CN114956115B - 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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- CN114956115B CN114956115B CN202110213227.4A CN202110213227A CN114956115B CN 114956115 B CN114956115 B CN 114956115B CN 202110213227 A CN202110213227 A CN 202110213227A CN 114956115 B CN114956115 B CN 114956115B
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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 144
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 141
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 92
- 239000002184 metal Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000003756 stirring Methods 0.000 claims abstract description 50
- 239000008367 deionised water Substances 0.000 claims abstract description 44
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 44
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 31
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 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 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 73
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- 238000005342 ion exchange Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 27
- 239000012670 alkaline solution Substances 0.000 claims description 17
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 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 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
- 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 8
- 159000000003 magnesium salts Chemical class 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
- 230000008569 process Effects 0.000 claims description 7
- 150000003839 salts 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
- 230000008025 crystallization Effects 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
- 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
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 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 18
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 17
- 229910001388 sodium aluminate Inorganic materials 0.000 description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000004115 Sodium Silicate Substances 0.000 description 10
- 229910052911 sodium silicate Inorganic materials 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- -1 compound Chemical compound 0.000 description 8
- 238000005216 hydrothermal crystallization Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000000151 deposition Methods 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
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 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
- 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
- 229910021536 Zeolite 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 238000004497 NIR spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000009849 deactivation Effects 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
- 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
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000010410 layer Substances 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 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
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
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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)
- Catalysts (AREA)
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 the magnesium-iron-based hydrotalcite-like compound, an alkali source, an aluminum source, a silicon source and a guiding agent with deionized water, and stirring to form 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 grains, and has unique advantages in catalytic cracking and alkylation reactions.
Description
Technical Field
The invention relates to a metal modified Y-type molecular sieve and a preparation method thereof, in particular to a method for synthesizing the metal modified Y-type molecular sieve in situ.
Background
The Y-type molecular sieve is a catalyst commonly used in petrochemical production process, has strong acidity, three-dimensional permeable pore canal structure and larger pore diameter, and has wide application in the processes of catalytic cracking, alkylation and the like. The Y-type molecular sieve has strong acidity, and many reactions are carried out by the catalysis of acid centers, but the strong acid centers also lead to easy deactivation of the Y-type molecular sieve. Therefore, in order to improve the carbon deposition resistance of the Y-type molecular sieve in various reaction processes, researchers adopt a plurality of methods to modify the Y-type molecular sieve so as to improve the stability of the Y-type molecular sieve in the reaction processes while keeping higher reactivity.
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 the pore canal in a post-treatment mode, so that the defects of complicated operation steps, high energy consumption and the like are overcome.
CN110075783a discloses a magnesium-iron-talc/hydroxyapatite composite material and application, which is prepared by using magnesium-iron-talc and hydroxyapatite and adopting a liquid phase deposition method, a hydrothermal synthesis method or an ultrasonic auxiliary method, wherein the liquid phase deposition method is to add the magnesium-iron-talc when preparing the hydroxyapatite; the hydrothermal synthesis method is to add hydroxyapatite in the preparation of magnesium molten iron talcum; the ultrasonic assisted method is that the distilled water mixed suspension of the magnesium iron hydrotalcite and the hydroxyapatite is carried out under the ultrasonic assisted and magnetic stirring. The magnesium molten iron talcum/hydroxyapatite composite can obtain the composite adsorbent with high adsorption performance and excellent reusability, fully utilizes the layered structure characteristic of hydrotalcite, simultaneously exerts the high chelation performance of phosphate to uranium, improves the adsorption performance of the composite material compared with hydrotalcite and hydroxyapatite monomers, and can reach the adsorption capacity of 296.1mg/g.
CN109513424a discloses a carbon/hydrotalcite composite adsorbent comprising a carbon substrate and hydrotalcite with double intercalation of carbonate and hydroxide carried 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 a raw material solution containing a carbon substrate, a cation source, a carbonate source and a hydroxyl source of synthetic hydrotalcite into 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 externally applied 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, wherein the molecular sieve prepared by the preparation method has the structure of a traditional Y-type molecular sieve, meanwhile, the crystal grains of the molecular sieve are smaller, and part of pore openings are passivated to lose part of acid centers.
In order to achieve the above purpose, the invention provides a preparation method of a metal modified Y-type molecular sieve, comprising the following steps:
mixing the magnesium-iron-based hydrotalcite-like compound, an alkali source, an aluminum source, a silicon source and a guiding agent with deionized water, and stirring to form 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 invention relates to a preparation method of a metal modified Y-type molecular sieve, wherein the mass ratio of magnesium-iron-based hydrotalcite like compound, an alkali source, an aluminum source, a silicon source, a guiding agent and deionized water is (0.01-0.05): (0.3-0.7): (0.17-0.33): (0.02-0.2): (2.5-10.0); the grain size of the magnesium-iron-based hydrotalcite-like compound is 10-50 nanometers.
The invention relates to a preparation method of a metal modified Y-type molecular sieve, wherein the preparation method of the magnesium-iron-based hydrotalcite-like compound comprises the following steps: dissolving magnesium salt and ferric 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 with an alkaline solution according to the following ratio of 1: mixing under stirring at a mass ratio of 1-5, immediately filtering and separating after mixing, and drying at 10-50 ℃ to obtain the magnesium-iron hydrotalcite-like compound;
Wherein the concentration of NH 4 + in the alkaline solution is 1.6-2.4mol/L.
The invention relates to a preparation method of a metal modified Y-type molecular sieve, wherein the total metal ions in a metal solution are Mg 2+ and the molar ratio of Fe 3+,Mg2+ to Fe 2+ 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): 1.
The invention relates to a preparation method of a metal modified Y-type molecular sieve, 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 the alkali source comprises one or two of sodium hydroxide and potassium hydroxide; the aluminum source comprises one or a combination of a plurality of pseudo-boehmite, sodium aluminate, sodium metaaluminate, aluminum hydroxide and aluminum sol; the silicon source comprises one of water glass and alkaline silica sol; the silicon source is calculated as silicon, the aluminum source is calculated as 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 guiding 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 comprising a directing agent.
The invention relates to a preparation method of a metal modified Y-type molecular sieve, wherein the mass ratio of an alkali source to an aluminum source to deionized water to a silicon source is (1.8-2.2) 1 (9.0-11.0) 11.0-13.0.
The invention relates to a preparation method of a metal modified Y-type molecular sieve, wherein the crystallization process further comprises the steps of filtering, drying and roasting a crystallized product, and the crystallization conditions are as follows: the temperature is 120-200 ℃ and the time is 12-196 hours; drying at 90-150deg.C for 8-12 hr; the roasting temperature is 450-600 ℃ and the roasting time is 4-10 hours.
The invention also discloses a preparation method of the metal modified Y-type molecular sieve, which comprises the step of carrying out ion exchange on metal modified Y-type molecular sieve raw powder and ammonium salt solution or dilute hydrochloric acid to obtain the metal modified H-Y-type molecular sieve.
In order to achieve the aim, 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 adverse effects of partial easily-deposited carbon acid centers on reactions by modifying the metal of the Y molecular sieve, thereby improving the stability of the Y molecular sieve in various reactions. In addition, the magnesium-iron-based hydrotalcite-like compound is used for modifying the molecular sieve, so that the grain size 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, has unique advantages in reactions such as catalytic cracking, alkylation and the like, and has better stability in various reactions.
Drawings
FIG. 1 is an XRD spectrum of a Y-type molecular sieve 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 a 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-like 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 describes the present invention in detail, and the present examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and processes are given, but the scope of protection of the present invention is not limited to the following examples, in which the experimental methods of specific conditions are not noted, and generally according to conventional conditions.
The invention discloses a preparation method of a metal modified Y-type molecular sieve, which comprises the following steps:
mixing the magnesium-iron-based hydrotalcite-like compound, an alkali source, an aluminum source, a silicon source and a guiding agent with deionized water, and stirring to form 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 10-150 nanometers, and is preferably 10-50 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-like compound has a space limiting 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, and ensures that the grain size of the synthesized Y-shaped molecular sieve is smaller, so that the molecular sieve has better carbon deposition resistance; (2) In the roasting process, the magnesium-iron-based hydrotalcite can be decomposed to form magnesium oxide and ferric oxide which are deposited at the openings of the Y-type molecular sieve grains contacted with the magnesium oxide and ferric oxide and cover part of acid centers, so that carbon deposition at the openings of molecular sieve pores in the reaction process can be inhibited.
In one embodiment, the preparation method of the magnesium-iron-based hydrotalcite-like compound of the present invention comprises: dissolving magnesium salt and ferric 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 with an alkaline solution according to the following ratio of 1: mixing under stirring at a mass ratio of 1-5, immediately filtering and separating after mixing, drying at 10-50deg.C, for example, vacuum drying for 5-48 hr to obtain magnesium-iron hydrotalcite compound;
Wherein the concentration of NH 4 + in the alkaline solution is 1.6-2.4mol/L.
In another embodiment, the magnesium salt is magnesium chloride and/or magnesium nitrate, the ferric salt is ferric chloride and/or ferric nitrate, and the molar ratio of total metal ions of Mg 2+ and Fe 3+,Mg2+ to Fe 2+ 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): 1.
The magnesium-iron hydrotalcite-like compound prepared by the invention is a layered double hydroxide composite metal hydroxide formed by orderly assembling Mg 2+、Fe3+ cations serving as a main layer plate and interlayer anions; wherein Mg 2+:Fe2+ = (2.3-4): 1, the interlayer anion may be Cl -、NO3 - or CO 3 2-.
The alkali source, aluminum source and silicon source used in the present invention may be any ones commonly used in the synthesis of Y-type molecular sieves in the prior art, and are not particularly limited. For example, the alkali source may include one or both of sodium hydroxide and potassium hydroxide; the aluminum source may include one or a combination of several of pseudo-boehmite, sodium aluminate, aluminum hydroxide and aluminum 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-like compound, 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 silicon source of the present invention is silicon and the aluminum source is aluminum, the molar ratio of silicon source to aluminum source is 3-6:1, 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 in the invention can be a general guiding agent for synthesizing a Y-type molecular sieve, and the invention particularly recommends a guiding agent, and the preparation method 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 comprising a directing agent. Wherein the mass ratio of the alkali source to the aluminum source to the deionized water to the silicon source is (1.8-2.2) 1 (9.0-11.0) 11.0.
The alkali source, the silicon source and the aluminum source used in the synthetic directing agent of the invention can be 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 respectively. In one embodiment, the alkali source used in the synthesis of the guiding agent is sodium hydroxide, the aluminum source is sodium aluminate, the silicon source is sodium silicate, and the mass ratio of sodium hydroxide, sodium aluminate, deionized water and sodium silicate is (1.8-2.2) 1 (9.0-11.0) 11.0-13.0.
In one embodiment, the crystallization method further comprises the steps of filtering, drying and roasting the crystallized product, wherein the crystallization conditions are as follows: the temperature is 120-200deg.C, preferably 120-150deg.C, and the time is 12-196 hr, preferably 24-72 hr; the drying temperature is 90-150deg.C, preferably 100-120deg.C, and the drying time is 8-12 hr; 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: maintaining at 330-360 deg.C for 3-6 hr, and maintaining at 530-560 deg.C for 4-8 hr.
In one embodiment, the invention 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, and filtering and drying to obtain the metal modified H-Y-type molecular sieve. The ion exchange is preferably repeated, and the mass ratio of the molecular sieve raw powder (sodium form) 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 a metal modified Y-type molecular sieve, the molecular sieve prepared by the preparation method has the structure of the traditional Y-type molecular sieve, and meanwhile, partial pore openings of the molecular sieve are passivated to lose partial acid centers, so that the pore openings of the molecular sieve are not easy to accumulate carbon compared with the traditional Y-type molecular sieve, and the molecular sieve can keep higher stability in the reaction process.
In addition, the invention uses the magnesium-iron-based hydrotalcite-like compound to modify the molecular sieve, thereby reducing the grain size of the molecular sieve and improving the carbon deposition resistance of the molecular sieve. In a word, the preparation method of the invention can obtain the metal modified molecular sieve with small crystal grains, so that the molecular sieve has higher anti-carbon property, and the anti-carbon property of the molecular sieve is further improved through the acidic passivation of partial pore openings of the molecular sieve, so that the metal modified Y-type molecular sieve has unique advantages in the reactions of catalytic cracking, alkylation and the like.
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The present example provides a metal modified Y-type molecular sieve prepared by the following three steps:
firstly, preparing the magnesium-iron-based hydrotalcite-like compound by the following method:
Taking a proper amount of magnesium nitrate and ferric chloride according to a molar ratio of 3:1, dissolving the mixture 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 the mass ratio of 2:1 are dissolved in deionized water to prepare alkaline solution with NH 4 + ion concentration of 2 mol/L;
mixing the metal solution with equal mass and the alkaline solution under stirring, immediately filtering and separating after mixing, and vacuum drying at normal temperature for 24 hours to obtain the magnesium-iron hydrotalcite compound, wherein XRD (X-ray diffraction) spectrogram and SEM (scanning electron microscope) chart of the magnesium-iron hydrotalcite compound are shown in figures 5 and 6.
Preparing a guiding agent for synthesizing the Y-type molecular sieve in the second step:
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 directing agent solution;
finally synthesizing a metal modified Y-type molecular sieve:
Sequentially adding 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 wt% SiO 2 content) into 4000g of deionized water, and stirring at normal temperature to form a sol solution;
Adding all the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
Transferring the sol into a hydrothermal crystallization kettle, crystallizing at 150 ℃ for 72 hours, filtering, washing, drying at 80 ℃ for 12 hours, heating to 350 ℃ for 2 hours according to the heating rate of 2 ℃/min, continuously heating to 550 ℃ for 6 hours according to the original heating rate, and roasting to obtain the metal modified NaY type molecular sieve.
Mixing the NaY molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1:10, carrying out ion exchange under the condition of water bath stirring at 85 ℃, repeating the filtering, drying and roasting operations in the last step after the ion exchange, and obtaining the metal modified HY type molecular sieve after the ion exchange for 3 times.
Comparative example 1
This comparative example provides a Y-type molecular sieve, which is not metal modified in comparative example 1, as compared to example 1, and is prepared 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 directing 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 wt% SiO 2 content) are added into 4000g of deionized water in sequence, and stirred at normal temperature until uniform sol solution is formed;
Adding all the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
Transferring the sol into a hydrothermal crystallization kettle, crystallizing at 150 ℃ for 72 hours, filtering, washing, drying at 80 ℃ for 12 hours, heating to 350 ℃ for 2 hours according to the heating rate of 2 ℃/min, continuously heating to 550 ℃ for 6 hours according to the original heating rate, and roasting to obtain the Y-type molecular sieve.
Mixing the NaY molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1:10, carrying out ion exchange under the condition of water bath stirring at 85 ℃, repeating the filtering, drying and roasting operations in the last step after the ion exchange, and obtaining the metal modified HY type molecular sieve after the ion exchange for 3 times.
Example 2
The present example provides a metal modified Y-type molecular sieve prepared by the steps of:
firstly, preparing the magnesium-iron-based hydrotalcite-like compound by the following method:
taking a proper amount of magnesium nitrate and ferric nitrate according to a mole ratio of 4:1, dissolving the mixture 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 the mass ratio of 1:1 are dissolved in deionized water to prepare alkaline solution with NH 4 + ion concentration of 2 mol/L;
mixing the metal solution with equal mass and the alkaline solution under the stirring condition, immediately filtering and separating after mixing, and vacuum drying at normal temperature for 24 hours to obtain the magnesium-iron hydrotalcite compound.
Preparing a guiding agent for synthesizing the Y-type molecular sieve in the second step:
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 vigorously, sealing and aging for 24 hours to prepare a directing agent solution;
finally synthesizing a 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 wt percent of SiO 2 content) are sequentially added into 4100g of deionized water, and stirred at normal temperature until sol solution is formed;
Adding all the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
Transferring the sol into a hydrothermal crystallization kettle, crystallizing for 120 hours at 180 ℃, filtering, washing, drying at 90 ℃ for 12 hours, heating to 300 ℃ for 2 hours according to the heating rate of 2 ℃/min, continuously heating to 500 ℃ for 6 hours according to the original heating rate, and roasting to obtain the metal modified NaY-type molecular sieve.
Mixing the NaY molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1:10, carrying out ion exchange under the condition of water bath stirring at 85 ℃, repeating the filtering, drying and roasting operations in the last step after the ion exchange, and obtaining the metal modified HY type molecular sieve after the ion exchange for 3 times.
Comparative example 2
Compared with the embodiment 2, the comparative example 2 does not add the magnesium-iron-based hydrotalcite-like precursor, but uses inorganic magnesium salt for in-situ doping modification, and the specific preparation steps are as follows:
Firstly, preparing a guiding agent for synthesizing a 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 vigorously, sealing and aging for 24 hours to prepare a directing agent solution;
finally synthesizing a metal modified Y-type molecular sieve:
2.0g of magnesium chloride, 44.9g of sodium hydroxide, 75.2g of sodium aluminate and 890g of silica sol (25 wt percent of SiO 2 content) are sequentially added into 4100g of deionized water, and stirred at normal temperature until uniform sol solution is formed;
Adding all the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
Transferring the sol into a hydrothermal crystallization kettle, crystallizing at 150 ℃ for 72 hours, filtering, washing, drying at 80 ℃ for 12 hours, heating to 350 ℃ according to the heating rate of 2 ℃/min for 2 hours, continuously heating to 550 ℃ according to the original heating rate for 6 hours, and roasting to obtain the metal modified Y-type molecular sieve.
Mixing the NaY molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1:10, carrying out ion exchange under the condition of water bath stirring at 85 ℃, repeating the filtering, drying and roasting operations in the last step after the ion exchange, and obtaining the metal modified HY type molecular sieve after the ion exchange for 3 times.
Example 3
The present example provides a metal modified Y-type molecular sieve prepared by the steps of:
firstly, preparing the magnesium-iron-based hydrotalcite-like compound by the following method:
taking a proper amount of magnesium chloride and ferric nitrate according to a molar ratio of 2.8:1, dissolving the mixture 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 the mass ratio of 1:1 are dissolved in deionized water to prepare alkaline solution with NH 4 + ion concentration of 2 mol/L;
mixing the metal solution with equal mass and the alkaline solution under the stirring condition, immediately filtering and separating after mixing, and vacuum drying at normal temperature for 24 hours to obtain the magnesium-iron hydrotalcite compound.
Preparing a guiding agent for synthesizing the Y-type molecular sieve in the second step:
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 directing agent solution;
finally synthesizing a 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 wt percent of SiO 2 content) are added into 4000g of deionized water in sequence, and stirred at normal temperature until sol solution is formed;
Adding all the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
transferring the sol into a hydrothermal crystallization kettle, crystallizing at 160 ℃ for 180 hours, filtering, washing, drying at 100 ℃ for 12 hours, heating to 600 ℃ according to the heating rate of 2 ℃/min, and roasting for 4 hours to obtain the metal modified NaY molecular sieve.
Mixing the NaY molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1:10, carrying out ion exchange under the condition of water bath stirring at 85 ℃, repeating the filtering, drying and roasting operations in the last step after the ion exchange, and obtaining the metal modified HY type molecular sieve after the ion exchange for 3 times.
Comparative example 3
This comparative example provides a metal modified Y-type molecular sieve, which is prepared by the following two steps, compared to example 3, in which comparative example 3 is modified in situ using an inorganic iron salt without the addition of a magnesium-iron based hydrotalcite-like precursor.
Firstly, preparing a guiding agent for synthesizing a 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 directing agent solution;
finally synthesizing a 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 wt percent of SiO 2 content) are added into 4000g of deionized water in sequence, and stirred at normal temperature until a uniform sol solution is formed;
Adding all the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
Transferring the sol into a hydrothermal crystallization kettle, crystallizing at 150 ℃ for 72 hours, filtering, washing, drying at 80 ℃ for 12 hours, heating to 350 ℃ according to the heating rate of 2 ℃/min for 2 hours, continuously heating to 550 ℃ according to the original heating rate for 6 hours, and roasting to obtain the metal modified Y-type molecular sieve.
Mixing the NaY molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1:10, carrying out ion exchange under the condition of water bath stirring at 85 ℃, repeating the filtering, drying and roasting operations in the last step after the ion exchange, and obtaining the metal modified HY type molecular sieve after the ion exchange for 3 times.
Example 4
The present example provides a metal modified Y-type molecular sieve prepared by the steps of:
firstly, preparing the magnesium-iron-based hydrotalcite-like compound by the following method:
taking a proper amount of magnesium chloride and ferric chloride according to a mole ratio of 4:1, dissolving the mixture 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 the mass ratio of 1:1 are dissolved in deionized water to prepare alkaline solution with NH 4 + ion concentration of 2 mol/L;
mixing the metal solution with equal mass and the alkaline solution under the stirring condition, immediately filtering and separating after mixing, and vacuum drying at normal temperature for 24 hours to obtain the magnesium-iron hydrotalcite compound.
Preparing a guiding agent for synthesizing the Y-type molecular sieve in the second step:
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 directing agent solution;
finally synthesizing a 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 wt percent of SiO 2 content) are added into 4500g of deionized water in sequence, and stirred at normal temperature until a uniform solution is formed;
Adding all the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
Transferring the sol into a hydrothermal crystallization kettle, crystallizing at 140 ℃ for 100 hours, filtering, washing, drying at 80 ℃ for 12 hours, heating to 500 ℃ according to the heating rate of 2 ℃/min, and roasting for 4 hours to obtain the metal modified NaY molecular sieve.
Mixing the NaY molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1:10, carrying out ion exchange under the condition of water bath stirring at 85 ℃, repeating the filtering, drying and roasting operations in the last step after the ion exchange, and obtaining the metal modified HY type molecular sieve after the ion exchange for 3 times.
Comparative example 4
Compared with the embodiment 4, the comparative example 4 does not add the magnesium-iron-based hydrotalcite-like precursor, but uses inorganic magnesium salt and inorganic ferric salt for in-situ doping modification, and the specific preparation steps are as follows:
Firstly, preparing a guiding agent for synthesizing a 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 directing agent solution;
and synthesizing a metal modified Y-type molecular sieve in the second step:
6.2g of magnesium nitrate, 2.0g of ferric nitrate, 52.6g of sodium hydroxide, 84.3g of pseudo-boehmite and 910g of silica sol (25 wt percent SiO 2 content) are added into 4500g of deionized water in sequence, and stirred at normal temperature until a uniform solution is formed;
Adding all the guiding agent solution into the sol solution obtained in the previous step, and continuously stirring;
Transferring the sol into a hydrothermal crystallization kettle, crystallizing at 140 ℃ for 100 hours, filtering, washing, drying at 80 ℃ for 12 hours, heating to 500 ℃ according to the heating rate of 2 ℃/min, and roasting for 4 hours to obtain the metal modified NaY molecular sieve.
Mixing the NaY molecular sieve with 1mol/L ammonium chloride according to the mass ratio of 1:10, carrying out ion exchange under the condition of water bath stirring at 85 ℃, repeating the filtering, drying and roasting operations in the last step after the ion exchange, and obtaining the metal modified HY type molecular sieve after the ion exchange for 3 times.
As can be seen from FIG. 1, both example 1 and comparative example 1 show typical diffraction peaks of the octahedral zeolite cage type molecular sieve, which shows that the crystal forms of the Y type molecular sieve synthesized by the two are complete.
As can be seen from fig. 2, example 2 and comparative example 2 show typical diffraction peaks of the octahedral zeolite cage molecular sieve, which shows that the crystal forms of the Y-type molecular sieve synthesized by the two are complete.
Fig. 3 is an SEM image of a sample of example 1 synthesized using the preparation method of the present invention, and fig. 4 is an SEM image of a sample synthesized in comparative example 1.
As can be seen from FIGS. 3 and 4, the sample of example 1 synthesized by the preparation method of the present invention has a grain size of about 200nm, and the sample of comparative example 1 has a grain size exceeding 1. Mu.m. Therefore, the preparation method can obviously reduce the grain size of the Y-type molecular sieve, and has obvious effect in reducing the grain size of the Y-type molecular sieve.
In order to fully explain the application effect of the metal modified Y-type molecular sieve prepared by the invention, the molecular sieve prepared by the example or the comparative example is put into a screw rod extrusion machine for extrusion molding, dried and roasted and then crushed to about 1 cm. The prepared molecular sieve is used as solid acid for alkylation reaction, and the specific reaction process is as follows:
100g of molecular sieve catalyst is taken and filled 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 tightly pressed by inert alumina pellets. After the pressure in the reactor was raised to 2.5MPa with nitrogen, the reactor temperature was raised to 65 ℃. After the temperature rise is finished, the isobutane and the fumaric acid are pressed into the reactor by a metering pump according to the mol ratio of 100:1, and the mass space velocity of the fumaric acid is adjusted to be 0.05h -1. Carrying out alkylation reaction under the above conditions, condensing and separating by adopting an ice-water mixture at the outlet of the reactor, and analyzing the content of olefin by chromatography, wherein the upper outlet of the condenser is non-condensable gas (including unreacted alkane and olefin); the condensate was subjected to near infrared spectroscopy to determine the octane number. The reaction results are shown in Table 1.
Table 1 results of alkylation reactions with catalysts of examples and comparative examples
As shown by the evaluation result of the alkylation reaction, the metal modified Y-type molecular sieve prepared by adopting the technical scheme of the invention has excellent alkylation reaction performance. The alkylation reaction service life and the product octane number of the Y-type molecular sieve after in-situ modification by adopting the magnesium-containing iron-based hydrotalcite-like compound are both higher than those of a comparative example, which shows that obvious progress can be made by adopting the preparation method disclosed by the invention.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The preparation method of the metal modified Y-type molecular sieve is characterized by comprising the following steps of:
mixing the magnesium-iron-based hydrotalcite-like compound, an alkali source, an aluminum source, a silicon source and a guiding agent with deionized water, and stirring to form 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, and the grain size of the magnesium-iron-based hydrotalcite is 10-50 nanometers; the mass ratio of the magnesium-iron-based hydrotalcite-like compound, 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): (0.02-0.2): (2.5-10.0).
2. The method for preparing a metal modified Y-type molecular sieve according to claim 1, wherein the method for preparing a magnesium-iron-based hydrotalcite-like compound comprises the steps of: dissolving magnesium salt and ferric 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 with an alkaline solution according to the following ratio of 1: mixing under stirring at a mass ratio of 1-5, immediately filtering and separating after mixing, and drying at 10-50 ℃ to obtain the magnesium-iron hydrotalcite-like compound;
Wherein the concentration of NH 4 + in the alkaline solution is 1.6-2.4mol/L.
3. The method for preparing a metal modified Y-type molecular sieve according to claim 2, wherein the total metal ions in the metal solution are Mg 2+ and the molar ratio of Fe 3+,Mg2+ to Fe 3+ 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): 1.
4. The method for preparing the metal modified Y-type molecular sieve according to claim 2, wherein the magnesium salt is magnesium chloride and/or magnesium nitrate, and the ferric salt is ferric chloride and/or ferric nitrate.
5. The method of preparing a 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 a combination of a plurality of pseudo-boehmite, sodium metaaluminate, aluminum hydroxide and aluminum sol; the silicon source comprises one of water glass and alkaline silica sol; the silicon source is calculated as silicon, the aluminum source is calculated as aluminum, and the molar ratio of the silicon source to the aluminum source is 3.03-5.88:1.
6. The method for preparing a metal modified Y-type molecular sieve according to 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 comprising a directing agent.
7. The method for preparing a metal modified Y-type molecular sieve according to claim 6, 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.
8. The method for preparing a metal modified Y-type molecular sieve according to claim 1, wherein the crystallization further comprises filtering, drying and roasting the crystallized product, and the crystallization conditions are as follows: the temperature is 120-200 ℃ and the time is 12-196 hours; drying at 90-150deg.C for 8-12 hr; the roasting temperature is 450-600 ℃ and the roasting time is 4-10 hours.
9. The method for preparing a metal modified Y-type molecular sieve according to claim 1, further comprising the step of carrying out ion exchange on the metal modified Y-type molecular sieve raw powder and an ammonium salt solution or dilute hydrochloric acid to obtain the metal modified H-Y-type molecular sieve.
10. A metal modified Y-type molecular sieve obtainable by the process of any one of claims 1 to 9.
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