CN111825101B - High-silicon Y molecular sieve and preparation method thereof - Google Patents
High-silicon Y molecular sieve and preparation method thereof Download PDFInfo
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- CN111825101B CN111825101B CN201910312310.XA CN201910312310A CN111825101B CN 111825101 B CN111825101 B CN 111825101B CN 201910312310 A CN201910312310 A CN 201910312310A CN 111825101 B CN111825101 B CN 111825101B
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- aluminum
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 73
- 239000010703 silicon Substances 0.000 title claims abstract description 71
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 56
- 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 56
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000499 gel Substances 0.000 claims description 27
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- IVMKBBDVVDYGPS-UHFFFAOYSA-N 1,4-dipropylpiperazine Chemical compound CCCN1CCN(CCC)CC1 IVMKBBDVVDYGPS-UHFFFAOYSA-N 0.000 claims description 3
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 3
- YFKIAMJNCAVCHI-UHFFFAOYSA-N 1-butyl-4-ethyl-2-methylpiperazine Chemical compound C(C)N1CCN(C(C1)C)CCCC YFKIAMJNCAVCHI-UHFFFAOYSA-N 0.000 claims description 3
- TXIOGJHPPVXTOY-UHFFFAOYSA-N 1-ethyl-4-methylpiperazine Chemical compound CCN1CCN(C)CC1 TXIOGJHPPVXTOY-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001231 choline Drugs 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004231 fluid catalytic cracking Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000013043 chemical agent Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 7
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- -1 hydroxyalkyl quaternary ammonium salt Chemical class 0.000 description 3
- GDCCFQMGFUZVKK-UHFFFAOYSA-N 1-butyl-2h-pyridine Chemical group CCCCN1CC=CC=C1 GDCCFQMGFUZVKK-UHFFFAOYSA-N 0.000 description 2
- UCRIXEWTILHNCG-UHFFFAOYSA-N 1-ethyl-2h-pyridine Chemical group CCN1CC=CC=C1 UCRIXEWTILHNCG-UHFFFAOYSA-N 0.000 description 2
- HZONRRHNQILCNO-UHFFFAOYSA-N 1-methyl-2h-pyridine Chemical group CN1CC=CC=C1 HZONRRHNQILCNO-UHFFFAOYSA-N 0.000 description 2
- BFEHJRCAUOMQSD-UHFFFAOYSA-N 1-propyl-2h-pyridine Chemical group CCCN1CC=CC=C1 BFEHJRCAUOMQSD-UHFFFAOYSA-N 0.000 description 2
- YDIKSFBWEVBVSF-UHFFFAOYSA-N 3-butyl-1-ethyl-2H-pyridine Chemical group C(C)N1CC(=CC=C1)CCCC YDIKSFBWEVBVSF-UHFFFAOYSA-N 0.000 description 2
- QNRNKMWBAVDKFO-UHFFFAOYSA-N CCCC1N(CC)C=CC=C1.O Chemical group CCCC1N(CC)C=CC=C1.O QNRNKMWBAVDKFO-UHFFFAOYSA-N 0.000 description 2
- MBSDDMITEXPELE-UHFFFAOYSA-N CCCCN1C(CCC)=CN(CC)C1.O Chemical compound CCCCN1C(CCC)=CN(CC)C1.O MBSDDMITEXPELE-UHFFFAOYSA-N 0.000 description 2
- ZCCKVYNZTXDCSL-UHFFFAOYSA-N CCCCN1C=CN(CC)C1.O Chemical compound CCCCN1C=CN(CC)C1.O ZCCKVYNZTXDCSL-UHFFFAOYSA-N 0.000 description 2
- RSPBWCUJEJVGCE-UHFFFAOYSA-N CCCCN1C=CN(CC2=CC=CC=C2)C1.O Chemical compound CCCCN1C=CN(CC2=CC=CC=C2)C1.O RSPBWCUJEJVGCE-UHFFFAOYSA-N 0.000 description 2
- LNYQIMXCGWHYBK-UHFFFAOYSA-N CCN1C=CN(CC2=CC=CC=C2)C1.O Chemical compound CCN1C=CN(CC2=CC=CC=C2)C1.O LNYQIMXCGWHYBK-UHFFFAOYSA-N 0.000 description 2
- ZOLROLDOWYPQAC-UHFFFAOYSA-N CN1C=CN(CC2=CC=CC=C2)C1.O Chemical compound CN1C=CN(CC2=CC=CC=C2)C1.O ZOLROLDOWYPQAC-UHFFFAOYSA-N 0.000 description 2
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229940024548 aluminum oxide Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 238000004400 29Si cross polarisation magic angle spinning Methods 0.000 description 1
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101150113959 Magix gene Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 1
- 229960003805 amantadine Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000563 toxic property Toxicity 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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-
- 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
- C01B39/205—Faujasite type, e.g. type X or Y using at least one organic template directing agent; Hexagonal faujasite; Intergrowth products of cubic and hexagonal faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The application discloses a high-silicon Y molecular sieve and a preparation method thereof, belonging to catalysisThe field of preparation of chemical agents. The anhydrous chemical composition of the high-silicon Y molecular sieve is kM.mR 1. NR2 (Si) x Al y )O 2 The ratio of silicon to aluminum is 7-30. The method comprises the following steps: a) Mixing raw materials containing an aluminum source, a silicon source, an alkali metal source, organic ammonium R1 and water, and then aging to obtain a directing agent; b) Mixing raw materials containing an aluminum source, a silicon source, an alkali metal source, a nitrogen-containing heterocyclic template agent R2 and water to obtain initial gel, and then adding the guiding agent to obtain synthetic gel; c) Crystallizing the synthetic gel. The high-silicon Y molecular sieve has good hydrothermal/thermal stability and catalytic activity, and can be applied to fluid catalytic cracking; the product synthesized by the preparation method has high crystallinity and purity, and can avoid the post-treatment process with complicated process, high energy consumption and heavy pollution.
Description
Technical Field
The application relates to a high-silicon Y molecular sieve and a preparation method thereof, in particular to a high-silicon Y molecular sieve with an FAU topological structure and a method for synthesizing the high-silicon Y molecular sieve by introducing a nitrogen-containing heterocyclic template agent into a synthesis gel system and adding a guiding agent, belonging to the field of catalyst preparation.
Background
The Y molecular sieve is a silico-aluminum molecular sieve with FAU topology, mainly applied to Fluid Catalytic Cracking (FCC), and is the most used molecular sieve material at present. The framework silica-alumina ratio of the Y molecular sieve plays a decisive role in the catalytic performance, wherein the higher the silica-alumina ratio is, the better the catalytic activity and the stability are. At present, the high-silicon Y molecular sieve used in industry is mainly obtained by dealumination through a chemical/physical method, the post-treatment method has the defects of complicated process, high energy consumption and heavy pollution, and the integrity of a crystal structure and the uniformity of aluminum distribution can be maintained while the defects are effectively avoided through direct hydrothermal synthesis. Therefore, the exploration of direct method for synthesizing the Y molecular sieve with high silica-alumina ratio has very important significance for the catalytic cracking process.
For synthesizing the high-silicon Y molecular sieve by the direct method, people firstly synthesize the high-silicon Y molecular sieve in a non-template system, namely, no organic template is added into reaction gel, and the aim of improving the silicon-aluminum ratio of the Y molecular sieve is achieved only by adjusting the gel proportion, the crystallization time, the preparation method of seed crystals or inorganic directing agents and the like, but the yield is very low, and the silicon-aluminum ratio is difficult to reach 6.
The use of organic structure directing agent brings the synthesis of Y molecular sieve into new field, in 1987, U.S. Pat. No. 4,714,601 discloses a FAU homogeneous polycrystal with silicon-aluminium ratio greater than 6 and named ECR-4, which is obtained by using alkyl or hydroxyalkyl quaternary ammonium salt as template agent and hydrothermal crystallization at 70-120 deg.C in the presence of seed crystal.
In 1990, U.S. Pat. No. 4,931,267 discloses a FAU polymorph named ECR-32 having a silicon to aluminum ratio of greater than 6, which is obtained by hydrothermal crystallization at 90-120 ℃ using tetrapropyl and/or tetrabutyl ammonium hydroxide as a structure directing agent and has high thermal stability.
In 1990, french Delprato et al (Zeolite, 1990,10 (6): 546-552) synthesized FAU molecular sieve with cubic structure for the first time by using crown ether as a template, the framework silica-alumina ratio is close to 9.0, which is the highest value that can be realized by the one-step method reported in the literature at present, but the expensive and extremely toxic properties of the crown ether limit the industrial application. Thereafter, U.S. Pat. No. 5,385,717 synthesized Y molecular sieves having a silica to alumina ratio greater than 6 using polyethylene oxide as a template.
Disclosure of Invention
According to one aspect of the application, a high-silicon Y molecular sieve is provided, the silicon-aluminum ratio of the molecular sieve is up to 7-30, the hydrothermal/thermal stability is good, the molecular sieve can be applied to Fluid Catalytic Cracking (FCC), and the molecular sieve has good catalytic reaction activity.
The high-silicon Y molecular sieve is characterized in that the anhydrous chemical composition of the high-silicon Y molecular sieve is shown as a formula I:
kM·mR1·nR2·(Si x Al y )O 2 formula I
Wherein M is at least one selected from alkali metal elements;
r1 represents organic ammonium; r2 represents a nitrogen-containing heterocyclic template agent;
k represents (Si) per mole x Al y )O 2 The mole number of the corresponding alkali metal element, k = 0-0.2;
m and n represent each mole of (Si) x Al y )O 2 The mole number of the corresponding organic ammonium R1 and the nitrogen heterocyclic ring template R2 is m = 0.01-0.2; n =0.01 to 0.2;
x and y represent mole fractions of Si and Al respectively, 2x/y = 7-30, and x + y =1.
Optionally, M is Na, K and/or Cs, preferably Na.
Alternatively, R1 is selected from at least one of the compounds having the structural formula shown in formula II:
wherein R is 11 、R 12 、R 13 And R 14 Independently selected from C 1 ～C 12 Alkyl of (C) 1 ～C 12 Alkoxy group of (C) 1 ～C 12 At least one of hydroxyalkyl groups of (a); x n- Is selected from OH - 、Cl - 、Br - 、I - 、NO 3 - 、HSO 4 - 、H 2 PO 3 - 、SO 4 2- 、HPO 3 2- 、PO 3 3- 。
Preferably, R1 is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and choline.
Optionally, R2 is selected from at least one of a nitrogen-containing heterocyclic compound and a derivative thereof.
Preferably, R2 is selected from the group consisting of pyridine, N-methylpyridine, N-ethylpyridine, N-propylpyridine, N-butylpyridine, N-ethyl-3-butylpyridine, 1-ethyl-2-propylpyridine hydroxide, piperidine, N-dimethylpiperidine, N-dimethyl-3, 5-diethylpiperidine hydroxide, N-dimethyl-3, 5-dipropylpiperidine hydroxide, N-diethyl-2, 6-dimethylpiperidine hydroxide, N, at least one of N-dimethyl-2, 6-diethylpiperidine, imidazole, 1-ethyl-3-butylimidazole hydroxide, 1-ethyl-3-butyl-4-propylimidazole hydroxide, 1-benzyl-3-methylimidazole hydroxide, 1-benzyl-3-ethylimidazole hydroxide, 1-benzyl-3-butylimidazole hydroxide, piperazine, N-methylpiperazine, 1, 4-dipropylpiperazine, 1-methyl-4-ethylpiperazine, and 1-ethyl-4-butyl-5-methylpiperazine.
Alternatively, k = 0.01-0.15; m =0.01 to 0.1; n =0.02 to 0.15.
Preferably, k =0.02 to 0.13; m =0.01 to 0.04; n =0.03 to 0.08.
Alternatively, with x + y =1, the upper limit of 2x/y is selected from 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, or 8, and the lower limit is selected from 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or 29.
According to another aspect of the application, a preparation method of a high-silicon Y molecular sieve is provided, and the method promotes the synthesis of the high-silicon (silicon-aluminum-oxide ratio is 7-30) Y molecular sieve by adding a guiding agent into a synthesis gel system and introducing a nitrogen-containing heterocyclic template agent into the synthesis gel system.
The preparation method of the high-silicon Y molecular sieve is characterized by comprising the following steps of:
a) Mixing raw materials containing an aluminum source, a silicon source, an alkali metal source, organic ammonium R1 and water, and then aging to obtain a directing agent;
b) Mixing raw materials containing an aluminum source, a silicon source, an alkali metal source, a nitrogen-containing heterocyclic template agent R2 and water to obtain initial gel, and then adding the guiding agent to obtain synthetic gel;
c) Crystallizing the synthesized gel to obtain the high-silicon Y molecular sieve.
Optionally, the silicon source in step a) and step b) is independently selected from at least one of methyl orthosilicate, ethyl orthosilicate, silica sol, solid silica gel, silica white and sodium silicate.
Optionally, the aluminum sources in step a) and step b) are independently selected from at least one of sodium metaaluminate, alumina, aluminum hydroxide, aluminum isopropoxide, aluminum 2-butoxide, aluminum chloride, aluminum sulfate, and aluminum nitrate.
Optionally, the alkali metal source in step a) and step b) is independently selected from at least one of sodium hydroxide, potassium hydroxide and cesium hydroxide.
Alternatively, in step a), R1 is selected from at least one of the compounds having the formula shown in formula II:
wherein R is 11 、R 12 、R 13 And R 14 Independently selected from C 1 ～C 12 Alkyl of (C) 1 ～C 12 Alkoxy group of (C) 1 ～C 12 At least one of hydroxyalkyl groups of (a); x n- Selected from OH - 、Cl - 、Br - 、I - 、NO 3 - 、HSO 4 - 、H 2 PO 3 - 、SO 4 2- 、HPO 3 2- 、PO 3 3- 。
Preferably, in step a), R1 is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and choline.
Alternatively, in step a), the aluminum source, the silicon source, the alkali metal source, the organic ammonium R1 and the water are mixed in the following molar ratios:
1Al 2 O 3 :(5～30)SiO 2 :(0～3)M 2 O:(5～40)R1:(100～600)H 2 O；
wherein the mole number of the silicon source is SiO 2 Counting; the mol number of the aluminum source is Al 2 O 3 Counting; the number of moles of the organic ammonium R1 is based on the number of moles of R1 per se; the molar number of the alkali metal source is equal to the metal oxide M corresponding to the corresponding alkali metal M 2 And the mole number of O.
Preferably, in step a), the aluminum source, the silicon source, the alkali metal source, the organic ammonium R1 and the water are mixed in the following molar ratios:
1Al 2 O 3 :(5～30)SiO 2 :(0～3)M 2 O:(7～40)R1:(100～600)H 2 O；
wherein the mole number of the silicon source is SiO 2 Counting; the mole number of the aluminum source is Al 2 O 3 Counting; the number of moles of the organic ammonium R1 is based on the number of moles of R1 per se; the molar number of the alkali metal source is equal to the metal oxide M corresponding to the corresponding alkali metal M 2 And the mole number of O.
Optionally, in step a), the aging is carried out at 25 to 140 ℃ for 1 to 30 days.
Preferably, in step a), the temperature of the aging is selected from the upper limit of 140 ℃, 130 ℃, 120 ℃, 110 ℃, 100 ℃, 90 ℃, 80 ℃, 70 ℃,60 ℃, 50 ℃, 40 ℃, 30 ℃ and the lower limit of 25 ℃, 30 ℃, 40 ℃, 50 ℃,60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃.
Preferably, in step a), the aging time is selected from the upper limit of 30 days, 29 days, 28 days, 27 days, 26 days, 25 days, 24 days, 23 days, 22 days, 21 days, 20 days, 19 days, 18 days, 17 days, 16 days, and the lower limit is selected from the lower limit of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 15 days.
More preferably, in step a), the aging is performed at 30 to 120 ℃ for 1 to 25 days.
Optionally, in step a), the aging is carried out in a static manner, for example in a standing manner.
Optionally, in step a), the aging is carried out in a dynamic manner, for example in a stirred or rotating manner.
Optionally, in step b), R2 is selected from at least one of a nitrogen-containing heterocyclic compound and a derivative thereof.
Preferably, in step b), R2 is selected from pyridine, N-methylpyridine, N-ethylpyridine, N-propylpyridine, N-butylpyridine, N-ethyl-3-butylpyridine, 1-ethyl-2-propylpyridine hydroxide, piperidine, N-dimethylpiperidine, N-dimethyl-3, 5-diethylpiperidine hydroxide, N-dimethyl-3, 5-dipropylpiperidine hydroxide, N-diethyl-2, 6-dimethylpiperidine hydroxide, N, at least one of N-dimethyl-2, 6-diethylpiperidine, imidazole, 1-ethyl-3-butylimidazole hydroxide, 1-ethyl-3-butyl-4-propylimidazole hydroxide, 1-benzyl-3-methylimidazole hydroxide, 1-benzyl-3-ethylimidazole hydroxide, 1-benzyl-3-butylimidazole hydroxide, piperazine, N-methylpiperazine, 1, 4-dipropylpiperazine, 1-methyl-4-ethylpiperazine, and 1-ethyl-4-butyl-5-methylpiperazine.
Alternatively, in step b), the aluminum source, the silicon source, the alkali metal source, the nitrogen-containing heterocyclic templating agent R2, and water are mixed in the following molar ratios:
1Al 2 O 3 :(10～200)SiO 2 :(0～30)M 2 O:(1～45)R2:(100～4000)H 2 O；
wherein the mole number of the silicon source is SiO 2 Counting; the mole number of the aluminum source is Al 2 O 3 Counting; the mole number of the nitrogen-containing heterocyclic template agent R2 is calculated by the mole number of the R2; the molar number of the alkali metal source is equal to the metal oxide M corresponding to the corresponding alkali metal M 2 And the mole number of O.
Preferably, in step b), the aluminum source, the silicon source, the alkali metal source, the nitrogen-containing heterocyclic templating agent R2, and water are mixed in the following molar ratios:
1Al 2 O 3 :(10～200)SiO 2 :(0.1～25)M 2 O:(3～40)R2:(150～3000)H 2 O；
wherein the mole number of the silicon source is SiO 2 Counting; the mole number of the aluminum source is Al 2 O 3 Counting; the mol number of the nitrogen-containing heterocyclic template agent R2 is calculated by the mol number of the R2; the number of moles of alkali metal source is equal to the number of moles of metal oxide M corresponding to the corresponding alkali metal M 2 And the mole number of O.
Optionally, in step b), the amount of the guiding agent added is such that SiO in the guiding agent 2 The content of SiO in the initial gel 2 5-20 wt% of the content.
Preferably, in step b), siO in the directing agent 2 The content of SiO in the initial gel 2 The upper limit of the content by mass percent is selected from 20wt percent, 19wt percent, 18wt percent, 17wt percent,16wt%, 15wt%, 14wt%, 13wt%, 12wt%, 11wt%, 10wt%, 9wt%, 8wt%, 7wt%, 6wt%, with the lower limit selected from the group consisting of 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%.
Optionally, in step b), the directing agent is added to the initial gel in the form of a solution.
Optionally, in the step b), after the initial gel is obtained, adding the directing agent and stirring for 1-4 hours to obtain the synthetic gel.
Optionally, in step c), the crystallization is performed at 90 to 140 ℃ for 3 to 15 days.
Preferably, in step c), the crystallization temperature has an upper limit selected from the group consisting of 140 ℃, 135 ℃, 130 ℃, 125 ℃, 120 ℃, 115 ℃, 110 ℃, 105 ℃, 100 ℃, 95 ℃, and a lower limit selected from the group consisting of 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃.
Preferably, in step c), the upper limit of the crystallization time is selected from 15 days, 14 days, 13 days, 12 days, 11 days, 10 days, 9 days, 8 days, 7 days, 6 days, 5 days and 4 days, and the lower limit is selected from 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days and 14 days.
Optionally, in step c), the crystallization is performed under autogenous pressure.
In the method, the crystallization mode in step c) may be dynamic crystallization or static crystallization, or may be a combination of two crystallization modes.
Optionally, in step c), the crystallization is performed in a dynamic or static manner.
Optionally, in step c), the crystallization is performed in a combination of dynamic and static manner, for example, in a first static and then dynamic manner.
In the present application, dynamic crystallization refers to that the slurry in the crystallization kettle is in a non-standing state, and static crystallization refers to that the slurry in the crystallization kettle is in a standing state.
Optionally, in step c), after the crystallization, filtering, washing and drying the solid product to obtain the high-silicon Y molecular sieve.
In the method, the washing, filtering, separating and drying of the obtained Y molecular sieve are all conventional operations, wherein the drying can be carried out by standing at 100-110 ℃ for 12 hours.
In a specific embodiment, the high silicon Y molecular sieve is synthesized as follows:
a1 Preparation of directing agent: aluminum source, silicon source, organic ammonium R1 and deionized water according to 1Al 2 O 3 :(5～30)SiO 2 :(0～2)Na 2 O:(5～40)R1:(100～600)H 2 Mixing and stirring the mixture for 2 hours according to the molar ratio of O to obtain a uniform mixture, and then continuously stirring/standing the mixture for 1 to 30 days at a temperature of between 25 and 140 ℃ to obtain a guiding agent;
b1 Preparation of a synthetic gel: aluminum source, silicon source, sodium hydroxide, nitrogen-containing heterocyclic template agent R2 and deionized water according to 1Al 2 O 3 :(10～200)SiO 2 :(0～30)Na 2 O:(1～45)R2:(100～4000)H 2 Mixing and stirring the mixture evenly at room temperature according to the molar ratio of O to obtain initial gel, adding a certain amount of guiding agent, and stirring for 1-4 hours to obtain synthetic gel;
c1 Synthesis of high silicon Y molecular sieves: crystallizing the synthesized gel at 90-140 deg.c under autogenous pressure for 3-15 days, filtering and separating the solid product after crystallization, washing with deionized water to neutrality and drying to obtain high silicon Y molecular sieve.
In accordance with yet another aspect of the present application, a catalyst is provided, and the high-silicon Y molecular sieve having FAU topology prepared according to the method described herein is useful in fluid catalytic cracking catalysts as well as supports and catalysts for bifunctional catalysis such as hydrocracking, hydrodesulfurization and the like.
In the context of the present application, the term "silicon to aluminum ratio" means in SiO as SiO in a molecular sieve 2 And Al 2 O 3 The molar ratio of silicon to aluminum is taken to have the same meaning as "2x/y" and "silicon to aluminum oxide ratio" as described herein.
The beneficial effects that can be produced by the application include but are not limited to:
1) The high-silicon Y molecular sieve has the advantages of high silicon-aluminum ratio of 7-30, good hydrothermal/thermal stability, application to Fluid Catalytic Cracking (FCC) and good catalytic reaction activity.
2) According to the preparation method of the high-silicon Y molecular sieve, the high-silicon-aluminum ratio Y molecular sieve can be synthesized by introducing the nitrogen-containing heterocyclic template agent into a synthesis gel system and adding the guiding agent, and the synthesized product has high crystallinity and purity.
3) The preparation method of the high-silicon Y molecular sieve can avoid the post-treatment process with complicated process, high energy consumption and heavy pollution, and has important significance in the field of actual chemical production.
Drawings
Fig. 1 is an X-ray diffraction (XRD) spectrum of sample Y1.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of sample Y1.
FIG. 3 is a silicon nuclear magnetization of sample Y1 ( 29 Si-NMR) spectrum.
Fig. 4 is an X-ray diffraction (XRD) spectrum of the comparative sample S1.
Fig. 5 is an X-ray diffraction (XRD) spectrum of the comparative sample T1.
Detailed Description
As mentioned above, the present application relates to a high silicon Y molecular sieve with FAU topology and its synthesis method, the anhydrous chemical composition of the molecular sieve is kNa. MR 1. NR2 (Si) x Al y )O 2 Wherein Na is sodium ion and k represents per mole (Si) x Al y )O 2 Corresponding to the mole number of Na ions, R1 represents organic ammonium, R2 is a nitrogen-containing heterocyclic template agent, and m and n represent (Si) per mole x Al y )O 2 The ratio of silicon to aluminum oxide (2 x/y) is 7-30 corresponding to the mole number of the template agents R1 and R2; according to the method, a nitrogen-containing heterocyclic template agent is introduced into a synthetic gel system, and a guiding agent is added to synthesize the high-silicon Y molecular sieve.
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and reagents in the examples of the present application were all purchased commercially.
The analysis method in the examples of the present application is as follows:
x-ray powder diffraction phase analysis (XRD) an X' Pert PRO X-ray diffractometer from pananace, netherlands (PANalytical), cu target, ka radiation source (λ =0.15418 nm), voltage 40kV, current 40mA was used.
The Scanning Electron Microscope (SEM) test adopts a Hitachi SU8020 field emission scanning electron microscope with the accelerating voltage of 2kV.
The elemental composition was determined using a Philips Magix 2424X-ray fluorescence Analyzer (XRF).
Silicon nuclear magnetism 29 Si-NMR) experiments were performed on a Bruker Avance III 600 (14.1 Tesla) spectrometer using a 7mm dual resonance probe, at 6kHz, using a high power proton decoupling procedure, sampling times of 1024, pi/4 pulse width of 2.5 μ s, sampling delay of 10s, chemical shift reference of 4, 4-dimethyl-4-propanesulfonic acid (DSS), calibrated to 0ppm.
Carbon nuclear magnetism ( 13 C MAS NMR) experiments were performed on a Bruker Avance III 600 (14.1 Tesla) spectrometer using a 4mm triple resonance probe, rotating at 12kHz, with amantadine as chemical shift reference, corrected to 0ppm.
Example 1: preparation of sample Y1
Preparing a guiding agent: 1.3g of sodium hydroxide (analytical grade, saikou chemical reagent Co., ltd., tianjin, kogyo, ltd.) and 1.7g of alumina (chemical grade, shanghai chemical reagent Co., ltd., china medicine) were dissolved in 84.1g of tetraethylammonium hydroxide (35 wt% aqueous solution, shanghai chemical reagent Co., ltd., china medicine) and stirred until clarified, 34.7g of ethyl orthosilicate (chemical grade, shanghai chemical reagent Co., china medicine) was added dropwise and stirred at room temperature for 2 hours, and then the obtained solution was allowed to stand at 50 ℃ for 12 hours and then was allowed to stand at 70 ℃ for 2 days.
Preparing a synthetic gel: 0.7g of sodium aluminate (Al) 2 O 3 ：48.3wt％，Na 2 O:36.3wt%, shanghai chemical reagent company, china medicine, 0.20g sodium hydroxide, 10.30g N, N-dimethyl-3, 5-dipropylpiperidine (25 wt%) were dissolved in 4.40g deionized water, stirred until it was clear, and 13.3g silicon was added dropwiseSol (SiO) 2 :30wt%, shenyang chemical Co., ltd.) was stirred for 2 hours, and 4.9g of the above directing agent was added thereto and stirred for 3 hours.
Synthesizing a high-silicon Y-type molecular sieve: and transferring the synthesized gel into a stainless steel reaction kettle, standing for 5 days at 120 ℃ under autogenous pressure, separating solid from liquid, washing to be neutral, and drying for 12 hours at 100 ℃ to obtain a sample Y1.
The X-ray powder diffraction pattern (XRD) of sample Y1 is shown in fig. 1, indicating that the sample is a molecular sieve having the FAU framework structure. A Scanning Electron Micrograph (SEM) of sample Y1 is shown in FIG. 2, which shows that the particles of this sample are platelet-shaped and have a size of 50nm to 200nm. Of sample Y1 29 Si MAS NMR spectra are shown in FIG. 3, and the calculated framework Si/Al ratio by fitting is consistent with that calculated by XRF, according to XRF and 13 c MAS NMR analysis normalization gave the elemental composition of sample Y1 as: 0.07 Na.0.02R1 2 ·0.05R2 1 (Si 0.86 Al 0.14 )O 2 Wherein, R1 2 Is tetraethylammonium hydroxide, R2 1 Is N, N-dimethyl-3, 5-dipropylpiperidine hydroxide.
Example 2: preparation of samples Y2 to Y30
The gel preparation process of the samples Y2 to Y30 is the same as that of example 1, the types of raw materials, the molar ratio, the crystallization conditions, the product structures and the silicon-aluminum ratio (the silicon-aluminum ratio of the product is determined by an X-ray fluorescence analyzer (XRF)) are shown in Table 1, and the aging temperature and time of the directing agents, the addition amounts of the directing agents and the sample compositions of the samples Y2 to Y30 are shown in Table 2.
Comparative example 1: preparation of comparative samples S1 to S30
The specific compounding process is the same as the preparation of sample Y1 in example 1, except that: the preparation step of the guiding agent is not needed, and the guiding agent is not added in the subsequent preparation step of the synthetic gel. The types of raw materials, molar ratios, crystallization conditions and product structures for synthesizing each product are detailed in table 3. The obtained samples were designated as comparative samples S1 to S30.
Comparative example 2: preparation of comparative samples T1 to T30
The specific compounding process is the same as the preparation of sample Y1 in example 1, except that: after the ingredients in the preparation step of the guiding agent are completed, the mixture is stirred for 2 hours at room temperature without aging. The types of raw materials, molar ratios, crystallization conditions, the addition amount of a directing agent and the structure of the product for synthesizing each product are shown in Table 4. The samples obtained are designated as comparative samples T1 to T30.
Example 3: characterization analysis of samples Y1-Y30 and comparative samples S1-S30 and T1-T30
The phases of the samples Y1 to Y30 and the comparative samples S1 to S30 and T1 to T30 were analyzed by X-ray diffraction.
The results show that the samples Y1 to Y30 prepared in examples 1 and 2 are all high-purity and high-crystallinity Y molecular sieves, and are typically represented by XRD spectrum of the sample Y1 as in fig. 1, fig. 2 is SEM photograph of the sample Y1, and fig. 3 is silicon nuclear magnetic spectrum of the sample Y1. The XRD spectrogram results of the samples Y2 to Y30 are similar to those in figure 1, namely the positions and the shapes of diffraction peaks are basically the same, and the relative peak intensity fluctuates within +/-5 percent according to the change of synthesis conditions, which indicates that the samples Y1 to Y30 have the structural characteristics of a Y molecular sieve and have no mixed crystals.
In tables 3 and 4, the comparative samples S1 to S30 and the comparative samples T1 to T30 are amorphous, wherein XRD patterns of the comparative sample S1 and the comparative sample T1 are shown in fig. 4 and 5, respectively, as typical representations. It can be seen that in the synthesis of the high-silicon Y molecular sieve according to the application, the addition of the directing agent is necessary, and the high-temperature aging is necessary in the preparation process of the directing agent to play a role in inducing crystallization, which is the key for synthesizing the high-silicon Y molecular sieve according to the application.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (17)
1. A high silicon Y molecular sieve having an anhydrous chemical composition according to formula I:
kM×mR1×nR2×(Si x Al y )O 2 formula I
Wherein M is at least one selected from alkali metal elements;
r1 represents organic ammonium; r2 represents a nitrogen-containing heterocyclic template agent;
k represents per mole (Si) x Al y )O 2 The mole number of the corresponding alkali metal element, k =0 to 0.2;
m and n represent each mole of (Si) x Al y )O 2 The mole number of the corresponding organic ammonium R1 and nitrogen-containing heterocyclic template agent R2, m =0.01~0.2；n=0.01~0.2；
x and y respectively represent mole fractions of Si and Al, 2x/y =7 to 30, x + y =1;
r2 is at least one selected from piperazine, N-methylpiperazine, 1, 4-dipropylpiperazine, 1-methyl-4-ethylpiperazine and 1-ethyl-4-butyl-5-methylpiperazine;
r1 is at least one selected from compounds having the structural formula shown in formula II:
Wherein R is 11 、R 12 、R 13 And R 14 Independently selected from C 1 ~C 12 Alkyl of (C) 1 ~C 12 Alkoxy group of (C) 1 ~C 12 At least one of hydroxyalkyl groups of (a); x n- Selected from OH - 、Cl - 、Br - 、I - 、NO 3 - 、HSO 4 - 、H 2 PO 3 - 、SO 4 2- 、HPO 3 2- 、PO 3 3- 。
2. The high silicon Y molecular sieve of claim 1, wherein M is Na, K and/or Cs.
3. The high silicon Y molecular sieve of claim 1, wherein R1 is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and choline.
4. The high silicon Y molecular sieve of claim 1, wherein k =0.01 to 0.15; m =0.01 to 0.1; n =0.02 to 0.15.
5. The high silicon Y molecular sieve of claim 1, wherein k =0.02 to 0.13; m =0.01 to 0.04; n =0.03 to 0.08.
6. The method of any of claims 1 to 5, comprising the steps of:
a) Mixing raw materials containing an aluminum source, a silicon source, an alkali metal source, organic ammonium R1 and water, and then aging to obtain a directing agent;
b) Mixing raw materials containing an aluminum source, a silicon source, an alkali metal source, a nitrogen-containing heterocyclic template agent R2 and water to obtain initial gel, and then adding the guiding agent to obtain synthetic gel;
c) Crystallizing the synthesized gel to obtain the high-silicon Y molecular sieve.
7. The method of claim 6, wherein the silicon source in step a) and step b) is independently selected from at least one of methyl orthosilicate, ethyl orthosilicate, silica sol, solid silica gel, silica white and sodium silicate;
the aluminum sources in step a) and step b) are independently selected from at least one of sodium metaaluminate, alumina, aluminum hydroxide, aluminum isopropoxide, aluminum 2-butoxide, aluminum chloride, aluminum sulfate, and aluminum nitrate;
the alkali metal source in step a) and step b) is independently selected from at least one of sodium hydroxide, potassium hydroxide and cesium hydroxide.
8. The process of claim 6, wherein in step a), the aluminum source, the silicon source, the alkali metal source, the organoammonium R1, and the water are mixed in the following molar ratios:
1Al 2 O 3 :(5~30)SiO 2 :(0~3)M 2 O:(5~40)R1:(100~600)H 2 O。
9. the process of claim 6, wherein in step a), the aluminum source, the silicon source, the alkali metal source, the organoammonium R1, and the water are mixed in the following molar ratios:
1Al 2 O 3 :(5~30)SiO 2 :(0~3)M 2 O:(7~40)R1:(100~600)H 2 O；
wherein the mole number of the silicon sourceWith SiO 2 Counting; the mole number of the aluminum source is Al 2 O 3 Counting; the number of moles of organoammonium R1 is based on the number of moles of R1 itself; the number of moles of alkali metal source is equal to the number of moles of metal oxide M corresponding to the corresponding alkali metal M 2 And the mole number of O.
10. The method according to claim 6, wherein in step a), the aging is carried out at 25 to 140 ℃ for 1 to 30 days.
11. The method according to claim 6, wherein in step a), the aging is carried out at 30 to 120 ℃ for 1 to 25 days.
12. The method of claim 6, wherein in step b), the aluminum source, the silicon source, the alkali metal source, the nitrogen-containing heterocyclic templating agent R2, and the water are mixed in the following molar ratios:
1Al 2 O 3 :(10~200)SiO 2 :(0~30)M 2 O:(1~45)R2:(100~4000)H 2 O。
13. the method of claim 6, wherein in step b), the aluminum source, the silicon source, the alkali metal source, the nitrogen-containing heterocyclic templating agent R2, and the water are mixed in the following molar ratios:
1Al 2 O 3 :(10~200)SiO 2 :(0.1~25)M 2 O:(3~40)R2:(150~3000)H 2 O；
wherein the mole number of the silicon source is SiO 2 Counting; the mol number of the aluminum source is Al 2 O 3 Counting; the mol number of the nitrogen-containing heterocyclic template agent R2 is calculated by the mol number of the R2; the number of moles of alkali metal source is equal to the number of moles of metal oxide M corresponding to the corresponding alkali metal M 2 And the mole number of O.
14. The method of claim 6, wherein in step b), the amount of the directing agent added is such that the SiO in the directing agent is 2 In an amount of SiO in the initial gel 2 The content is 5 to 20wt%.
15. The method according to claim 6, wherein in step c), the crystallization is carried out at 90 to 140 ℃ for 3 to 15 days.
16. The process according to claim 6, wherein in step c) the crystallization is carried out in a dynamic or static manner.
17. The method according to claim 6, wherein in step c) the crystallization is performed in a combination of dynamic and static conditions.
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| CN201910312310.XA CN111825101B (en) | 2019-04-18 | 2019-04-18 | High-silicon Y molecular sieve and preparation method thereof |
| KR1020217033741A KR102622825B1 (en) | 2019-04-18 | 2019-09-17 | High-silica Y molecular sieve with FAU topological structure and method for producing the same |
| AU2019441814A AU2019441814B2 (en) | 2019-04-18 | 2019-09-17 | High-silica Y molecular sieve having FAU topology and preparation method therefor |
| US17/604,377 US20220306481A1 (en) | 2019-04-18 | 2019-09-17 | High-silica y molecular sieve having fau topology and preparation method therefor |
| JP2021558687A JP7261316B2 (en) | 2019-04-18 | 2019-09-17 | High silica Y molecular sieve with FAU topology structure and its preparation method |
| PCT/CN2019/106165 WO2020211281A1 (en) | 2019-04-18 | 2019-09-17 | High-silica y molecular sieve having fau topology and preparation method therefor |
| EP19925079.6A EP3957603A4 (en) | 2019-04-18 | 2019-09-17 | High-silica y molecular sieve having fau topology and preparation method therefor |
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