CN114956115A - Metal modified Y-type molecular sieve and preparation method thereof - Google Patents
Metal modified Y-type molecular sieve and preparation method thereof Download PDFInfo
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- CN114956115A CN114956115A CN202110213227.4A CN202110213227A CN114956115A CN 114956115 A CN114956115 A CN 114956115A CN 202110213227 A CN202110213227 A CN 202110213227A CN 114956115 A CN114956115 A CN 114956115A
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- 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 150
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 147
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 91
- 239000002184 metal Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 64
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 50
- 238000003756 stirring Methods 0.000 claims abstract description 50
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000008367 deionised water Substances 0.000 claims abstract description 46
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 30
- 239000010703 silicon Substances 0.000 claims abstract description 30
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 78
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 34
- 238000005342 ion exchange Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 25
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 18
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 18
- 239000012670 alkaline solution Substances 0.000 claims description 17
- -1 magnesium-iron hydrotalcite compound Chemical class 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 12
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 159000000003 magnesium salts Chemical class 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 150000002505 iron Chemical class 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 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 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 10
- 238000003442 catalytic alkylation reaction Methods 0.000 abstract description 4
- 238000004523 catalytic cracking Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 20
- 230000002194 synthesizing effect Effects 0.000 description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000004115 Sodium Silicate Substances 0.000 description 10
- 229910052911 sodium silicate Inorganic materials 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 238000005216 hydrothermal crystallization Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 7
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 7
- 238000005804 alkylation reaction Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910019089 Mg-Fe Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000004497 NIR spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
Images
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
- 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
- C01B39/026—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a metal modified Y-type molecular sieve and a preparation method thereof, wherein the preparation method comprises the following steps: mixing magnesium-iron-based hydrotalcite, an alkali source, an aluminum source, a silicon source, a guiding agent and deionized water, and stirring to form a uniform sol solution; crystallizing the sol solution under a hydrothermal condition to obtain metal modified Y-type molecular sieve raw powder; wherein the magnesium-iron-based hydrotalcite is nano magnesium-iron-based hydrotalcite. The preparation method can obtain the metal modified molecular sieve with small crystal grains, and has unique advantages in catalytic cracking and alkylation reactions.
Description
Technical Field
The invention relates to a metal modified Y-shaped molecular sieve and a preparation method thereof, in particular to a method for in-situ synthesis of the metal modified Y-shaped molecular sieve.
Background
The Y-type molecular sieve is a catalyst commonly used in the petrochemical production process, has a strong acidity, a three-dimensional transparent pore structure and a large pore diameter, and is widely applied to the processes of catalytic cracking, alkylation and the like. The Y-type molecular sieve has strong acidity, many reactions are carried out by virtue of the catalytic action of acid centers, and the Y-type molecular sieve is easy to deactivate due to the strong acid centers. Therefore, in order to improve the carbon deposition resistance of the Y-type molecular sieve in various reaction processes, researchers modify the Y-type molecular sieve by adopting a plurality of methods, so as to improve the stability of the Y-type molecular sieve in the reaction processes while retaining higher reaction activity.
The traditional Y-type molecular sieve modification means comprise hydrothermal treatment, acid washing, alkali washing, ion exchange and the like, and the technical means can only remove acid centers in the molecular sieve or introduce other ions into pore channels in a post-treatment mode, so that the defects of complex operation steps, high energy consumption and the like are overcome on the whole.
CN110075783A discloses a magnesium-iron hydrotalcite/hydroxyapatite composite material and application thereof, wherein the magnesium-iron hydrotalcite and hydroxyapatite are prepared by a liquid phase deposition method, a hydrothermal synthesis method or an ultrasonic-assisted method, wherein the liquid phase deposition method is to add the magnesium-iron hydrotalcite during the preparation of the hydroxyapatite; the hydrothermal synthesis method is to add hydroxyapatite when preparing the magnesium iron hydrotalcite; the ultrasonic-assisted method is carried out by mixing a distilled water mixed suspension of magnesium-iron hydrotalcite and hydroxyapatite under ultrasonic assistance and magnetic stirring. The magnesium-iron hydrotalcite/hydroxyapatite composite adsorbent is high in adsorption performance and excellent in reusability, the high chelating performance of phosphate radicals to uranium is exerted while the layered structure characteristics of hydrotalcite are fully utilized, the adsorption performance of the composite material is improved compared with that of hydrotalcite and hydroxyapatite monomers, and the adsorption capacity can reach 296.1 mg/g.
CN109513424A discloses a carbon/hydrotalcite composite adsorbent, which comprises a carbon substrate and a carbonate and hydroxyl double-intercalated hydrotalcite loaded on the surface of the carbon substrate. The invention also discloses a preparation method of the carbon/hydrotalcite composite adsorbent, which comprises the steps of placing raw material solution containing a carbon substrate, a cation source for synthesizing hydrotalcite, a carbonate source and a hydroxide source in a closed container and aging at 90-130 ℃ to prepare the carbon/hydrotalcite composite adsorbent. The preparation process is simple and easy to operate, and the prepared magnetic composite adsorbent can realize rapid separation under the condition of an external magnetic field, is an environment functional material and can be widely applied to treatment of domestic sewage and industrial wastewater.
Disclosure of Invention
The invention mainly aims to provide a metal modified Y-type molecular sieve and a preparation method thereof, the molecular sieve prepared by the preparation method has the structure of the traditional Y-type molecular sieve, meanwhile, the molecular sieve has smaller crystal grains, partial orifices are passivated to lose partial acid centers, and compared with the traditional Y-type molecular sieve, the molecular sieve and particularly the orifices of the molecular sieve are not easy to deposit carbon and can keep higher stability in partial reaction processes.
In order to achieve the purpose, the invention provides a preparation method of a metal modified Y-type molecular sieve, which comprises the following steps:
mixing magnesium-iron-based hydrotalcite, an alkali source, an aluminum source, a silicon source, a guiding agent and deionized water, and stirring to form a uniform sol solution; crystallizing the sol solution under a hydrothermal condition to obtain metal modified Y-type molecular sieve raw powder;
wherein the magnesium-iron-based hydrotalcite is nano magnesium-iron-based hydrotalcite.
The preparation method of the metal modified Y-type molecular sieve comprises the following steps of (0.01-0.05) mass ratio of magnesium-iron hydrotalcite to alkali source to aluminum source to silicon source to guiding agent to deionized water (0.3-0.7) mass ratio of magnesium-iron hydrotalcite to alkali source to aluminum source to silicon source to guiding agent to deionized water (0.17-0.33) mass ratio of magnesium-iron hydrotalcite to alkali source to aluminum source to silicon source to guiding agent to deionized water (2.5-10.0); the grain size of the magnesium-iron-based hydrotalcite is 10-50 nanometers.
The invention relates to a preparation method of a metal modified Y-type molecular sieve, wherein the preparation method of magnesium iron-based hydrotalcite comprises the following steps: dissolving magnesium salt and iron salt in deionized water to form a metal solution with the total metal ion molar concentration of 0.8-1.2mol/L, and mixing the metal solution and an alkaline solution according to the ratio of 1: mixing at a mass ratio of 1-5 under stirring, filtering and separating immediately after mixing, and drying at 10-50 ℃ to obtain the magnesium-iron hydrotalcite compound;
wherein, NH is contained in the alkaline solution 4 + The concentration is 1.6-2.4 mol/L.
The invention relates to a preparation method of a metal modified Y-type molecular sieve, wherein total metal ions in a metal solution are Mg 2+ And Fe 3+ ，Mg 2+ With Fe 2+ The molar ratio of (A) to (B) is 2.3-4: 1; the alkaline solution is formed by dissolving ammonium carbonate and ammonia water in deionized water according to the mass ratio of (0-5) to 1.
The preparation method of the metal modified Y-type molecular sieve comprises the following steps of preparing a magnesium salt, a ferric salt and a ferric salt, wherein the magnesium salt is magnesium chloride and/or magnesium nitrate, and the ferric salt is ferric chloride and/or ferric nitrate.
The invention relates to a preparation method of a metal modified Y-type molecular sieve, wherein an alkali source comprises one or two of sodium hydroxide and potassium hydroxide; the aluminum source comprises one or a combination of more of pseudo-boehmite, sodium aluminate, sodium metaaluminate, aluminum hydroxide and alumina sol; the silicon source comprises one of water glass and alkaline silica sol; the silicon source is calculated by silicon, the aluminum source is calculated by aluminum, and the molar ratio of the silicon source to the aluminum source is 3.03-5.88: 1.
the invention relates to a preparation method of a metal modified Y-type molecular sieve, wherein the preparation method of a directing agent comprises the following steps: mixing an alkali source, an aluminum source and deionized water, stirring and dissolving completely, adding a silicon source, stirring vigorously, sealing, and aging at 10-40 ℃ for 20-30 hours to obtain a solution containing a directing agent.
The preparation method of the metal modified Y-type molecular sieve comprises the following steps of (1.8-2.2) mixing an alkali source, an aluminum source, deionized water and a silicon source in a mass ratio of (9.0-11.0) to (11.0-13.0).
The preparation method of the metal modified Y-type molecular sieve comprises the following steps of filtering, drying and roasting a crystallized product after crystallization, wherein the crystallization conditions are as follows: the temperature is 120-; drying at 90-150 deg.C for 8-12 hr; the roasting temperature is 450-600 ℃ and the roasting time is 4-10 hours.
The preparation method of the metal modified Y-type molecular sieve further comprises the step of carrying out ion exchange on the original powder of the metal modified Y-type molecular sieve and an ammonium salt solution or dilute hydrochloric acid to obtain the metal modified H-Y-type molecular sieve.
In order to achieve the purpose, the invention also provides the metal modified Y-type molecular sieve obtained by the preparation method.
The invention has the beneficial effects that:
the invention provides an in-situ metal modification method of a Y molecular sieve, which can eliminate the adverse effect of part of easily carbon-deposited acid centers on the reaction by carrying out metal modification on the Y molecular sieve, thereby improving the stability of the Y molecular sieve in various reactions. In addition, the magnesium-iron hydrotalcite is used for modifying the molecular sieve, so that the crystal grains of the molecular sieve can be reduced, and the carbon deposition resistance can be improved. Therefore, the preparation method of the invention can obtain the metal modified molecular sieve with small crystal grains, and the molecular sieve has unique advantages in catalytic cracking, alkylation and other reactions, and has better stability in various reactions.
Drawings
FIG. 1 is an XRD spectrum of Y-type molecular sieves synthesized in example 1 and comparative example 1;
FIG. 2 is an XRD spectrum of the Y-type molecular sieves synthesized in example 2 and comparative example 2;
FIG. 3 is an SEM image of the metal-modified Y-type molecular sieve synthesized in example 1;
FIG. 4 is an SEM image of a Y-type molecular sieve synthesized in comparative example 1;
fig. 5 is an XRD spectrum of the magnesium-iron hydrotalcite compound synthesized in example 1;
fig. 6 is an SEM image of the magnesium-iron hydrotalcite-like compound synthesized in example 1.
Detailed Description
The following examples of the present invention are described in detail, and the present invention is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are experimental methods without specific conditions noted, and generally follow conventional conditions.
The invention discloses a preparation method of a metal modified Y-type molecular sieve, which comprises the following steps:
mixing magnesium-iron-based hydrotalcite, an alkali source, an aluminum source, a silicon source, a guiding agent and deionized water, and stirring to form a uniform sol solution; crystallizing the sol solution under a hydrothermal condition to obtain metal modified Y-type molecular sieve raw powder;
wherein, the magnesium-iron-based hydrotalcite of the invention is nano magnesium-iron-based hydrotalcite, and the grain size of the magnesium-iron-based hydrotalcite is 10 to 150 nanometers, preferably 10 to 50 nanometers.
The nano magnesium iron-based hydrotalcite is added in the process of preparing the Y-type molecular sieve, and has the following two functions: (1) the magnesium-iron-based hydrotalcite has a space restriction effect on crystal grains formed in the crystallization process of the molecular sieve, can inhibit the growth of the crystal grains of the molecular sieve to a certain extent, enables the grain size of the synthesized Y-type molecular sieve to be smaller, and further enables the molecular sieve to have better carbon deposition resistance; (2) during the roasting process, the magnesium-iron hydrotalcite can be decomposed to form magnesium oxide and iron oxide which are deposited at the openings of the Y-shaped molecular sieve grains in contact with the magnesium-iron hydrotalcite and cover part of acid centers, so that carbon deposition at the openings of the molecular sieve during the reaction process can be inhibited.
In one embodiment, the method for preparing magnesium iron-based hydrotalcite according to the present invention comprises: dissolving magnesium salt and iron salt in deionized water to form a metal solution with the total metal ion molar concentration of 0.8-1.2mol/L, and mixing the metal solution and an alkaline solution according to the ratio of 1: mixing at a mass ratio of 1-5 under stirring, filtering and separating immediately after mixing, and drying at 10-50 deg.C in vacuum for 5-48 hr to obtain magnesium iron hydrotalcite compound;
wherein, NH is contained in the alkaline solution 4 + The concentration is 1.6-2.4 mol/L.
In another embodiment, the magnesium salt is magnesium chloride and/or magnesium nitrate, the iron salt is ferric chloride and/or ferric nitrate, and the total metal ion is Mg 2+ And Fe 3+ ，Mg 2+ With Fe 2+ In a molar ratio of 2.3-4: 1. The alkaline solution is formed by dissolving ammonium carbonate and ammonia water in deionized water according to the mass ratio of (0-5) to 1.
The magnesium-iron hydrotalcite compound prepared by the invention is Mg 2+ 、Fe 3+ The cations are main laminate and are orderly assembled with interlayer anions to form layered double-hydroxyl composite metal hydroxide; wherein Mg 2+ :Fe 2+ 1 (2.3-4), and the interlayer anion may be Cl - 、NO 3 - Or CO 3 2- 。
The alkali source, the aluminum source and the silicon source used in the present invention can be any of those commonly used in the prior art for synthesizing the Y-type molecular sieve, and are not particularly limited. For example, the alkali source may include one or both of sodium hydroxide and potassium hydroxide; the aluminum source can comprise one or a combination of more of pseudo-boehmite, sodium aluminate, aluminum hydroxide and alumina sol; the silicon source may comprise one of water glass, alkaline silica sol.
In one embodiment, the mass ratio of the magnesium-iron-based hydrotalcite, the alkali source, the aluminum source, the silicon source, the directing agent and the deionized water is (0.01-0.05): (0.3-0.7): 0.17-0.33):1: (0.02-0.2): 2.5-10.0).
In another embodiment, the molar ratio of the silicon source to the aluminum source is 3 to 6: 1, in yet another embodiment, the molar ratio of the silicon source to the aluminum source is from 3.03 to 5.88: 1.
the guiding agent can be a general guiding agent for synthesizing the Y-type molecular sieve, and the invention particularly recommends a guiding agent, and the preparation method comprises the following processes: mixing an alkali source, an aluminum source and deionized water, stirring and dissolving completely, adding a silicon source, stirring vigorously, sealing, and aging at 10-40 ℃ for 20-30 hours to obtain a solution containing a directing agent. Wherein the mass ratio of the alkali source, the aluminum source, the deionized water and the silicon source is (1.8-2.2):1, (9.0-11.0): 11.0-13.0.
The alkali source, the silicon source and the aluminum source used in the synthesis of the directing agent can be respectively the same as or different from the alkali source, the silicon source and the aluminum source used in the preparation method of the metal modified Y-type molecular sieve. In one embodiment, the alkali source used in the process of synthesizing the directing agent is sodium hydroxide, the aluminum source is sodium aluminate, the silicon source is sodium silicate, and the mass ratio of the sodium hydroxide to the sodium aluminate to the deionized water to the sodium silicate is (1.8-2.2):1: (9.0-11.0): 11.0-13.0).
In one embodiment, the crystallization process further comprises filtering, drying and roasting the crystallized product, wherein the crystallization conditions are as follows: the temperature is 120-200 ℃, preferably 120-150 ℃, and the time is 12-196 hours, preferably 24-72 hours; the drying temperature is 90-150 ℃, preferably 100-120 ℃, and the drying time is 8-12 hours; the roasting temperature is 450-600 ℃ and the roasting time is 4-10 hours. In another embodiment, the firing conditions of the present invention are: 330-360 ℃ for 3-6h, and 530-560 ℃ for 4-8 h.
In one embodiment, the method further comprises the steps of carrying out ion exchange on the obtained metal modified Y-type molecular sieve raw powder and an ammonium salt solution or dilute hydrochloric acid, filtering and drying to obtain the metal modified H-Y-type molecular sieve. The ion exchange is preferably carried out a plurality of times, and the mass ratio of the molecular sieve raw powder (sodium type) to the ammonium salt solution or the dilute hydrochloric acid solution is preferably 1.0 (10-50).
Therefore, the invention provides a preparation method of the metal modified Y-type molecular sieve, the molecular sieve prepared by the preparation method has the structure of the traditional Y-type molecular sieve, meanwhile, partial orifices of the molecular sieve are passivated, so that partial acid centers are lost, and compared with the traditional Y-type molecular sieve, the orifices of the molecular sieve are not easy to deposit carbon, and higher stability can be kept in the reaction process.
In addition, the magnesium-iron hydrotalcite is used for modifying the molecular sieve, so that the crystal grains of the molecular sieve can be reduced, and the carbon deposition resistance of the molecular sieve is improved. In a word, the preparation method can obtain the metal modified molecular sieve with small crystal grains, so that the molecular sieve has higher carbon deposition resistance, and the carbon deposition resistance of the molecular sieve is further improved by performing acid passivation on part of orifices of the molecular sieve, so that the metal modified Y-type molecular sieve has unique advantages in catalytic cracking, alkylation and other reactions.
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
This example provides a metal modified Y-type molecular sieve, which is prepared by the following three steps:
firstly, preparing a magnesium-iron-based hydrotalcite compound by the following method:
taking a proper amount of magnesium nitrate and ferric chloride according to a molar ratio of 3: dissolving the mixture in deionized water in a ratio of 1 to prepare a metal solution with a total metal ion concentration of 1 mol/L;
taking a proper amount of ammonium carbonate and ammonia water solution according to the mass ratio of 2: 1 is dissolved in deionized water to prepare NH 4 + Alkaline solution with the ion concentration of 2 mol/L;
mixing the metal solution with equal mass and alkaline solution under stirring, filtering and separating immediately after mixing, and vacuum drying at room temperature for 24 hr to obtain Mg-Fe hydrotalcite compound, wherein XRD spectrogram and SEM chart of Mg-Fe hydrotalcite compound are shown in figures 5 and 6.
The second step is to prepare a guiding agent for synthesizing the Y-type molecular sieve:
adding 2.1g of sodium hydroxide, 1.04g of sodium aluminate and 10.4g of deionized water into a beaker, stirring and dissolving completely, adding 11.6g of sodium silicate solution, stirring vigorously, sealing and aging for 24 hours to prepare a guiding agent solution;
finally synthesizing the metal modified Y-type molecular sieve:
5.1g of the magnesium-iron-based hydrotalcite prepared in the first step, 54.5g of sodium hydroxide, 88.2g of sodium aluminate, and 800g of silica sol (30% by weight of SiO) 2 Content) of the mixture is sequentially added into 4000g of deionized water and stirred at normal temperature until sol solution is formed;
adding the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
and transferring the sol solution into a hydrothermal crystallization kettle, crystallizing for 72 hours at 150 ℃, filtering, washing, drying for 12 hours at 80 ℃, heating to 350 ℃ at the heating rate of 2 ℃/min for 2 hours, continuously heating to 550 ℃ at the original heating rate for 6 hours, roasting, and obtaining the metal modified NaY type molecular sieve after roasting.
Mixing the NaY type molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1: mixing at a ratio of 10, performing ion exchange under the condition of stirring in water bath at 85 ℃, repeating the operations of filtering, drying and roasting in the previous step after the ion exchange, and obtaining the metal modified HY type molecular sieve after 3 times of ion exchange.
Comparative example 1
This comparative example provides a Y-type molecular sieve, which, compared to example 1, is not modified with metal in comparative example 1, and the specific preparation steps are as follows:
firstly, preparing a guiding agent for synthesizing the Y-type molecular sieve by the following method:
adding 2.1g of sodium hydroxide, 1.04g of sodium aluminate and 10.4g of deionized water into a beaker, stirring and dissolving completely, adding 11.6g of sodium silicate solution, stirring vigorously, sealing and aging for 24 hours to prepare a guiding agent solution;
then synthesizing a Y-type molecular sieve:
54.5g of sodium hydroxide, 88.2g of sodium aluminate, and 800g of silica sol (30% by weight of SiO) 2 Content) is added into 4000g of deionized water in sequence, and stirred at normal temperature until uniform sol solution is formed;
adding the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
and transferring the sol solution into a hydrothermal crystallization kettle, crystallizing for 72 hours at 150 ℃, filtering, washing, drying for 12 hours at 80 ℃, heating to 350 ℃ at the heating rate of 2 ℃/min, maintaining for 2 hours, continuing heating to 550 ℃ at the original heating rate, maintaining for 6 hours, and roasting to obtain the Y-type molecular sieve.
Mixing the NaY type molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1: mixing at a ratio of 10, performing ion exchange under the condition of stirring in water bath at 85 ℃, repeating the filtering, drying and roasting operations in the previous step after the ion exchange, and obtaining the metal modified HY type molecular sieve after 3 times of ion exchange.
Example 2
This example provides a metal modified Y-type molecular sieve, which is prepared by the following steps:
firstly, preparing a magnesium-iron-based hydrotalcite compound by the following method:
taking a proper amount of magnesium nitrate and ferric nitrate according to a molar ratio of 4:1 proportion is dissolved in deionized water to prepare a metal solution with the total metal ion concentration of 1 mol/L;
taking a proper amount of ammonium carbonate and ammonia water solution according to a mass ratio of 1: 1 is dissolved in deionized water to prepare NH 4 + Alkaline solution with the ion concentration of 2 mol/L;
and mixing the metal solution with equal mass with the alkaline solution under the condition of stirring, immediately performing suction filtration and separation after mixing, and performing vacuum drying at normal temperature for 24 hours to obtain the magnesium-iron hydrotalcite compound.
The second step is to prepare a guiding agent for synthesizing the Y-type molecular sieve:
adding 2.0g of sodium hydroxide, 1.00g of sodium aluminate and 11.0g of deionized water into a beaker, stirring and dissolving completely, adding 12.0g of sodium silicate solution, stirring violently, sealing and aging for 24 hours to prepare a guiding agent solution;
finally synthesizing the metal modified Y-type molecular sieve:
3.6g of the magnesium-iron hydrotalcite prepared in the first step, 44.9g of sodium hydroxide, 75.2g of sodium aluminate, and 890g of silica sol (25% by weight of SiO) 2 Content) in orderAdding into 4100g deionized water, stirring at normal temperature to form sol solution;
adding the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
and transferring the sol solution into a hydrothermal crystallization kettle, crystallizing at 180 ℃ for 120 hours, filtering, washing, drying at 90 ℃ for 12 hours, heating to 300 ℃ at a heating rate of 2 ℃/min for 2 hours, continuing heating to 500 ℃ at the original heating rate, maintaining for 6 hours, roasting, and obtaining the metal modified NaY type molecular sieve.
Mixing the NaY type molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1: mixing at a ratio of 10, performing ion exchange under the condition of stirring in water bath at 85 ℃, repeating the operations of filtering, drying and roasting in the previous step after the ion exchange, and obtaining the metal modified HY type molecular sieve after 3 times of ion exchange.
Comparative example 2
Compared with example 2, in comparative example 2, the metal-modified Y-type molecular sieve is modified by in-situ doping inorganic magnesium salt instead of magnesium-iron hydrotalcite precursor, and the preparation method comprises the following specific steps:
firstly, preparing a guiding agent for synthesizing the Y-type molecular sieve:
adding 2.0g of sodium hydroxide, 1.00g of sodium aluminate and 11.0g of deionized water into a beaker, stirring and dissolving completely, adding 12g of sodium silicate solution, stirring violently, sealing and aging for 24 hours to prepare a guiding agent solution;
and finally synthesizing the metal modified Y-type molecular sieve:
2.0g of magnesium chloride, 44.9g of sodium hydroxide, 75.2g of sodium aluminate, 890g of silica sol (25% by weight of SiO) 2 Content) of the sol is sequentially added into 4100g of deionized water and stirred at normal temperature until uniform sol solution is formed;
adding the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
and (3) transferring the sol solution into a hydrothermal crystallization kettle, crystallizing for 72 hours at 150 ℃, filtering, washing, drying for 12 hours at 80 ℃, heating to 350 ℃ at the heating rate of 2 ℃/min for 2 hours, continuously heating to 550 ℃ at the original heating rate for 6 hours, roasting, and obtaining the metal modified Y-type molecular sieve.
Mixing the NaY type molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1: mixing at a ratio of 10, performing ion exchange under the condition of stirring in water bath at 85 ℃, repeating the operations of filtering, drying and roasting in the previous step after the ion exchange, and obtaining the metal modified HY type molecular sieve after 3 times of ion exchange.
Example 3
This example provides a metal modified Y-type molecular sieve, which is prepared by the following steps:
firstly, preparing a magnesium-iron-based hydrotalcite compound by the following method:
taking a proper amount of magnesium chloride and ferric nitrate according to a molar ratio of 2.8: dissolving the mixture in deionized water in a ratio of 1 to prepare a metal solution with a total metal ion concentration of 1 mol/L;
taking a proper amount of ammonium carbonate and ammonia water solution according to a mass ratio of 1: 1 is dissolved in deionized water to prepare NH 4 + Alkaline solution with the ion concentration of 2 mol/L;
and mixing the metal solution with equal mass with the alkaline solution under the condition of stirring, immediately performing suction filtration and separation after mixing, and performing vacuum drying at normal temperature for 24 hours to obtain the magnesium-iron hydrotalcite compound.
The second step is to prepare a guiding agent for synthesizing the Y-type molecular sieve:
adding 2.0g of sodium hydroxide, 1.0g of sodium aluminate and 11.0g of deionized water into a beaker, stirring and dissolving completely, adding 12.0g of sodium silicate solution, stirring vigorously, sealing and aging for 24 hours to prepare a guiding agent solution;
finally synthesizing the metal modified Y-type molecular sieve:
6.2g of the magnesium-iron hydrotalcite prepared in the first step, 71.2g of sodium hydroxide, 91.5g of pseudo-boehmite, and 870g of silica sol (25% by weight of SiO) 2 Content) of the mixture is sequentially added into 4000g of deionized water and stirred at normal temperature until sol solution is formed;
adding the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
and transferring the sol solution into a hydrothermal crystallization kettle, crystallizing for 180 hours at 160 ℃, filtering, washing, drying for 12 hours at 100 ℃, heating to 600 ℃ at a heating rate of 2 ℃/min, roasting, and roasting for 4 hours to obtain the metal modified NaY type molecular sieve.
Mixing the NaY type molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1: mixing at a ratio of 10, performing ion exchange under the condition of stirring in water bath at 85 ℃, repeating the operations of filtering, drying and roasting in the previous step after the ion exchange, and obtaining the metal modified HY type molecular sieve after 3 times of ion exchange.
Comparative example 3
The comparative example provides a metal modified Y-type molecular sieve, and compared with example 3, comparative example 3 does not add a magnesium iron-based hydrotalcite precursor but performs in-situ doping modification using an inorganic iron salt, and is prepared through the following two steps.
Firstly, preparing a guiding agent for synthesizing the Y-type molecular sieve:
adding 2.0g of sodium hydroxide, 1.04g of sodium aluminate and 10.4g of deionized water into a beaker, stirring and dissolving completely, adding 11.6g of sodium silicate solution, stirring vigorously, sealing and aging for 24 hours to prepare a guiding agent solution;
finally synthesizing the metal modified Y-type molecular sieve:
2.0g of ferric chloride, 71.2g of sodium hydroxide, 91.5g of sodium aluminate, and 870g of silica sol (25% by weight of SiO) 2 Content) is added into 4000g of deionized water in sequence, and stirred at normal temperature until uniform sol solution is formed;
adding the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
and (3) transferring the sol solution into a hydrothermal crystallization kettle, crystallizing for 72 hours at 150 ℃, filtering, washing, drying for 12 hours at 80 ℃, heating to 350 ℃ at the heating rate of 2 ℃/min for 2 hours, continuously heating to 550 ℃ at the original heating rate for 6 hours, roasting, and obtaining the metal modified Y-type molecular sieve.
Mixing the NaY type molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1: mixing at a ratio of 10, performing ion exchange under the condition of stirring in water bath at 85 ℃, repeating the operations of filtering, drying and roasting in the previous step after the ion exchange, and obtaining the metal modified HY type molecular sieve after 3 times of ion exchange.
Example 4
This example provides a metal modified Y-type molecular sieve, which is prepared by the following steps:
firstly, preparing a magnesium-iron-based hydrotalcite compound by the following method:
taking a proper amount of magnesium chloride and ferric chloride according to a molar ratio of 4: dissolving the mixture in deionized water in a ratio of 1 to prepare a metal solution with a total metal ion concentration of 1 mol/L;
taking a proper amount of ammonium carbonate and ammonia water solution according to a mass ratio of 1: 1 is dissolved in deionized water to prepare NH 4 + Alkaline solution with the ion concentration of 2 mol/L;
and mixing the metal solution with equal mass and the alkaline solution under the condition of stirring, immediately filtering and separating after mixing, and drying in vacuum for 24 hours at normal temperature to obtain the magnesium-iron hydrotalcite compound.
The second step is to prepare a guiding agent for synthesizing the Y-type molecular sieve:
adding 1.9g of sodium hydroxide, 1.1g of sodium aluminate and 12.0g of deionized water into a beaker, stirring and dissolving completely, adding 12.0g of sodium silicate solution, stirring vigorously, sealing and aging for 24 hours to prepare a guiding agent solution;
finally synthesizing the metal modified Y-type molecular sieve:
8.8g of magnesium-iron hydrotalcite, 52.6g of sodium hydroxide, 84.3g of pseudo-boehmite, and 910g of silica sol (25% by weight of SiO) 2 Content) were added to 4500g of deionized water in sequence, and stirred at normal temperature until a homogeneous solution was formed;
adding the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
and transferring the sol solution into a hydrothermal crystallization kettle, crystallizing for 100 hours at 140 ℃, filtering, washing, drying for 12 hours at 80 ℃, heating to 500 ℃ at a heating rate of 2 ℃/min, roasting, and roasting for 4 hours to obtain the metal modified NaY type molecular sieve.
Mixing the NaY type molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1: mixing at a ratio of 10, performing ion exchange under the condition of stirring in water bath at 85 ℃, repeating the filtering, drying and roasting operations in the previous step after the ion exchange, and obtaining the metal modified HY type molecular sieve after 3 times of ion exchange.
Comparative example 4
Compared with example 4, in comparative example 4, the metal-modified Y-type molecular sieve is modified by in-situ doping by using inorganic magnesium salt and inorganic iron salt instead of adding magnesium-iron hydrotalcite precursor, and the preparation method specifically comprises the following steps:
firstly, preparing a guiding agent for synthesizing the Y-type molecular sieve:
adding 1.9g of sodium hydroxide, 1.1g of sodium aluminate and 12.0g of deionized water into a beaker, stirring and dissolving completely, adding 12.0g of sodium silicate solution, stirring vigorously, sealing and aging for 24 hours to prepare a guiding agent solution;
the second step is to synthesize a metal modified Y-type molecular sieve:
6.2g of magnesium nitrate, 2.0g of iron nitrate, 52.6g of sodium hydroxide, 84.3g of pseudo-boehmite, and 910g of silica sol (25% by weight of SiO) 2 Content) were added to 4500g of deionized water in sequence, and stirred at normal temperature until a homogeneous solution was formed;
adding the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
and transferring the sol solution into a hydrothermal crystallization kettle, crystallizing for 100 hours at 140 ℃, filtering, washing, drying for 12 hours at 80 ℃, heating to 500 ℃ at a heating rate of 2 ℃/min, roasting, and roasting for 4 hours to obtain the metal modified NaY type molecular sieve.
Mixing the NaY type molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1: mixing at a ratio of 10, performing ion exchange under the condition of stirring in water bath at 85 ℃, repeating the operations of filtering, drying and roasting in the previous step after the ion exchange, and obtaining the metal modified HY type molecular sieve after 3 times of ion exchange.
As can be seen from FIG. 1, both example 1 and comparative example 1 exhibit typical diffraction peaks of faujasite cage type molecular sieve, which indicates that the crystal forms of the synthesized Y type molecular sieve are relatively complete.
As can be seen from fig. 2, example 2 and comparative example 2 exhibit typical diffraction peaks of faujasite cage type molecular sieves, which indicates that the crystal forms of the synthesized Y type molecular sieves are relatively complete.
Fig. 3 is an SEM image of a sample of example 1 synthesized by the preparation method of the present invention, and fig. 4 is an SEM image of a synthesized sample of comparative example 1.
As can be seen from FIGS. 3 and 4, the grain size of the sample of example 1 synthesized by the preparation method of the present invention is about 200nm, and the grain size of the sample of comparative example 1 exceeds 1 μm. Therefore, the preparation method can obviously reduce the grain size of the Y-type molecular sieve, and the preparation method has obvious effect on reducing the grain size of the Y-type molecular sieve.
In order to fully illustrate the application effect of the metal modified Y-shaped molecular sieve prepared by the invention, the molecular sieve prepared in the embodiment or the comparative example is put into a screw rod extruder to be extruded and formed, and is crushed to about 1cm after being dried and roasted. The prepared molecular sieve is used as a solid acid for alkylation reaction, and the specific reaction process is as follows:
100g of molecular sieve catalyst is loaded into a constant temperature section of an isothermal fixed bed reactor with the length of 150cm and the inner diameter of 8cm, and the upper end and the lower end of the catalyst are compacted by inert alumina pellets. After the pressure in the reactor was increased to 2.5MPa with nitrogen, the temperature in the reactor was increased to 65 ℃. After the temperature rise is finished, pressing isobutane and the fumaric into the reactor by using a metering pump according to the molar ratio of 100:1, and adjusting the mass space velocity of the fumaric to be 0.05h -1 . Performing alkylation reaction under the above conditions, condensing and separating the outlet of the reactor by using an ice-water mixture, introducing non-condensable gas (including unreacted alkane and alkene) into the outlet of the condenser, and performing chromatographic analysis on the content of the alkene; the octane number of the condensate is measured by adopting a near infrared spectroscopy method. The reaction results are shown in Table 1.
TABLE 1 results of alkylation reaction of the catalysts of examples and comparative examples
According to the evaluation result of the alkylation reaction, the metal modified Y-type molecular sieve prepared by the technical scheme of the invention has excellent alkylation reaction performance. The alkylation reaction life and the product octane number of the Y-type molecular sieve after the magnesium-containing iron-based hydrotalcite is modified in situ are higher than those of a comparative example, which shows that the preparation method disclosed by the invention can make obvious progress.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A preparation method of a metal modified Y-type molecular sieve is characterized by comprising the following steps:
mixing magnesium-iron-based hydrotalcite, an alkali source, an aluminum source, a silicon source, a guiding agent and deionized water, and stirring to form a uniform sol solution; crystallizing the sol solution under a hydrothermal condition to obtain metal modified Y-type molecular sieve raw powder;
wherein the magnesium-iron-based hydrotalcite is nano magnesium-iron-based hydrotalcite.
2. The method for preparing the metal modified Y-type molecular sieve of claim 1, wherein the mass ratio of the magnesium-iron-based hydrotalcite to the alkali source to the aluminum source to the silicon source to the directing agent to the deionized water is (0.01-0.05): 0.3-0.7): 0.17-0.33):1: (0.02-0.2): 2.5-10.0); the grain size of the magnesium-iron-based hydrotalcite is 10-50 nanometers.
3. The method for preparing the metal-modified Y-type molecular sieve according to claim 1, wherein the method for preparing the magnesium iron-based hydrotalcite comprises the following steps: dissolving magnesium salt and iron salt in deionized water to form a metal solution with the total metal ion molar concentration of 0.8-1.2mol/L, and mixing the metal solution and an alkaline solution according to the ratio of 1: mixing at a mass ratio of 1-5 under stirring, filtering and separating immediately after mixing, and drying at 10-50 ℃ to obtain the magnesium-iron hydrotalcite compound;
wherein, NH is contained in the alkaline solution 4 + The concentration is 1.6-2.4 mol/L.
4. The method for preparing the metal modified Y-type molecular sieve of claim 3, wherein the total metal ions in the metal solution are Mg 2+ And Fe 3+ ，Mg 2+ With Fe 2+ The molar ratio of (A) to (B) is 2.3-4: 1; the alkaline solution is formed by dissolving ammonium carbonate and ammonia water in deionized water according to the mass ratio of (0-5) to 1.
5. The method for preparing the metal modified Y-type molecular sieve of claim 3, wherein the magnesium salt is magnesium chloride and/or magnesium nitrate, and the iron salt is ferric chloride and/or ferric nitrate.
6. The method for preparing the metal modified Y-type molecular sieve according to claim 1, wherein the alkali source comprises one or both of sodium hydroxide and potassium hydroxide; the aluminum source comprises one or the combination of more of pseudo-boehmite, sodium aluminate, sodium metaaluminate, aluminum hydroxide and alumina sol; the silicon source comprises one of water glass and alkaline silica sol; the silicon source is calculated by silicon, the aluminum source is calculated by aluminum, and the molar ratio of the silicon source to the aluminum source is 3.03-5.88: 1.
7. the method for preparing the metal modified Y-type molecular sieve of claim 1, wherein the method for preparing the directing agent comprises: mixing an alkali source, an aluminum source and deionized water, stirring and dissolving completely, adding a silicon source, stirring vigorously, sealing, and aging at 10-40 ℃ for 20-30 hours to obtain a solution containing a directing agent.
8. The method for preparing the metal modified Y-type molecular sieve of claim 7, wherein the mass ratio of the alkali source, the aluminum source, the deionized water and the silicon source is (1.8-2.2):1, (9.0-11.0): (11.0-13.0).
9. The method for preparing the metal modified Y-type molecular sieve of claim 1, wherein the crystallization further comprises filtering, drying and roasting the crystallized product, and the crystallization conditions are as follows: the temperature is 120-; drying at 90-150 deg.C for 8-12 hr; the roasting temperature is 450-600 ℃ and the roasting time is 4-10 hours.
10. The method for preparing the metal modified Y-type molecular sieve according to claim 1, further comprising performing ion exchange on the raw powder of the metal modified Y-type molecular sieve and an ammonium salt solution or dilute hydrochloric acid to obtain the metal modified H-Y-type molecular sieve.
11. A metal-modified Y-type molecular sieve obtainable by the process of any one of claims 1 to 10.
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Citations (6)
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|---|---|---|---|---|
| US20050032632A1 (en) * | 2003-08-05 | 2005-02-10 | Janssen Marcel J.G. | Molecular sieve catalyst compositions, their production and use in conversion processes |
| CN103539151A (en) * | 2012-07-11 | 2014-01-29 | 中国石油大学(北京) | Preparation method of high silica-alumina ratio Y type zeolite rich in secondary pores |
| CN103771433A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of heteroatomic SAPO-11 molecular sieve |
| CN106809856A (en) * | 2015-12-01 | 2017-06-09 | 中国石油天然气股份有限公司 | A kind of catalyst for heavy oil catalytic cracking and preparation method thereof |
| CN108311098A (en) * | 2018-03-01 | 2018-07-24 | 中国石油大学(北京) | The method of sulfur dioxide in Y type molecular sieve adsorbent and preparation method and removing iso-butane |
| CN110653004A (en) * | 2019-09-05 | 2020-01-07 | 上海化工研究院有限公司 | Catalyst for trapping and catalyzing VOCs degradation and preparation method and application thereof |
-
2021
- 2021-02-24 CN CN202110213227.4A patent/CN114956115A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050032632A1 (en) * | 2003-08-05 | 2005-02-10 | Janssen Marcel J.G. | Molecular sieve catalyst compositions, their production and use in conversion processes |
| CN103539151A (en) * | 2012-07-11 | 2014-01-29 | 中国石油大学(北京) | Preparation method of high silica-alumina ratio Y type zeolite rich in secondary pores |
| CN103771433A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of heteroatomic SAPO-11 molecular sieve |
| CN106809856A (en) * | 2015-12-01 | 2017-06-09 | 中国石油天然气股份有限公司 | A kind of catalyst for heavy oil catalytic cracking and preparation method thereof |
| CN108311098A (en) * | 2018-03-01 | 2018-07-24 | 中国石油大学(北京) | The method of sulfur dioxide in Y type molecular sieve adsorbent and preparation method and removing iso-butane |
| CN110653004A (en) * | 2019-09-05 | 2020-01-07 | 上海化工研究院有限公司 | Catalyst for trapping and catalyzing VOCs degradation and preparation method and application thereof |
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