodium salt: (8-20) Na 2 O：Al 2 O 3 ：(10-20)SiO 2 ：(100-350)H 2 O, uniformly dispersing a silicon source A, an aluminum source A and sodium salt in an aqueous solution A, and performing first aging treatment to obtain a guiding agent A;
subsequently, according to (2-4) Na 2 O：Al 2 O 3 ：(6-15)SiO 2 ：(100-300)H 2 Uniformly dispersing a guiding agent A, a silicon source B, an aluminum source B and an alkali source A in an aqueous solution B according to the molar ratio of O, performing a second aging treatment, and performing a first crystallization treatment at 85-100 ℃ to obtain zeolite gel seed crystals;
step 2, crystallizing to form NaY zeolite with high silicon-aluminum ratio
According to (10-20) Na 2 O：Al 2 O 3 ：(10-20)SiO 2 ：(100-350)H 2 Uniformly dispersing a silicon source C and an aluminum source C in an aqueous solution C according to the molar ratio of O, and aging for the third time to obtain a guiding agent B;
subsequently, according to (2-4) Na 2 O：Al 2 O 3 ：(7-12)SiO 2 ：(100-300)H 2 And uniformly dispersing the directing agent B, the silicon source D, the zeolite gel seed crystal, the alkali source B and the aluminum source D in the water solution D according to the mole ratio of O, and performing secondary crystallization treatment at 85-100 ℃ after the fourth aging treatment to obtain the NaY zeolite with high silicon-aluminum ratio.
Further, the silicon source A and the silicon source B are selected from one or two of water glass and alkaline silica sol.
Further, the aluminum source A and the aluminum source B are selected from one or two of sodium metaaluminate and high-alkali sodium metaaluminate.
Further, the sodium salt is one or more of NaCl, naBr and NaI.
Further, the silicon source C and the silicon source D are selected from one or more of silica sol, water glass, white carbon black and silica gel.
Further, the aluminum source C and the aluminum source D are selected from one or more of sodium metaaluminate, high alkali sodium metaaluminate, aluminum sulfate, aluminum nitrate and aluminum hydroxide.
Further, the sodium salt accounts for 3-18 wt% of the guiding agent A.
Further, the zeolite gel seed crystal accounts for 1-20wt% of the guiding agent B.
Further, the temperature of the first aging treatment is 20-35 ℃, and the aging time is 12-24 hours.
Further, the temperature of the second aging treatment is 30-60 ℃ and the aging time is 1-12 h.
Further, the time of the first crystallization treatment is 6-60 hours.
Further, the temperature of the third aging treatment is 20-35 ℃ and the aging time is 12-24 h.
Further, the temperature of the fourth aging treatment is 30-65 ℃ and the aging time is 1-12 h.
Further, the time of the second crystallization treatment is 12-60 h.
The second object of the invention is to provide the NaY zeolite with high silicon-aluminum ratio prepared by the preparation method.
Further, the crystallinity of the NaY zeolite with high silicon-aluminum ratio is more than or equal to 90 percent, and the silicon-aluminum ratio is 5.5 to 7.0.
The third object of the invention is to provide an application of the NaY zeolite with high silicon-aluminum ratio in preparing an adsorbent and a catalyst.
Compared with the prior art, the invention has the following beneficial effects:
firstly, a guiding agent A prepared from sodium salt, a silicon source A, an aluminum source A and water is used as a guiding agent of zeolite gel crystal seeds, the guiding agent A reacts with a silicon source B, an aluminum source B and an alkali source A to form zeolite gel crystal seeds containing abundant high-silicon crystal nucleus precursors, and then the obtained zeolite gel crystal seeds are used as precursor materials to regulate and control the polymerization reaction of silicon-aluminum substances in the crystal growth process, wherein the zeolite gel crystal seeds contain abundant high-silicon crystal nucleus precursors, so that abundant crystal nuclei are provided for the zeolite crystallization process, and the crystallization time is shortened; and the gel silica-alumina environment is regulated and controlled, and the silicon is promoted to enter the zeolite framework, so that the silica-alumina ratio in the zeolite framework is high, and the property of the NaY zeolite with high silica-alumina ratio can be improved finally.
The preparation method disclosed by the invention has the advantages that no organic template agent or organic additive is required to be added, the process is simple, the environment is protected, the rapid preparation can be realized, the preparation can be realized in the existing industrial production device, other equipment is not required to be added, and the preparation method is suitable for industrial production.
The high silicon-aluminum ratio NaY zeolite prepared by the method has the crystallinity of more than 90 percent and the silicon-aluminum ratio of 5.5-7.0, has the advantages of heat stability and acidity, and has very important significance for improving the performance of the catalytic cracking catalyst.
Drawings
FIG. 1 is an XRD pattern of a high silica to alumina ratio NaY zeolite of example 1 of the present invention;
FIG. 2 is an XRD pattern of the high silica to alumina ratio NaY zeolite of example 2 of the present invention;
FIG. 3 is an XRD pattern of the high silica to alumina ratio NaY zeolite of example 3 of the present invention;
FIG. 4 is an XRD pattern of the high silica to alumina ratio NaY zeolite of example 4 of the present invention;
FIG. 5 is an XRD pattern of the high silica to alumina ratio NaY zeolite of example 5 of the present invention;
FIG. 6 is an XRD pattern of the high silica to alumina ratio NaY zeolite of example 6 of the present invention;
FIG. 7 is an XRD pattern of the high silica to alumina ratio NaY zeolite of comparative example 1 of the present invention;
FIG. 8 is an XRD pattern of the high silica to alumina ratio NaY zeolite of comparative example 2 of the present invention;
FIG. 9 is an XRD pattern of the high silica to alumina ratio NaY zeolite of comparative example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The invention provides a high silicon-aluminum ratio NaY zeolite, and a preparation method thereof comprises the following steps:
step 1, preparing zeolite gel seed crystal
1.1 preparation of guiding agent A
Uniformly dispersing a silicon source A, an aluminum source A and sodium salt in an aqueous solution A, and obtaining a guiding agent A after first aging treatment;
the present invention is not limited to the specific types of the silicon source A, the aluminum source A and the sodium salt, so long as the silicon source A, the aluminum source A and the sodium salt can form a mixture with the aqueous solution A, sodium salt, na 2 O、Al 2 O 3 、SiO 2 And H 2 The molar ratio of O was (5.0X10) -2 -20) sodium salt: (8-20) Na 2 O：Al 2 O 3 ：(10-20)SiO 2 ：(100-350)H 2 O is as follows, wherein Na 2 O is derived from a silicon source A and an aluminum source A, al 2 O 3 Derived from an aluminum source A, siO 2 From a silicon source a. In the invention, the silicon source A is selected from one or two of water glass and alkaline silica sol; the aluminum source A is selected from one or two of sodium metaaluminate and high-alkali sodium metaaluminate; the sodium salt is any one of NaCl, naBr and NaI.
The invention is not limited to specific process parameters of the first aging treatment, as long as the silicon source A, the aluminum source A and the sodium salt can be fully contacted with the aqueous solution A to form the guiding agent A with uniform components, and the invention can age for 12-24 hours at the temperature of 20-35 ℃. In order to make the contact between the silicon source A, the aluminum source A and the sodium salt and the aqueous solution A more sufficient, the silicon source A, the aluminum source A and the sodium salt are mixed by adopting a mechanical stirring mode, wherein the invention does not particularly limit the specific process parameters of stirring, and the time is generally 1-2 h as long as the materials are stirred according to actual conditions.
1.2 formation of zeolite gel seed crystals
Uniformly dispersing a guiding agent A, a silicon source B, an aluminum source B and an alkali source A in an aqueous solution B, performing a second aging treatment, and performing a first crystallization treatment at 85-100 ℃ to obtain zeolite gel seed crystals;
it should be noted thatThe present invention is not limited to the specific types of the silicon source B, the aluminum source B and the alkali source A, so long as Na is contained in the mixture of the directing agent A and the silicon source B, the aluminum source B and the alkali source A and the aqueous solution B 2 O、Al 2 O 3 、SiO 2 And H 2 O molar ratio of (2-4) Na 2 O：Al 2 O 3 ：(6-15)SiO 2 ：(100-300)H 2 O is the silicon source B is one or two selected from water glass and alkaline silica sol; when the aluminum source B is selected from one or two of sodium metaaluminate and sodium high-alkali metaaluminate, and sodium metaaluminate and/or sodium high-alkali metaaluminate are used as the aluminum source B, the sodium metaaluminate and the sodium high-alkali metaaluminate have strong alkalinity and are also used as the alkali source A, so that an additional alkali source is not required to be added; the sodium salt accounts for 3-18 wt% of the guiding agent A.
The invention is not limited to specific process parameters of the second aging treatment, as long as the guiding agent A and the silicon source B, the aluminum source B and the alkali source A and the aqueous solution B can be fully contacted to form zeolite gel seed crystal precursors with uniform components, and the invention can age for 1-12 hours at the temperature of 30-60 ℃. In order to make the contact between the guiding agent A and the silicon source B, the aluminum source B and the alkali source A and the aqueous solution B more complete, the guiding agent A and the aqueous solution B are mixed by adopting a mechanical stirring mode, wherein the method is not particularly limited to specific technological parameters of stirring, and the method is determined according to actual conditions, and the time is generally 1-2 h as long as materials are stirred.
The invention is not limited to specific technological parameters of the first crystallization treatment, and only needs to prepare the zeolite gel seed crystal solid material, and optionally, the invention can crystallize at the temperature of 85-100 ℃ for 6-60 h.
Step 2, crystallizing to form NaY zeolite with high silicon-aluminum ratio
2.1 preparation of guiding agent B
Uniformly dispersing a silicon source C and an aluminum source C in the aqueous solution C, and performing aging treatment for the third time to obtain a guiding agent B;
the present invention is not limited to the specific type of the silicon source C and the aluminum source C, so long as Na is contained in the mixture of the silicon source C and the aluminum source C with the aqueous solution C 2 O、Al 2 O 3 、SiO 2 And H 2 O molar ratio of (10-20) Na 2 O：Al 2 O 3 ：(10-20)SiO 2 ：(100-350)H 2 O is the silicon source C is one or more selected from silica sol, water glass, white carbon black and silica gel; the aluminum source C is selected from one or more of sodium metaaluminate, high alkali sodium metaaluminate, aluminum sulfate, aluminum nitrate and aluminum hydroxide.
The invention is not limited to the specific process parameters of the third aging treatment, as long as the silicon source C and the aluminum source C can be fully contacted with the aqueous solution C to form a uniform guiding agent B, and optionally, the invention can age for 12-24 hours at the temperature of 20-35 ℃. In order to make the silicon source C and the aluminum source C fully contacted with the aqueous solution C, the silicon source C and the aluminum source C are mixed by adopting a mechanical stirring mode, wherein the invention does not particularly limit the specific process parameters of stirring, and the invention is determined according to actual conditions, and the time is generally 1-2 h as long as materials are stirred.
2.2 formation of NaY zeolite with high silica-alumina ratio
Uniformly dispersing a guiding agent B, a silicon source D, zeolite gel seed crystals, an alkali source B and an aluminum source D in an aqueous solution D, performing a fourth aging treatment, and performing a second crystallization treatment at 85-100 ℃ to obtain NaY zeolite with high silicon-aluminum ratio;
the specific types of the silicon source D, the zeolite gel seed crystal, the alkali source B and the aluminum source D are not limited in the present invention, so long as Na is contained in the mixture of the directing agent B and the silicon source D, the zeolite gel seed crystal, the alkali source B and the aluminum source D with the aqueous solution C 2 O、Al 2 O 3 、SiO 2 And H 2 O molar ratio of (2-4) Na 2 O：Al 2 O 3 ：(7-12)SiO 2 ：(100-300)H 2 O is the silicon source D is one or more selected from silica sol, water glass, white carbon black and silica gel; the aluminum source D is selected from one or more of sodium metaaluminate, high-alkali sodium metaaluminate, aluminum sulfate, aluminum nitrate and aluminum hydroxide, and when sodium metaaluminate and/or high-alkali sodium metaaluminate are used as the aluminum source D, the sodium metaaluminate and the high-alkali sodium metaaluminate have strong alkalinity and are also used as the alkali source B, so that the reaction can be realized without additional alkali source; and, boilThe use level of the stone gel seed crystal accounts for 1-20wt% of the guiding agent B.
The invention does not limit the specific technological parameters of the second crystallization treatment, only the NaY zeolite solid material with high silicon-aluminum ratio can be prepared, and the invention can be used for crystallization treatment for 12-60 h at the temperature of 85-100 ℃.
Example 1
The embodiment provides a high silica alumina ratio NaY zeolite, and the preparation method thereof is as follows:
s1, preparation of zeolite gel seed crystals:
s1.1 preparation of guiding agent A
30.08g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt.%), 20.50g of sodium meta-aluminate (Al) with high alkali content was added 2 O 3 The content of Na is 3.16wt percent 2 Uniformly mixing 10.40g of NaCl and 8.56g of deionized water, stirring at 35 ℃ and a stirring rate of 150r/min for 1h, and standing and aging for 12h to obtain a guiding agent A; wherein, water glass is used as a silicon source A, sodium metaaluminate with high alkali is used as an aluminum source A, and NaCl is used as a sodium salt A.
S1.2 obtaining NaY zeolite gel seed crystals
118.32g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content of 8.96 wt%) is placed in a beaker, placed in a water bath at 60 deg.C, and under stirring condition, the above-mentioned directing agent A and 23.90g of high-alkali sodium metaaluminate (Al) are added 2 O 3 The content of Na is 3.16wt percent 2 O content of 21.11 wt%) and 24g deionized water were stirred at a stirring rate of 150r/min for 30 minutes, and then 79.20g aluminum sulfate (Al) 2 O 3 The mixture is stirred for 30 minutes at the stirring rate of 150r/min and is uniformly mixed, and then the mixture is stood and aged for 1 hour to prepare reaction mixture gel; and (3) putting the reaction mixture gel into a reaction kettle, crystallizing for 6 hours in an oven at 90 ℃, filtering, washing and drying to obtain NaY zeolite gel seed crystals, wherein water glass is used as a silicon source B, sodium metaaluminate with high alkali and aluminum sulfate are used as an aluminum source B, and meanwhile, the water glass and sodium metaaluminate with high alkali are used as an alkali source A.
S2, preparation of NaY zeolite with high silicon-aluminum ratio
S2.1 preparation of guiding agent B
18.85g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt.%, 20.80g of sodium meta-aluminate (Al) with high alkali content was added 2 O 3 The content of Na is 3.16wt percent 2 Mixing the mixture with water in the amount of 21.11wt% O and 6.56g water, stirring at 25 deg.c, ageing for 24 hr to obtain guide agent B; wherein, water glass is used as a silicon source C, and sodium metaaluminate with high alkali is used as an aluminum source C.
S2.2 obtaining NaY zeolite with high silicon-aluminum ratio
104.32g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content of 8.96 wt%) is placed in a beaker, and placed in a water bath at 60 deg.C, under the condition of stirring, the above-mentioned directing agent B and 5g of zeolite gel seed crystal prepared in the step (1) and 18.15g of high-alkali sodium metaaluminate (Al are added 2 O 3 The content of Na is 3.16wt percent 2 O content 21.11 wt%) and 24g of water, and after stirring for 30 minutes, 59.83g of aluminum sulfate (Al) was added 2 O 3 The content of the catalyst is 7.6wt percent), and the mixture is stirred and mixed uniformly and aged for 12 hours to prepare a reaction mixture gel; and (3) putting the reaction mixture gel into a reaction kettle, crystallizing for 24 hours at 90 ℃, filtering, washing and drying to obtain NaY zeolite with high silicon-aluminum ratio, wherein water glass is used as a silicon source D, high alkali sodium metaaluminate and aluminum sulfate are used as an aluminum source D, and simultaneously, the water glass and the high alkali sodium metaaluminate are used as an alkali source B together.
XRD characterization results of the high silica alumina ratio NaY zeolite prepared in the embodiment are shown in figure 1;
the relative crystallinity of the sample prepared in this example was 93%, and silicon aluminum (SiO) 2 /Al 2 O 3 ) The molar ratio was 6.65.
Example 2
The embodiment provides a high silica alumina ratio NaY zeolite, and the preparation method thereof is as follows:
s1, preparation of zeolite gel seed crystals:
s1.1 preparation of guiding agent A
20.88g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt.%) and 20.50g of high-alkali sodium metaaluminate was added(Al 2 O 3 The content of Na is 3.16wt percent 2 Uniformly mixing 21.11wt% of O, 1.70g of NaBr and 8.56g of water, uniformly stirring at 25 ℃, and aging for 24 hours to prepare a guiding agent A; wherein, water glass is used as a silicon source A, sodium metaaluminate with high alkali is used as an aluminum source A, and NaBr is used as a sodium salt A.
S1.2 obtaining NaY zeolite gel seed crystals
118.18g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content of 8.96 wt%) is placed in a beaker, placed in a water bath at 30 deg.C, and under the condition of stirring, the above-mentioned directing agent A and 5.90g of high-alkali sodium metaaluminate (Al) are added 2 O 3 The content of Na is 3.16wt percent 2 O content of 21.11 wt%) and 37.02g deionized water, stirring for 30 minutes, and adding 49.20g aluminum sulfate (Al) 2 O 3 The content of the catalyst is 7.6wt percent), and the mixture is stirred and mixed uniformly and aged for 12 hours to prepare a reaction mixture gel; and (3) putting the reaction mixture gel into a reaction kettle, crystallizing for 24 hours at 100 ℃, filtering, washing and drying to obtain NaY zeolite gel seed crystals, wherein water glass is used as a silicon source B, sodium metaaluminate with high alkali and aluminum sulfate are used as an aluminum source B together, and meanwhile, the water glass and sodium metaaluminate with high alkali are also used as an alkali source A together.
S2, preparation of NaY zeolite with high silicon-aluminum ratio
S2.1 preparation of guiding agent B
16.80g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt.%, 18.65g of sodium meta-aluminate (Al) with high alkali content was added 2 O 3 The content of Na is 3.16wt percent 2 Mixing the mixture with the deionized water of which the O content is 21.11 weight percent and 8.86g uniformly, stirring uniformly at 20 ℃, and aging for 12 hours to prepare a guiding agent B; wherein, water glass is used as a silicon source C, and sodium metaaluminate with high alkali is used as an aluminum source C.
S2.2 obtaining NaY zeolite with high silicon-aluminum ratio
114.32g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content of 8.96 wt%) is placed in a beaker, placed in a water bath at 30 deg.C, under the condition of stirring, added with the above-mentioned directing agent B and 3g of zeolite gel seed crystal prepared in the step (1) and 13.44g of high-alkali sodium metaaluminate (Al 2 O 3 The content is 3.16wt％，Na 2 O content of 21.11 wt%) and 18.51g deionized water, and after stirring for 30 minutes, 29.33g aluminum sulfate (Al) was added 2 O 3 The content of the catalyst is 7.6wt percent), and the mixture is stirred and mixed uniformly and aged for 1h to prepare a reaction mixture gel; and (3) putting the reaction mixture gel into a reaction kettle, crystallizing for 12 hours at 90 ℃, filtering, washing and drying to obtain NaY zeolite with high silicon-aluminum ratio, wherein water glass is used as a silicon source D, high alkali sodium metaaluminate and aluminum sulfate are used as an aluminum source D, and simultaneously, the water glass and the high alkali sodium metaaluminate are used as an alkali source B together.
XRD characterization results of the high silica alumina ratio NaY zeolite prepared in the embodiment are shown in figure 2;
the relative crystallinity of the sample prepared in this example was 92% and was based on silicon aluminum (SiO 2 /Al 2 O 3 ) The molar ratio was 5.96.
Example 3
The embodiment provides a high silica alumina ratio NaY zeolite, and the preparation method thereof is as follows:
s1, preparation of zeolite gel seed crystals:
s1.1 preparation of guiding agent A
20.88g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt.%), 20.50g of sodium meta-aluminate (Al) with high alkali content was added 2 O 3 The content of Na is 3.16wt percent 2 Mixing uniformly the mixture of 21.11wt% of O, 8.50g of NaI and 8.56g of deionized water, stirring uniformly at 20 ℃, and aging for 16 hours to prepare a guiding agent A; wherein, water glass is used as a silicon source A, sodium metaaluminate with high alkali is used as an aluminum source A, and NaI is used as a sodium salt A.
S1.2 obtaining NaY zeolite gel seed crystals
108.18g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content of 8.96 wt%) is placed in a beaker, placed in a water bath at 50 deg.C, and under stirring condition the above-mentioned directing agent A and 10.90g of high-alkali sodium metaaluminate (Al) are added 2 O 3 The content of Na is 3.16wt percent 2 O content of 21.11 wt%) and 27.02g deionized water, and after stirring for 30 minutes, 54.48g aluminum sulfate (Al) was added 2 O 3 The mixture is stirred and mixed evenly with the content of 7.6 weight percent, and aged for 1 hour to prepare a reaction mixtureGel; the reaction mixture gel is put into a reaction kettle to be crystallized for 40 hours at 96 ℃, and then is filtered, washed and dried to obtain NaY zeolite gel seed crystal, in the embodiment, sodium silicate is used as a silicon source B, sodium high-alkali metaaluminate and aluminum sulfate are used as an aluminum source B together, and simultaneously, sodium silicate and sodium high-alkali metaaluminate are used as an alkali source A together.
S2, preparation of NaY zeolite with high silicon-aluminum ratio
S2.1 preparation of guiding agent B
20.80g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt.%, 20.65g of sodium high alkali metaaluminate (Al) was added 2 O 3 The content of Na is 3.16wt percent 2 Mixing the mixture with the O content of 21.11wt percent and 8.36g deionized water uniformly, stirring uniformly at 35 ℃, and aging for 18 hours to prepare a guiding agent B; wherein, water glass is used as a silicon source C, and sodium metaaluminate with high alkali is used as an aluminum source C.
S2.2 obtaining NaY zeolite with high silicon-aluminum ratio
110.32g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content of 8.96 wt%) in a beaker, placing in a water bath at 50 deg.C, stirring, adding the above-mentioned directing agent B and 5g of zeolite gel seed crystal prepared in the step (1) and 10.44g of high-alkali sodium metaaluminate (Al 2 O 3 The content of Na is 3.16wt percent 2 O content of 21.11 wt%) and 20.51g deionized water, and after stirring for 30 minutes, 49.33g aluminum sulfate (Al) was added 2 O 3 The content of the catalyst is 7.6wt percent), and the mixture is stirred and mixed uniformly and aged for 3 hours to prepare a reaction mixture gel; and (3) putting the reaction mixture gel into a reaction kettle, crystallizing for 15 hours at 100 ℃, filtering, washing and drying to obtain NaY zeolite with high silicon-aluminum ratio, wherein water glass is used as a silicon source D, high alkali sodium metaaluminate and aluminum sulfate are used as an aluminum source D, and simultaneously, the water glass and the high alkali sodium metaaluminate are used as an alkali source B together.
XRD characterization results of the high silica alumina ratio NaY zeolite prepared in the embodiment are shown in figure 3;
the relative crystallinity of the sample prepared in this example was 94% and the relative crystallinity of silicon aluminum (SiO) 2 /Al 2 O 3 ) The molar ratio was 6.03.
Example 4
The embodiment provides a high silica alumina ratio NaY zeolite, and the preparation method thereof is as follows:
s1, preparation of zeolite gel seed crystals:
s1.1 preparation of guiding agent A
30.08g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt.%), 20.50g of sodium meta-aluminate (Al) with high alkali content was added 2 O 3 The content of Na is 3.16wt percent 2 Uniformly mixing 21.11wt% of O, 5.20g of NaCl and 8.56g of deionized water, uniformly stirring at 25 ℃, and aging for 20 hours to prepare a guiding agent A; wherein, water glass is used as a silicon source A, sodium metaaluminate with high alkali is used as an aluminum source A, and NaCl is used as a sodium salt A.
S1.2 obtaining NaY zeolite gel seed crystals
118.32g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content of 8.96 wt%) is placed in a beaker, placed in a water bath at 50 deg.C, under stirring condition the above-mentioned directing agent A and 23.90g of high-alkali sodium metaaluminate (Al) are added 2 O 3 The content of Na is 3.16wt percent 2 O content of 21.11 wt%) and 24g deionized water, and after stirring for 30 minutes, 79.20g aluminum sulfate (Al) was added 2 O 3 The content of the catalyst is 7.6wt%) and is stirred and mixed uniformly, and aged for 6 hours to prepare a reaction mixture gel; and (3) putting the reaction mixture gel into a reaction kettle, crystallizing for 30 hours at 98 ℃, filtering, washing and drying to obtain NaY zeolite gel seed crystals, wherein water glass is used as a silicon source B, sodium metaaluminate with high alkali and aluminum sulfate are used as an aluminum source B, and meanwhile, the water glass and sodium metaaluminate with high alkali are used as an alkali source A.
S2, preparation of NaY zeolite with high silicon-aluminum ratio
S2.1 preparation of guiding agent B
18.85g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt.%, 20.80g of sodium meta-aluminate (Al) with high alkali content was added 2 O 3 The content of Na is 3.16wt percent 2 Mixing the mixture with the O content of 21.11wt percent and 6.56g deionized water uniformly, stirring uniformly at 32 ℃, and aging for 18 hours to prepare a guiding agent B; wherein, water glass is used as a silicon source C, and sodium metaaluminate with high alkali is used as an aluminum source C.
S2.2 obtaining NaY zeolite with high silicon-aluminum ratio
104.32g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content of 8.96 wt%) in a beaker, placing in a water bath at 50 deg.C, stirring, adding the above-mentioned directing agent B and 5g of zeolite gel seed crystal prepared in the step (1) and 18.15g of high-alkali sodium metaaluminate (Al 2 O 3 The content of Na is 3.16wt percent 2 O content of 21.11 wt%) and 24g deionized water, and after stirring for 30 minutes, 59.83g aluminum sulfate (Al) was added 2 O 3 The content of the catalyst is 7.6wt%) and is stirred and mixed uniformly, and aged for 6 hours to prepare a reaction mixture gel; and (3) putting the reaction mixture gel into a reaction kettle, crystallizing for 24 hours at 98 ℃, filtering, washing and drying to obtain NaY zeolite with high silicon-aluminum ratio, wherein water glass is used as a silicon source D, high alkali sodium metaaluminate and aluminum sulfate are used as an aluminum source D, and simultaneously, the water glass and the high alkali sodium metaaluminate are used as an alkali source B together.
XRD characterization results of the high silica alumina ratio NaY zeolite prepared in the embodiment are shown in figure 4;
the relative crystallinity of the sample prepared in this example was 92% and was based on silicon aluminum (SiO 2 /Al 2 O 3 ) The molar ratio was 5.88.
Example 5
The embodiment provides a high silica alumina ratio NaY zeolite, and the preparation method thereof is as follows:
s1, preparation of zeolite gel seed crystals:
s1.1 preparation of guiding agent A
20.88g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt.%), 20.50g of sodium meta-aluminate (Al) with high alkali content was added 2 O 3 The content of Na is 3.16wt percent 2 Uniformly mixing 21.11wt% of O, 5.00g of NaBr and 8.56g of deionized water, uniformly stirring at 25 ℃, and aging for 24 hours to prepare a guiding agent A; wherein, water glass is used as a silicon source A, sodium metaaluminate with high alkali is used as an aluminum source A, and NaBr is used as a sodium salt A.
118.18g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt%) was placed in a beaker and placed in water at 30 ℃Bath, adding the guiding agent A and 5.90g of high alkali sodium metaaluminate (Al) under stirring 2 O 3 The content of Na is 3.16wt percent 2 O content of 21.11 wt%) and 37.02g deionized water, stirring for 30 minutes, and adding 49.20g aluminum sulfate (Al) 2 O 3 The content of the catalyst is 7.6wt percent), and the mixture is stirred and mixed uniformly and aged for 12 hours to prepare a reaction mixture gel; and (3) putting the reaction mixture gel into a reaction kettle, crystallizing for 8 hours at 100 ℃, filtering, washing and drying to obtain NaY zeolite gel seed crystals, wherein water glass is used as a silicon source B, sodium metaaluminate with high alkali and aluminum sulfate are used as an aluminum source B, and meanwhile, the water glass and sodium metaaluminate with high alkali are used as an alkali source A.
S2, preparation of NaY zeolite with high silicon-aluminum ratio
S2.1 preparation of guiding agent B
16.80g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt.%, 18.65g of sodium meta-aluminate (Al) with high alkali content was added 2 O 3 The content of Na is 3.16wt percent 2 Mixing the mixture with the deionized water of which the O content is 21.11 weight percent and 8.86g uniformly, stirring uniformly at 20 ℃, and aging for 12 hours to prepare a guiding agent B; wherein, water glass is used as a silicon source C, and sodium metaaluminate with high alkali is used as an aluminum source C.
S2.2 obtaining NaY zeolite with high silicon-aluminum ratio
114.32g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content of 8.96 wt%) in a beaker, placing in a water bath at 30 deg.C, stirring, adding the above-mentioned directing agent B and 5.00g of zeolite gel seed crystal prepared in step (1) and 13.44g of high-alkali sodium metaaluminate (Al 2 O 3 The content of Na is 3.16wt percent 2 O content of 21.11 wt%) and 18.51g deionized water, and after stirring for 30 minutes, 29.33g aluminum sulfate (Al) was added 2 O 3 The content of the catalyst is 7.6wt percent), and the mixture is stirred and mixed uniformly and aged for 1h to prepare a reaction mixture gel; and (3) putting the reaction mixture gel into a reaction kettle, crystallizing for 28 hours at 96 ℃, filtering, washing and drying to obtain NaY zeolite with high silicon-aluminum ratio, wherein water glass is used as a silicon source D, high alkali sodium metaaluminate and aluminum sulfate are used as an aluminum source D, and simultaneously, the water glass and the high alkali sodium metaaluminate are used as an alkali source B together.
XRD characterization results of the high silica alumina ratio NaY zeolite prepared in the embodiment are shown in figure 5;
the relative crystallinity of the sample prepared in this example was 95% and the silica alumina (SiO) 2 /Al 2 O 3 ) The molar ratio was 6.08.
Example 6
The embodiment provides a high silica alumina ratio NaY zeolite, and the preparation method thereof is as follows:
s1, preparation of zeolite gel seed crystals:
s1.1 preparation of guiding agent A
20.88g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt.%), 20.50g of sodium meta-aluminate (Al) with high alkali content was added 2 O 3 The content of Na is 3.16wt percent 2 Uniformly mixing 21.11wt% of O, 10.00g of NaI and 8.56g of deionized water, uniformly stirring at 20 ℃, and aging for 16 hours to prepare a guiding agent A; the method comprises the steps of carrying out a first treatment on the surface of the Wherein, water glass is used as a silicon source A, sodium metaaluminate with high alkali is used as an aluminum source A, and NaI is used as a sodium salt A.
108.18g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content of 8.96 wt%) is placed in a beaker, placed in a water bath at 50 deg.C, and under stirring condition the above-mentioned directing agent A and 10.90g of high-alkali sodium metaaluminate (Al) are added 2 O 3 The content of Na is 3.16wt percent 2 O content of 21.11 wt%) and 27.02g deionized water, and after stirring for 30 minutes, 54.48g aluminum sulfate (Al) was added 2 O 3 The content of the catalyst is 7.6wt percent), and the mixture is stirred and mixed uniformly and aged for 1h to prepare a reaction mixture gel; and (3) putting the reaction mixture gel into a reaction kettle, crystallizing for 20 hours at 96 ℃, filtering, washing and drying to obtain NaY zeolite gel seed crystals, wherein water glass is used as a silicon source B, sodium metaaluminate with high alkali and aluminum sulfate are used as an aluminum source B, and meanwhile, the water glass and sodium metaaluminate with high alkali are used as an alkali source A.
S2, preparation of NaY zeolite with high silicon-aluminum ratio
S2.1 preparation of guiding agent B
20.80g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content was 8.96 wt.%, 20.65g of sodium high alkali metaaluminate (Al) was added 2 O 3 The content of Na is 3.16wt percent 2 Mixing the mixture with the O content of 21.11wt percent and 8.36g deionized water uniformly, stirring uniformly at 35 ℃, and aging for 18 hours to prepare a guiding agent B; wherein, water glass is used as a silicon source C, and sodium metaaluminate with high alkali is used as an aluminum source C.
S2.2 obtaining NaY zeolite with high silicon-aluminum ratio
110.32g of water glass (SiO) 2 The content of Na is 27.6wt% 2 O content of 8.96 wt%) in a beaker, placing in a water bath at 50 deg.C, adding the above-mentioned directing agent B and 10.00g of zeolite gel seed crystal prepared in the step (1) and 10.44g of high-alkali sodium metaaluminate (Al 2 O 3 The content of Na is 3.16wt percent 2 O content of 21.11 wt%) and 20.51g deionized water, and after stirring for 30 minutes, 49.33g aluminum sulfate (Al) was added 2 O 3 The content of the catalyst is 7.6wt percent), and the mixture is stirred and mixed uniformly and aged for 1h to prepare a reaction mixture gel; and (3) putting the reaction mixture gel into a reaction kettle, crystallizing for 26 hours at the temperature of 100 ℃, filtering, washing and drying to obtain NaY zeolite with high silicon-aluminum ratio, wherein water glass is used as a silicon source D, high alkali sodium metaaluminate and aluminum sulfate are used as an aluminum source D, and simultaneously, the water glass and the high alkali sodium metaaluminate are used as an alkali source B together.
XRD characterization results of the high silica alumina ratio NaY zeolite prepared in the embodiment are shown in FIG. 6;
the relative crystallinity of the sample prepared in this example was 90% and the silica alumina (SiO) 2 /Al 2 O 3 ) The molar ratio was 6.25.
Example 7
This example provides a high silica to alumina ratio NaY zeolite and the process for its preparation differs from example 1 only in that:
s1.1, according to 5.0X10 -2 Sodium salt: 8Na 2 O：Al 2 O 3 ：10SiO 2 ：100H 2 O, uniformly dispersing a silicon source A, an aluminum source A and sodium salt in deionized water; in this embodiment, the silicon source A is alkaline silica sol; the aluminum source A is sodium metaaluminate; and the sodium salt accounts for 3wt% of the guiding agent A;
the temperature of the first aging treatment is 20 ℃ and the aging time is 12 hours;
s1.2 according to 2Na 2 O：Al 2 O 3 ：6SiO 2 ：100H 2 O, uniformly dispersing a guiding agent A, a silicon source B, an aluminum source B and an alkali source A in deionized water; in this embodiment, the silicon source B is an alkaline silica sol; the aluminum source B is sodium metaaluminate, and the sodium metaaluminate and the alkaline silica sol are simultaneously used as an alkaline source A;
the temperature of the second aging treatment is 30 ℃, and the aging time is 1h; the temperature of the first crystallization treatment is 60 ℃, and the crystallization time is 6 hours.
S2.1 according to 10Na 2 O：Al 2 O 3 ：10SiO 2 ：100H 2 O, uniformly dispersing a silicon source C and an aluminum source C in deionized water; in this embodiment, silica sol is used as the silicon source C;
the temperature of the third aging treatment is 20 ℃, and the aging time is 12 hours.
S2.2 according to 2Na 2 O：Al 2 O 3 ：7SiO 2 ：100H 2 O, uniformly dispersing a guiding agent B, a silicon source D, zeolite gel seed crystals, an alkali source B and an aluminum source D in deionized water; in the embodiment, silica sol is used as a silica source D, high-alkali sodium metaaluminate and aluminum nitrate are used as an aluminum source C, the silica sol and the high-alkali sodium metaaluminate are simultaneously used as an alkali source B, and the use amount of zeolite gel crystal seeds accounts for 1wt% of the guiding agent B;
the temperature of the fourth aging treatment is 30 ℃, and the aging time is 1h;
the second crystallization treatment time was 12h.
Example 8
This example provides a high silica to alumina ratio NaY zeolite and the process for its preparation differs from example 1 only in that:
s1.1, according to 20 sodium salt: 20Na (sodium carbonate) 2 O：Al 2 O 3 ：20SiO 2 ：350H 2 O, uniformly dispersing a silicon source A, an aluminum source A and sodium salt in deionized water; in this embodiment, the silicon source A is alkaline silica sol; the aluminum source A is sodium metaaluminate; and the sodium salt accounts for 18wt% of the guiding agent A;
the temperature of the first aging treatment is 35 ℃, and the aging time is 24 hours.
S1.2 according to 4Na 2 O：Al 2 O 3 ：15SiO 2 ：300H 2 O, uniformly dispersing a guiding agent A, a silicon source B, an aluminum source B and an alkali source A in deionized water; in this embodiment, the silicon source B is an alkaline silica sol; the aluminum source B is sodium metaaluminate, and the sodium metaaluminate and the alkaline silica sol are simultaneously used as an alkaline source A;
the temperature of the second aging treatment is 60 ℃, and the aging time is 12 hours;
the temperature of the first crystallization treatment is 100 ℃ and the time is 60 hours.
S2.1 according to 20Na 2 O：Al 2 O 3 ：20SiO 2 ：350H 2 O, uniformly dispersing a silicon source C and an aluminum source C in deionized water; in this embodiment, silica sol is used as the silicon source C;
the temperature of the third aging treatment is 35 ℃, and the aging time is 24 hours.
S2.2 according to 4Na 2 O：Al 2 O 3 ：12SiO 2 ：300H 2 O, uniformly dispersing a guiding agent B, a silicon source D, zeolite gel seed crystals, an alkali source B and an aluminum source D in deionized water; in the embodiment, silica sol is used as a silica source D, high-alkali sodium metaaluminate and aluminum nitrate are used as an aluminum source C, the silica sol and the high-alkali sodium metaaluminate are simultaneously used as an alkali source B, and the use amount of zeolite gel crystal seeds is 20wt% of the guiding agent B;
the temperature of the fourth aging treatment is 65 ℃ and the aging time is 12 hours;
the second crystallization treatment time was 60h.
Example 9
This example provides a high silica to alumina ratio NaY zeolite and the process for its preparation differs from example 1 only in that:
in this embodiment, both silicon source C and silicon source D are selected from silica gel; the aluminum source C and the aluminum source D are both selected from sodium metaaluminate and aluminum hydroxide.
Comparative example 1
This comparative example provides a high silica to alumina ratio NaY zeolite and the process for its preparation differs from example 1 only in that:
in this comparative example, no sodium salt (NaCl, naBr, and NaI) was added, and no zeolite gel seed crystals were added.
XRD characterization results of the high silica alumina ratio NaY zeolite prepared in the embodiment are shown in figure 7;
the relative crystallinity of the sample prepared in this example was 85% and the silica alumina (SiO) 2 /Al 2 O 3 ) The molar ratio was 5.41.
Comparative example 2
This comparative example provides a high silica to alumina ratio NaY zeolite and the process for its preparation differs from example 2 only in that:
in this comparative example, no sodium salt (NaCl, naBr, and NaI) was added, and no zeolite gel seed crystals were added.
The temperature of the second crystallization treatment is 100 ℃, and the crystallization time is 40h.
XRD characterization results of the high silica alumina ratio NaY zeolite prepared in the comparative example are shown in FIG. 8;
the sample prepared in this comparative example had a relative crystallinity of 70% and contained NaP hetero-crystals, silicon aluminum (SiO) 2 /Al 2 O 3 ) The molar ratio was 5.31.
Comparative example 3
This comparative example provides a high silica to alumina ratio NaY zeolite and the process for its preparation differs from example 2 only in that:
in this comparative example, no sodium salt (NaCl, naBr, and NaI) was added, and no zeolite gel seed crystals were added;
the temperature of the second crystallization treatment is 100 ℃, and the crystallization time is 40h.
XRD characterization results of the high silica alumina ratio NaY zeolite prepared in the comparative example are shown in FIG. 9;
the sample prepared in this comparative example had a relative crystallinity of 85% and contained NaP hetero-crystals, silicon aluminum (SiO) 2 /Al 2 O 3 ) The molar ratio was 5.30.
In the above examples and comparative examples of the present invention, the relative crystallinity and silica/alumina ratio of the synthesized NaY zeolite were measured using a BRUKER D8 ADVANCE (BRUKER, germany) X-ray diffractometer under the following experimental conditions: cuKa radiation (0.1541 nm), tube voltage 30kV, tube current 20mA. The relative crystallinity was determined according to SH/T0340-92 standard method (chemical industry Standard Association, china Standard Press, 2000). The Si/Al ratio was measured according to SH/T0339-92 standard method (chemical industry Standard Association, china Standard Press, 2000), and after calculating the unit cell constant of NaY zeolite according to the formula (1), the unit cell constant was calculated according to the formula Breck-Flanigen: si/al= (25.858- α)/(α -24.191).
Wherein,
a-the unit cell constant of the crystal,
lambda-CuK alpha 1 radiation wavelength
h2+k2+l2-X-ray diffraction miller index sum of squares.
The zeolite standard used in examples and comparative examples as the crystallinity standard used in crystallization examples and comparative examples was derived from an industrial NaY reference, and the SiO of the zeolite was measured by X-ray diffraction 2 /Al 2 O 3 5.0, and the crystallinity thereof was set to 100%.
The high silica alumina ratio NaY zeolite with high crystallinity, which is suitable for industrial production, is prepared in examples 1-6 of the invention, and has parallel effects, and the comparison study is carried out on the high silica alumina ratio NaY zeolite prepared in examples 1-6 and comparative examples 1-3, and the specific study results are shown in table 1:
TABLE 1 examples 1-6, comparative examples 1-3 relative crystallinity, silicon to aluminum ratio, unit cell constant and crystal phase analysis table
According to XRD patterns of the samples shown in figures 1-9, the relevant data shown in table 1 are obtained through calculation and analysis, and the result shows that the NaY zeolite prepared by the method has the advantages of high crystallinity and high silicon-aluminum ratio, the NaY zeolite prepared by the method is used as a post-modified raw material, and the prepared catalyst has higher stability and more strong acid centers and is also more beneficial to the conversion of heavy oil molecules.
It should be apparent that the embodiments described above are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (8)
1. The preparation method of the NaY zeolite with high silicon-aluminum ratio is characterized by comprising the following steps:
step 1, preparing zeolite gel seed crystal
According to (5.0X10) -2 -20) sodium salt: (8-20) Na 2 O：Al 2 O 3 ：(10-20)SiO 2 ：(100-350)H 2 O, uniformly dispersing a silicon source A, an aluminum source A and sodium salt in an aqueous solution A, and performing first aging treatment to obtain a guiding agent A;
subsequently, according to (2-4) Na 2 O：Al 2 O 3 ：(6-15)SiO 2 ：(100-300)H 2 Uniformly dispersing a guiding agent A, a silicon source B, an aluminum source B and an alkali source A in an aqueous solution B according to the molar ratio of O, performing a second aging treatment, and performing a first crystallization treatment at 85-100 ℃ to obtain zeolite gel seed crystals;
step 2, crystallizing to form NaY zeolite with high silicon-aluminum ratio
According to (10-20) Na 2 O：Al 2 O 3 ：(10-20)SiO 2 ：(100-350)H 2 O mole ratio, uniformly dispersing silicon source C and aluminium source C in water solution C, and after third ageing treatment obtainingA guiding agent B;
subsequently, according to (2-4) Na 2 O：Al 2 O 3 ：(7-12)SiO 2 ：(100-300)H 2 Uniformly dispersing a guiding agent B, a silicon source D, zeolite gel seed crystals, an alkali source B and an aluminum source D in an aqueous solution D according to the molar ratio of O, performing a second crystallization treatment at 85-100 ℃ after the fourth aging treatment, and obtaining the NaY zeolite with high silicon-aluminum ratio;
the silicon source A and the silicon source B are selected from one or two of water glass and alkaline silica sol;
the aluminum source A and the aluminum source B are selected from one or two of sodium metaaluminate and high-alkali sodium metaaluminate;
the sodium salt is one or more of NaCl, naBr and NaI;
the zeolite gel seed crystal accounts for 10-20wt% of the guiding agent B.
2. The method of claim 1, wherein the silicon source C and the silicon source D are each selected from one or more of silica sol, water glass, white carbon black, and silica gel;
the aluminum source C and the aluminum source D are selected from one or more of sodium metaaluminate, high-alkali sodium metaaluminate, aluminum sulfate, aluminum nitrate and aluminum hydroxide.
3. The preparation method according to claim 1, wherein the sodium salt is used in an amount of 3 to 18wt% of the guiding agent a.
4. The method according to claim 1, wherein the first aging treatment is carried out at a temperature of 20 to 35 ℃ for 12 to 24 hours;
the temperature of the second aging treatment is 30-60 ℃ and the aging time is 1-12 h;
the time of the first crystallization treatment is 6-60 h.
5. The method according to claim 1, wherein the temperature of the third aging treatment is 20 to 35 ℃ and the aging time is 12 to 24 hours;
the temperature of the fourth aging treatment is 30-65 ℃ and the aging time is 1-12 h;
the time of the second crystallization treatment is 12-60 h.
6. A high silica to alumina ratio NaY zeolite prepared by the process of any one of claims 1 to 5.
7. The NaY zeolite with high silica-alumina ratio according to claim 6, wherein the crystallinity of the NaY zeolite with high silica-alumina ratio is not less than 90% and the silica-alumina ratio is 5.5-7.0.
8. Use of a NaY zeolite of high silica alumina ratio according to claim 6 for the preparation of adsorbents and catalysts.
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| CN1837046A (en) * | 2006-04-24 | 2006-09-27 | 南开大学 | Process for synthesis of nano mordenite molecular sieve |
| CN101254929A (en) * | 2008-04-07 | 2008-09-03 | 华东理工大学 | Method for preparing high silica alumina ratio NaY molecular sieve |
| CN104118885A (en) * | 2013-04-23 | 2014-10-29 | 中国石油天然气股份有限公司 | Method for synthesizing NaY zeolite with high silicon-aluminum ratio |
| CN107986291A (en) * | 2017-12-13 | 2018-05-04 | 山东齐鲁华信高科有限公司 | The synthetic method of thin bar-shaped ZSM-22 molecular sieves |
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| CN1837046A (en) * | 2006-04-24 | 2006-09-27 | 南开大学 | Process for synthesis of nano mordenite molecular sieve |
| CN101254929A (en) * | 2008-04-07 | 2008-09-03 | 华东理工大学 | Method for preparing high silica alumina ratio NaY molecular sieve |
| CN104118885A (en) * | 2013-04-23 | 2014-10-29 | 中国石油天然气股份有限公司 | Method for synthesizing NaY zeolite with high silicon-aluminum ratio |
| CN107986291A (en) * | 2017-12-13 | 2018-05-04 | 山东齐鲁华信高科有限公司 | The synthetic method of thin bar-shaped ZSM-22 molecular sieves |
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