WO2021004492A1 - 基于硅和锗的scm-25分子筛、其制备方法及其用途 - Google Patents
基于硅和锗的scm-25分子筛、其制备方法及其用途 Download PDFInfo
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- WO2021004492A1 WO2021004492A1 PCT/CN2020/100969 CN2020100969W WO2021004492A1 WO 2021004492 A1 WO2021004492 A1 WO 2021004492A1 CN 2020100969 W CN2020100969 W CN 2020100969W WO 2021004492 A1 WO2021004492 A1 WO 2021004492A1
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- WIPO (PCT)
- Prior art keywords
- molecular sieve
- source
- ray diffraction
- germanium
- following table
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 185
- 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 185
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 105
- 239000000203 mixture Substances 0.000 claims abstract description 71
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 67
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 52
- 239000010703 silicon Substances 0.000 claims abstract description 51
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 30
- 229910005793 GeO 2 Inorganic materials 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 50
- -1 halogen ion Chemical class 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000002425 crystallisation Methods 0.000 claims description 35
- 230000008025 crystallization Effects 0.000 claims description 35
- 238000001354 calcination Methods 0.000 claims description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
- 239000011737 fluorine Substances 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 15
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 15
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 10
- 229910052735 hafnium Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical group 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- 229910052810 boron oxide Inorganic materials 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 6
- 229910003437 indium oxide Inorganic materials 0.000 claims description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 239000005909 Kieselgur Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 5
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 5
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- WNPMJIKMURUYFG-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Ge+2].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Ge+2].[N+](=O)([O-])[O-] WNPMJIKMURUYFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 31
- 239000000243 solution Substances 0.000 description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000011065 in-situ storage Methods 0.000 description 14
- 239000011148 porous material Substances 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 238000010304 firing Methods 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000014509 gene expression Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 3
- AMGNHZVUZWILSB-UHFFFAOYSA-N 1,2-bis(2-chloroethylsulfanyl)ethane Chemical compound ClCCSCCSCCCl AMGNHZVUZWILSB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 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 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 description 1
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 1
- RSYUFYQTACJFML-DZGCQCFKSA-N afzelechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C=C1 RSYUFYQTACJFML-DZGCQCFKSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 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
- 239000010425 asbestos Substances 0.000 description 1
- 229950003143 basic zinc acetate Drugs 0.000 description 1
- UCRXQUVKDMVBBM-UHFFFAOYSA-N benzyl 2-amino-3-(4-phenylmethoxyphenyl)propanoate Chemical compound C=1C=CC=CC=1COC(=O)C(N)CC(C=C1)=CC=C1OCC1=CC=CC=C1 UCRXQUVKDMVBBM-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- FLVFLHZPYDNHJE-UHFFFAOYSA-N chloro hypochlorite;hafnium Chemical compound [Hf].ClOCl FLVFLHZPYDNHJE-UHFFFAOYSA-N 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- FYWVTSQYJIPZLW-UHFFFAOYSA-K diacetyloxygallanyl acetate Chemical compound [Ga+3].CC([O-])=O.CC([O-])=O.CC([O-])=O FYWVTSQYJIPZLW-UHFFFAOYSA-K 0.000 description 1
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 229910000373 gallium sulfate Inorganic materials 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 description 1
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 description 1
- FEEFWFYISQGDKK-UHFFFAOYSA-J hafnium(4+);tetrabromide Chemical compound Br[Hf](Br)(Br)Br FEEFWFYISQGDKK-UHFFFAOYSA-J 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- JCPDISNOORFYFA-UHFFFAOYSA-H tetrazinc;oxygen(2-);hexaacetate Chemical compound [O-2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O JCPDISNOORFYFA-UHFFFAOYSA-H 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Images
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- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- 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
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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- 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
- B01J29/047—Germanosilicates; Aluminogermanosilicates
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- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/615—100-500 m2/g
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- 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
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
Definitions
- the invention relates to a SCM-25 molecular sieve, its synthesis method and its use.
- molecular sieves are a kind of porous crystalline material. So far, 245 kinds of molecular sieves with known structures have been discovered, and molecular sieves with new structures are constantly emerging. Due to the regular molecular size pore structure, strong acidity and high hydrothermal stability, molecular sieves are widely used in the fields of catalysis, adsorption and ion exchange, and they play an irreplaceable role.
- the framework of molecular sieve is usually formed by coordinating tetrahedrons (TO 4 ) connected by common vertices (usually oxygen atoms). For molecular sieves, the tetrahedrons in the framework are mainly SiO 4 tetrahedra and AlO 4 tetrahedra.
- These two tetrahedra can be replaced by other tetrahedra to form molecular sieves or molecular sieves with different framework structures.
- AlO 4 tetrahedron can be replaced by GaO 4 or ZnO 4 tetrahedron to form the framework of heteroatom molecular sieve together with SiO 4 tetrahedron.
- Ge and Si have similar coordination properties, and can also form tetrahedral coordination structure. , Through the connection of GeO 4 and SiO 4 , a large number of new germanium-containing molecular sieves or molecular sieve-like structures can be formed.
- the invention provides a molecular sieve based on silicon and germanium and a method for synthesizing the molecular sieve.
- the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
- the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
- the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
- the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
- a molecular sieve having an X-ray diffraction pattern basically as shown in the following table:
- the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
- the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
- a molecular sieve having an X-ray diffraction pattern basically as shown in the following table:
- the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
- the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
- a molecular sieve having an X-ray diffraction pattern basically as shown in the following table:
- the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
- the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
- a molecular sieve having an X-ray diffraction pattern basically as shown in the following table:
- the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
- the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
- the silicon-germanium molar ratio is 0.1 ⁇ n ⁇ 30, preferably 0.25 ⁇ n ⁇ 20, more preferably 0.5 ⁇ n ⁇ 15, more preferably 1 ⁇ n ⁇ 5; 0.05 ⁇ k ⁇ 1.0, preferably 0.05 ⁇ k ⁇ 0.5, more preferably 0.1 ⁇ k ⁇ 0.5, more preferably 0.1 ⁇ k ⁇ 0.4;
- Q is an organic template, 0.01 ⁇ m ⁇ 1.0, preferably 0.02 ⁇ m ⁇ 0.5, more preferably 0.05 ⁇ m ⁇ 0.5, more preferably 0.05 ⁇ m ⁇ 0.3;
- the organic template is selected from the quaternary ammonium form containing 1,1,3,5-tetraalkylpiperidinium ion or the following structural formula, preferably 1,1,3,5-tetramethylpiperidine
- R 1 -R 4 are each independently H or C 1-4 alkyl, preferably C 1-2 alkyl, more preferably -CH 3,
- X - is a halogen ion (such as Cl -, Br - and I -) and hydroxide ions (OH -), preferably a hydroxide ion (OH -); 0.005 ⁇ p ⁇ 0.5, preferably 0.01 ⁇ p ⁇ 0.4, more preferably 0.01 ⁇ p ⁇ 0.3, more preferably 0.02 ⁇ p ⁇ 0.2.
- a method for preparing a molecular sieve based on silicon and germanium comprising forming a silicon source, a germanium source, a fluorine source, an organic template Q and water or a silicon source, a germanium source, a fluorine source, an organic template Q and water The step of crystallizing the mixture of, to obtain the molecular sieve; and optionally, the step of calcining the obtained molecular sieve;
- the organic template Q is selected from the quaternary ammonium form containing 1,1,3,5-tetraalkylpiperidinium ion or the following structural formula, preferably 1,1,3,5-tetramethylpiperidine hydrogen Oxide
- R 1 -R 4 are each independently H or C 1-4 alkyl, preferably C 1-2 alkyl, more preferably -CH 3,
- X - is a halogen ion (such as Cl -, Br - and I -) and hydroxide ions (OH -), preferably a hydroxide ion (OH -).
- the silicon source is selected from the group consisting of water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite, and orthosilica At least one of the group consisting of tetraethyl acid;
- the germanium source is selected from the group consisting of germanium oxide, germanium nitrate and tetraalkoxy germanium (where alkoxy refers to C 1 -C 6 alkoxy) At least one of.
- the organic template Q the silicon source (calculated by SiO 2 ), the germanium source (calculated by GeO 2 ), the fluorine source (calculated by F) and the moles of water
- the fluorine source includes at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride, preferably hydrogen At least one of the group consisting of hydrofluoric acid and ammonium fluoride.
- crystallization conditions include crystallization at 100-200°C for 30-400 hours; preferably 110-190°C for 48-360 hours; more preferably 120- Crystallize at 180°C for 72-320 hours.
- the mixture also includes a source of elements other than silicon and germanium, preferably selected from a source of boron, aluminum, gallium, titanium, zirconium, and hafnium Source, tin source, zinc source, iron source, chromium source and indium source; more preferably selected from the group consisting of boron oxide source, aluminum oxide source, gallium oxide source, titanium oxide source, zirconium oxide source, oxide At least one oxide source in the group consisting of a hafnium source, a tin oxide source, a zinc oxide source, an iron oxide source, a chromium oxide source, and an indium oxide source; the oxide source (based on the corresponding oxide)
- the molar ratio of the germanium source (calculated as GeO 2 ) is (0.01-0.1):1, preferably (0.015-0.08):1.
- a molecular sieve composition comprising the molecular sieve of any one of the above technical solutions or a molecular sieve synthesized according to the preparation method of any one of the above technical solutions, and a binder.
- the silicon and germanium-based molecular sieves involved have a framework structure that has never been obtained before in the field.
- the silicon and germanium-based molecular sieve has a regular molecular size pore structure, strong acidity, ion exchange performance and high thermal stability.
- the related preparation method of molecular sieve based on silicon and germanium has simple synthesis steps, strong operability, wide synthesis range, and is convenient for promotion.
- the present invention also provides the following embodiments:
- a molecular sieve SCM-25 said SCM-25 molecular sieve having an X-ray diffraction pattern basically as shown in the following table:
- the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
- the silicon-germanium molar ratio is 0.1 ⁇ n ⁇ 30, preferably 0.25 ⁇ n ⁇ 20, more preferably 0.5 ⁇ n ⁇ 15, more preferably 1 ⁇ n ⁇ 5;
- 0.05 ⁇ k ⁇ 1.0 preferably 0.05 ⁇ k ⁇ 0.5, more preferably 0.1 ⁇ k ⁇ 0.5, more preferably 0.1 ⁇ k ⁇ 0.4;
- Q is an organic template, 0.01 ⁇ m ⁇ 1.0, preferably 0.02 ⁇ m ⁇ 0.5, more preferably 0.05 ⁇ m ⁇ 0.5, more preferably 0.05 ⁇ m ⁇ 0.3; the organic template is selected from containing 1,1,3,5 -Tetraalkylpiperidinium ion or quaternary ammonium form as shown in the following structural formula, preferably 1,1,3,5-tetramethylpiperidine hydroxide;
- R 1 -R 4 are each independently H or C 1-4 alkyl, preferably C 1-2 alkyl, more preferably -CH 3,
- X - is a halogen ion (such as Cl -, Br - and I -) and hydroxide ions (OH -), preferably a hydroxide ion (OH -);
- a preparation method of SCM-25 molecular sieve comprising combining silicon source, germanium source, fluorine source, organic template Q and water or a mixture formed by silicon source, germanium source, fluorine source, organic template Q and water The step of crystallization to obtain the molecular sieve; and optionally, the step of calcining the obtained molecular sieve;
- the organic template Q is selected from the quaternary ammonium form containing 1,1,3,5-tetraalkylpiperidinium ion or the following structural formula, preferably 1,1,3,5-tetramethylpiperidine hydrogen Oxide
- R 1 -R 4 are each independently H or C 1-4 alkyl, preferably C 1-2 alkyl, more preferably -CH 3,
- X - is a halogen ion (such as Cl -, Br - and I -) and hydroxide ions (OH -), preferably a hydroxide ion (OH -).
- the silicon source is selected from the group consisting of water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, At least one selected from the group consisting of zeolite molecular sieve and tetraethylorthosilicate;
- the germanium source is selected from at least one selected from the group consisting of germanium oxide, germanium nitrate and tetraalkoxy germanium;
- the fluorine source includes at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride It is preferably at least one of the group consisting of hydrofluoric acid and ammonium fluoride.
- crystallization conditions include crystallization at 100-200°C for 30-400 hours; preferably 110-190°C for 48-360 hours ; It is more preferable to crystallize at 120-180°C for 72-320 hours.
- the mixture also includes a source of elements other than silicon and germanium, preferably selected from boron source, aluminum source, gallium source, titanium source, At least one of zirconium source, hafnium source, tin source, zinc source, iron source, chromium source and indium source; more preferably selected from boron oxide source, aluminum oxide source, gallium oxide source, titanium oxide source, oxide source At least one oxide source in the group consisting of a zirconium source, a hafnium oxide source, a tin oxide source, a zinc oxide source, an iron oxide source, a chromium oxide source, and an indium oxide source;
- a source of elements other than silicon and germanium preferably selected from boron source, aluminum source, gallium source, titanium source, At least one of zirconium source, hafnium oxide source, a tin oxide source, a zinc oxide source, an iron oxide source, a chromium oxide source, and an indium oxide source;
- the molar ratio of the oxide source (based on the corresponding oxide) to the germanium source (based on GeO 2 ) is (0.01-0.1):1, preferably (0.015-0.08):1.
- a molecular sieve composition comprising the molecular sieve SCM-25 of any one of embodiments 1 to 6 or a molecular sieve SCM-25 synthesized according to the method of synthesizing the molecular sieve SCM-25 of any one of embodiments 7 to 11, and Knot agent.
- Figure 1 is an X-ray diffraction (XRD) pattern of the sample obtained in Example 1 before firing;
- Figure 2 is an X-ray diffraction (XRD) pattern of the sample obtained in Example 1 after firing;
- Figure 3 is a scanning electron microscope (SEM) photograph of the sample obtained in Example 1;
- Figure 4 is the N 2 adsorption-desorption isotherm of the sample obtained in Example 1 at 77K;
- the silicon and germanium-based molecular sieve of the present invention is sometimes also referred to as the molecular sieve of the present invention, or SCM-25 molecular sieve, or SCM-25 molecular sieve based on silicon and germanium.
- the expression "the molecular sieve is based on silicon and germanium” or a similar expression means that the framework of the molecular sieve contains silicon and germanium. In a special case, this type of expression may mean that the framework of the molecular sieve consists only of silicon and germanium.
- the expression "not more than 10% of the Ge atoms in the molecular sieve are replaced by atoms of at least one element other than silicon and germanium” or similar expressions means that the Ge atoms in the molecular sieve framework are replaced by at least one element other than silicon and germanium.
- the elements of silicon and germanium are substituted by atoms, and this substituted element occupies the position before the Ge atom.
- the so-called specific surface area refers to the total area of a sample per unit mass, including internal surface area and external surface area.
- Non-porous samples have only external surface area, such as Portland cement, some clay mineral particles, etc.; porous and porous samples have external surface area and internal surface area, such as asbestos fiber, diatomaceous earth, and molecular sieves.
- the surface area of pores with a pore diameter of less than 2nm in porous and porous samples is the internal surface area.
- the surface area after deducting the internal surface area is called the external surface area.
- the external surface area per unit mass sample is the external specific surface area.
- the so-called pore volume refers to the volume of pores per unit mass of a porous material.
- the so-called total pore volume refers to the volume of all pores per unit mass of molecular sieve (generally only pores with a channel diameter of less than 50 nm are counted).
- the so-called micropore volume refers to the volume of all micropores per unit mass of molecular sieve (generally refers to pores with a channel diameter of less than 2nm).
- w, m, s, and vs represent the intensity of diffraction peaks, w is weak, m is medium, s is strong, and vs is very strong, which is understood by those skilled in the art.
- w is less than 20%; m is 20%-40% (not including 40%); s is 40%-70%; vs is greater than 70%, where the percentage is relative to the maximum in the XRD spectrum
- the intensity of the strong peak, that is, the strongest peak in the XRD spectrum is defined as 100%.
- XRD X-ray diffraction spectrum
- a molecular sieve based on silicon and germanium which has an X-ray diffraction pattern substantially as shown in the following table:
- the X-ray diffraction pattern further includes X-ray diffraction peaks substantially as described in the following table:
- the X-ray diffraction pattern optionally further includes X-ray diffraction peaks substantially as shown in the following table,
- the molecular sieve of the present invention has a schematic chemical composition I as shown in the formula "SiO 2 ⁇ 1/nGeO 2 ". It is known that molecular sieves sometimes (especially immediately after synthesis) contain a certain amount of water, but the present invention does not believe that it is necessary to limit the amount of water, because the presence or absence of water does not substantially Affect the XRD spectrum of the molecular sieve. In view of this, the schematic chemical composition actually represents the anhydrous chemical composition of the molecular sieve. Moreover, it is obvious that the schematic chemical composition I represents the framework chemical composition of the molecular sieve of the present invention.
- the silicon-germanium molar ratio is 0.1 ⁇ n ⁇ 30, preferably 0.25 ⁇ n ⁇ 20, more preferably 0.5 ⁇ n ⁇ 15, more preferably 1 ⁇ n ⁇ 5.
- the molecular sieve may generally further contain organic matter (especially organic template) and water, such as those filled in its pores. Therefore, the molecular sieve of the present invention may also have a schematic chemical composition II as shown in the formula "kF ⁇ mQ ⁇ SiO 2 ⁇ 1/nGeO 2 ⁇ pH 2 O".
- the molecular sieve with the schematic chemical composition I can be obtained.
- the firing can be carried out in any manner conventionally known in the art.
- the firing temperature is generally from 300°C to 750°C, preferably from 400°C to 600°C, and the firing time is generally from 1 hour to 10 hours, preferably From 3 hours to 6 hours.
- the firing can be carried out in an oxygen-containing atmosphere, such as air or oxygen atmosphere, and the firing can also be carried out in situ.
- the schematic chemical composition I is sometimes also called the schematic chemical composition after calcination
- the schematic chemical composition II is sometimes also called the synthetic schematic chemical composition.
- the silicon-germanium molar ratio is 0.1 ⁇ n ⁇ 30, preferably 0.25 ⁇ n ⁇ 20, more preferably 0.5 ⁇ n ⁇ 15, more preferably 1 ⁇ n ⁇ 5.
- F is fluorine, and 0.05 ⁇ k ⁇ 1.0, preferably 0.05 ⁇ k ⁇ 0.5, more preferably 0.1 ⁇ k ⁇ 0.5, more preferably 0.1 ⁇ k ⁇ 0.4.
- Q is an organic template, 0.01 ⁇ m ⁇ 1.0, preferably 0.02 ⁇ m ⁇ 0.5, more preferably 0.05 ⁇ m ⁇ 0.5, more preferably 0.05 ⁇ m ⁇ 0.3.
- the organic template is selected from the group containing 1,1,3,5-tetraalkylpiperidinium ion or the quaternary ammonium form represented by the following structural formula, 1,1,3,5-tetramethylpiperidine hydroxide is preferred.
- These organic templating agents can be used singly or in combination of multiple in a desired ratio.
- R 1 -R 4 are each independently H or C 1-4 alkyl, preferably C 1-2 alkyl, more preferably -CH 3,
- X - is a halogen ion (such as Cl -, Br - and I -) and hydroxide ions (OH -), preferably a hydroxide ion (OH -);
- 0.005 ⁇ p ⁇ 0.5 preferably 0.01 ⁇ p ⁇ 0.4, more preferably 0.01 ⁇ p ⁇ 0.3, more preferably 0.02 ⁇ p ⁇ 0.2.
- the framework germanium can be partially replaced by trivalent or tetravalent elements other than silicon and germanium, and the replacement rate does not exceed 10%.
- the parameter "replacement rate" is dimensionless.
- the element other than silicon and germanium is selected from at least one of the group consisting of boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium and indium, and is preferably selected from the group consisting of aluminum and titanium At least one of.
- the substitution rate 2X 2 O 3 /(2X 2 O 3 +GeO 2 ) ⁇ 100%, where X is a trivalent element; germanium is tetravalent
- the substitution rate YO 2 /(YO 2 +GeO 2 ) ⁇ 100%, where Y is a tetravalent element.
- the specific surface area (BET method) of the molecular sieve of the present invention is 200-800 m 2 /g, preferably 250-700 m 2 /g.
- the pore volume (t-plot method) of the molecular sieve of the present invention is 0.1-0.35 cm 3 /g, preferably 0.12-0.3 cm 3 /g.
- the molecular sieve of the present invention can be synthesized by the following method.
- the present invention also relates to a method for preparing a molecular sieve based on silicon and germanium, which includes combining a silicon source, a germanium source, a fluorine source, an organic template agent Q and water or a silicon source, a germanium source, a fluorine source, and an organic template.
- the step of crystallizing the mixture of agent Q and water hereinafter collectively referred to as mixture to obtain the molecular sieve.
- the organic template in the preparation method of the molecular sieve, is selected from the quaternary ammonium form containing 1,1,3,5-tetraalkylpiperidinium ion or the following structural formula, preferably 1,1,3,5-Tetramethylpiperidine hydroxide.
- These organic templating agents can be used singly or in combination of multiple in a desired ratio.
- R 1 -R 4 are each independently H or C 1-4 alkyl, preferably C 1-2 alkyl, more preferably -CH 3,
- X - is a halogen ion (such as Cl -, Br - and I -) and hydroxide ions (OH -), preferably a hydroxide ion (OH -).
- the crystallization step can be performed in any manner conventionally known in the art.
- any silicon source conventionally used in the art for this purpose can be used.
- water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite, or tetraethylorthosilicate, etc. can be mentioned.
- These silicon sources can be used singly or in combination of multiple in a desired ratio.
- germanium source any germanium source conventionally used in the art for this purpose can be used, including but not limited to germanium oxide, germanium nitrate and tetraalkoxy.
- germanium oxide germanium oxide
- germanium nitrate germanium nitrate
- tetraalkoxy germanium oxide
- alkoxy refers to C 1 -C 6 alkoxy.
- any fluorine source conventionally used in the art for this purpose can be used, for example, fluoride or its aqueous solution, such as hydrofluorine Acid, ammonium fluoride, sodium fluoride, potassium fluoride, especially hydrofluoric acid.
- fluoride or its aqueous solution such as hydrofluorine Acid, ammonium fluoride, sodium fluoride, potassium fluoride, especially hydrofluoric acid.
- the crystallization conditions include: crystallization at 100-200°C for 30-400 hours; preferably 110-190°C for 48-360 hours; more preferably 120 Crystallize at -185°C for 72-320 hours, for example at 120-180°C for 72-320 hours.
- the source of valence elements is preferably a source of oxides of trivalent or tetravalent elements other than silicon and germanium.
- the oxide source it is preferably selected from boron oxide source, aluminum oxide source, gallium oxide source, titanium oxide source, zirconium oxide source, hafnium oxide source, tin oxide source, zinc oxide source, iron oxide source, chromium oxide source and At least one oxide source in the group consisting of indium oxide sources; as the alumina source, specific examples include those selected from the group consisting of aluminum hydroxide, sodium aluminate, aluminum salt, kaolin and montmorillonite At least one.
- the boron oxide source include at least one selected from the group consisting of boron oxide, borax, sodium metaborate, and boric acid.
- the tin oxide source include at least one selected from the group consisting of tin tetrachloride, stannous chloride, alkyl tin, tin alkoxide, and organotinate.
- the zirconium oxide source include at least one selected from the group consisting of zirconium salts (such as zirconium nitrate and zirconium sulfate), alkyl zirconium, zirconium alkoxide, and organic zirconate.
- titanium oxide source specific examples include tetraalkyl titanates (such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetra n-butyl titanate), TiCl 4 One or more of hexafluorotitanic acid, Ti(SO 4 ) 2 and their hydrolyzed products.
- tetraalkyl titanates such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetra n-butyl titanate
- TiCl 4 One or more of hexafluorotitanic acid
- Ti(SO 4 ) 2 titanium oxide source
- gallium oxide source specific examples include those selected from gallium nitrate, gallium oxide, gallium halides (such as gallium chloride, gallium bromide), gallium sulfate, gallium isopropoxide, gallium acetate, and gallium ethoxylate
- hafnium oxide source specific examples include hafnium oxide, hafnium halides (such as hafnium chloride, hafnium bromide), hafnium sulfate, hafnium tert-butoxide, hafnium oxychloride, At least one of the group consisting of hafnium ethoxylate;
- zinc oxide source specific examples include those selected from zinc oxide, zinc halide (such as zinc chloride), zinc acetate, basic zinc carbonate, zinc sulfate, At least one of the group consisting of zinc nitrate, zinc lactate, and zinc gluconate;
- iron oxide source specific examples include those selected from iron sulfate, iron nitrate, iron halides (such as iron trichloride), and At least one of the group consisting of iron and iron citrate;
- chromium oxide source specific examples include those selected from the group consisting of chromium trioxide, chromine
- the molar ratio of the oxide source (calculated by the corresponding oxide) to the germanium source (calculated by GeO 2 ) is generally It is (0.01-0.1):1, preferably (0.015-0.08):1.
- the molecular sieve in the preparation method of the molecular sieve, after the crystallization is completed, the molecular sieve can be separated from the obtained reaction mixture as a product by any conventionally known separation method, thereby obtaining the product.
- the molecular sieve of the invention is also referred to as the molecular sieve of the invention in a synthetic state.
- the separation method for example, a method of filtering, washing and drying the obtained reaction mixture can be cited.
- the filtering, washing and drying can be performed in any manner conventionally known in the art.
- the obtained reaction mixture may be simply filtered with suction.
- washing for example, washing with deionized water is used.
- drying temperature for example, 40 to 250°C, preferably 60 to 150°C, and as the drying time, for example, 8 to 30 hours, preferably 10 to 20 hours. This drying may be carried out under normal pressure or under reduced pressure.
- the molecular sieve obtained by crystallization can be calcined as required to remove the organic template and possible moisture, etc., thereby obtaining the calcined Molecular sieve, also known as the molecular sieve of the present invention in its calcined form.
- the firing can be carried out in any manner conventionally known in the art, for example, the firing temperature is generally 300 to 800°C, preferably 400 to 650°C, and the firing time is generally 1 to 10 hours, preferably 3 to 6 hours.
- the calcination can be performed in an oxygen-containing atmosphere, such as air or oxygen; the calcination can also be performed in situ. Preferably, roasting is performed in situ.
- the molecular sieve of the present invention can be in any physical form, such as powder, granules or molded products (such as strips, clover, etc.). These physical forms can be obtained in any manner conventionally known in the art and are not particularly limited.
- the molecular sieve of the present invention can be used in combination with other materials, thereby obtaining a molecular sieve composition.
- these other materials include active materials and inactive materials.
- the active material include synthetic zeolite and natural zeolite
- examples of the inactive material (generally referred to as a binder) include clay, clay, silica gel, and alumina. These other materials can be used alone or in combination of multiple types in any ratio.
- the amount of the other materials you can directly refer to the conventional amount in this field, and there is no particular limitation.
- the molecular sieve or the molecular sieve composition of the present invention can be used as an adsorbent, for example, to separate at least one component from a mixture of multiple components in the gas or liquid phase. Therefore, at least one component can be partially or substantially separated from the mixture of various components by contacting the mixture with the molecular sieve or the molecular sieve composition of the present invention to selectively adsorb this component.
- the molecular sieve or the molecular sieve composition of the present invention can also be used as a catalyst (or as its catalytically active component) directly or after necessary processing or transformation (such as ion exchange, etc.) for molecular sieves conventionally performed in the art. Minute).
- reactants such as hydrocarbons
- the target product can be obtained.
- the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining and placed in an oven at 170°C for crystallization for 288 hours. After the reaction, the solid is filtered, washed, dried, and calcined in air to obtain a molecular sieve.
- the product molecular sieve has a specific surface area of 498 m 2 /g and a micropore volume of 0.18 cm 3 /g.
- the XRD pattern of the sample before calcination is shown in Fig. 1, the XRD pattern after calcination is shown in Fig. 2, the scanning electron microscope picture is shown in Fig. 3, the N 2 adsorption-desorption isotherm at 77K temperature is shown in Fig. 4, molecular sieve
- the skeleton structure diagram is shown in Figure 5.
- the XRD pattern of the product obtained after in-situ calcination of the sample before calcination is consistent with Figure 1, and the characteristic data of the XRD pattern and the calculated interplanar spacing data are shown in the above table.
- the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining, and placed in an oven at 160° C. for crystallization for 240 hours. After the reaction, the solid is filtered, washed, dried, and calcined in air to obtain molecular sieves.
- the XRD pattern is similar to Figure 2.
- the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
- the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining and placed in an oven at 175°C for crystallization for 216 hours. After the reaction, the solid is filtered, washed, dried, and calcined in air to obtain molecular sieves.
- the XRD pattern is similar to Figure 2.
- the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
- the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining, and placed in an oven at 165°C for crystallization for 180 hours. After the reaction, the solid is filtered, washed, dried, and calcined in air to obtain molecular sieves.
- the XRD pattern is similar to Figure 2.
- the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
- the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining, and placed in a 150°C oven for crystallization for 192 hours. After the reaction, the solids are filtered, washed, dried, and calcined to obtain molecular sieves.
- the XRD pattern is similar to Figure 2.
- the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
- the above mixture was put into a crystallization kettle with a polytetrafluoroethylene lining, and placed in an oven at 165° C. for crystallization for 250 hours. After the reaction, the solid is filtered, washed, dried, and calcined. The solid obtained is an aluminum-containing molecular sieve.
- the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
- the above mixture was put into a crystallization kettle with a polytetrafluoroethylene lining, and placed in an oven at 155°C for crystallization for 300 hours. After the reaction, the solid is filtered, washed, dried, and calcined. The solid obtained is aluminum-containing molecular sieve.
- the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
- the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining and placed in an oven at 185°C for crystallization for 168 hours. After the reaction, the solid is filtered, washed, dried, and calcined. The solid obtained is an aluminum-containing molecular sieve.
- the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
- the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining and placed in an oven at 130°C for crystallization for 192 hours. After the reaction, the solid is filtered, washed, dried, and calcined. The solid obtained is an iron-containing molecular sieve.
- the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
- the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining and placed in an oven at 175°C for crystallization for 144 hours. After the reaction, the solid is filtered, washed, dried, and calcined to obtain a titanium-containing molecular sieve.
- the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
- the above mixture was put into a crystallization kettle with polytetrafluoroethylene lining, and placed in an oven at 180°C for crystallization for 168 hours. After the reaction, the solid is filtered, washed, dried, and calcined. The solid obtained is a molecular sieve containing boron and titanium.
- the characteristic data of the XRD pattern of the product obtained after in-situ calcination of the sample before calcination and the calculated interplanar spacing data are shown in the above table.
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Abstract
Description
2θ(°) |
6.53±0.3 |
7.05±0.3 |
9.56±0.3 |
10.77±0.3 |
12.84±0.3 |
18.80±0.3 |
22.60±0.3 |
2θ(°) |
7.81±0.3 |
14.37±0.3 |
14.76±0.3 |
15.45±0.3 |
16.35±0.3 |
17.52±0.3 |
19.79±0.3 |
2θ(°) |
21.46±0.3 |
22.04±0.3 |
23.64±0.3 |
24.54±0.3 |
25.14±0.3 |
26.11±0.3。 |
2θ(°) |
6.53±0.15 |
7.05±0.15 |
9.56±0.15 |
10.77±0.15 |
12.84±0.15 |
18.80±0.15 |
22.60±0.15 |
2θ(°) |
7.81±0.15 |
14.37±0.15 |
14.76±0.15 |
15.45±0.15 |
16.35±0.15 |
17.52±0.15 |
19.79±0.15 |
2θ(°) |
21.46±0.15 |
22.04±0.15 |
23.64±0.15 |
24.54±0.15 |
25.14±0.15 |
26.11±0.15。 |
2θ(°) | 相对强度(I/I 0)×100 |
6.53±0.15 | m或s |
7.05±0.15 | vs |
9.56±0.15 | w或m |
10.77±0.15 | s |
12.84±0.15 | w或m |
18.80±0.15 | m或s |
22.60±0.15 | m或s |
2θ(°) | 相对强度(I/I 0)×100 |
7.81±0.15 | w |
14.37±0.15 | w |
14.76±0.15 | w |
15.45±0.15 | w |
16.35±0.15 | w |
17.52±0.15 | w |
19.79±0.15 | w |
2θ(°) | 相对强度(I/I 0)×100 |
21.46±0.15 | w或m |
22.04±0.15 | w或m |
23.64±0.15 | m |
24.54±0.15 | m |
25.14±0.15 | m |
26.11±0.15 | w或m。 |
2θ(°) |
6.995±0.200 |
10.730±0.200 |
22.515±0.200 |
6.505±0.200 |
18.755±0.200 |
2θ(°) |
23.585±0.200 |
24.470±0.200 |
25.065±0.200 |
21.980±0.200 |
7.870±0.200 |
9.560±0.200 |
2θ(°) |
12.845±0.200 |
14.320±0.200 |
14.725±0.200 |
15.380±0.200 |
16.295±0.200 |
17.490±0.200 |
19.745±0.200 |
21.400±0.200 |
26.055±0.200。 |
2θ(°) | 相对强度 |
6.995±0.200 | vs |
10.730±0.200 | s |
22.515±0.200 | s |
6.505±0.200 | m或s |
18.755±0.200 | m或s |
2θ(°) | 相对强度 |
23.585±0.200 | m |
24.470±0.200 | m |
25.065±0.200 | m |
21.980±0.200 | w或m |
7.870±0.200 | w |
9.560±0.200 | w |
2θ(°) | 相对强度 |
12.845±0.200 | w |
14.320±0.200 | w |
14.725±0.200 | w |
15.380±0.200 | w |
16.295±0.200 | w |
17.490±0.200 | w |
19.745±0.200 | w |
21.400±0.200 | w |
26.055±0.200 | w。 |
Claims (18)
- 一种分子筛,所述分子筛具有基本上如下表所示的X射线衍射图谱:
2θ(°) 6.53±0.3 7.05±0.3 9.56±0.3 10.77±0.3 12.84±0.3 18.80±0.3 22.60±0.3 优选地,所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰:2θ(°) 7.81±0.3 14.37±0.3 14.76±0.3 15.45±0.3 16.35±0.3 17.52±0.3 19.79±0.3 更优选地,所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰,2θ(°) 21.46±0.3 22.04±0.3 23.64±0.3 24.54±0.3 25.14±0.3 26.11±0.3。 - 权利要求1的分子筛,其中所述分子筛是基于硅和锗的。
- 前述权利要求中任一项的分子筛,所述分子筛具有基本上如下表所示的X射线衍射图谱:
2θ(°) 6.53±0.15 7.05±0.15 9.56±0.15 10.77±0.15 12.84±0.15 18.80±0.15 22.60±0.15 优选地,所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰:2θ(°) 7.81±0.15 14.37±0.15 14.76±0.15 15.45±0.15 16.35±0.15 17.52±0.15 19.79±0.15 更优选地,所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰,2θ(°) 21.46±0.15 22.04±0.15 23.64±0.15 24.54±0.15 25.14±0.15 26.11±0.15。 - 前述权利要求中任一项的分子筛,所述分子筛具有基本上如下表所示的X射线衍射图谱:
2θ(°) 相对强度(I/I 0)×100 6.53±0.15 m或s 7.05±0.15 vs 9.56±0.15 w或m 10.77±0.15 s 12.84±0.15 w或m 18.80±0.15 m或s 22.60±0.15 m或s 优选地,所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰:2θ(°) 相对强度(I/I 0)×100 7.81±0.15 w 14.37±0.15 w 14.76±0.15 w 15.45±0.15 w 16.35±0.15 w 17.52±0.15 w 19.79±0.15 w 更优选地,所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰,2θ(°) 相对强度(I/I 0)×100 21.46±0.15 w或m 22.04±0.15 w或m 23.64±0.15 m 24.54±0.15 m 25.14±0.15 m 26.11±0.15 w或m。 - 前述权利要求中任一项的分子筛,所述分子筛具有基本上如下表所示的X射线衍射图谱:
2θ(°) 6.995±0.200 10.730±0.200 22.515±0.200 6.505±0.200 18.755±0.200 优选地,所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰:2θ(°) 23.585±0.200 24.470±0.200 25.065±0.200 21.980±0.200 7.870±0.200 9.560±0.200 更优选地,所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰,2θ(°) 12.845±0.200 14.320±0.200 14.725±0.200 15.380±0.200 16.295±0.200 17.490±0.200 19.745±0.200 21.400±0.200 26.055±0.200。 - 前述权利要求中任一项的分子筛,所述分子筛具有基本上如下表所示的X射线衍射图谱:
2θ(°) 相对强度 6.995±0.200 vs 10.730±0.200 s 22.515±0.200 s 6.505±0.200 m或s 18.755±0.200 m或s 优选地,所述X射线衍射图谱还包括基本上如下表所述的X-射线衍射峰:2θ(°) 相对强度 23.585±0.200 m 24.470±0.200 m 25.065±0.200 m 21.980±0.200 w或m 7.870±0.200 w 9.560±0.200 w 更优选地,所述X-射线衍射图谱任选进一步包括基本上如下表所示的X-射线衍射峰,2θ(°) 相对强度 12.845±0.200 w 14.320±0.200 w 14.725±0.200 w 15.380±0.200 w 16.295±0.200 w 17.490±0.200 w 19.745±0.200 w 21.400±0.200 w 26.055±0.200 w。 - 前述权利要求中任一项的分子筛,其特征在于,所述分子筛焙烧后的形式中具有如式“SiO 2·1/n GeO 2”所示的示意性化学组成,其中硅锗摩尔比0.1≤n≤30,优选0.25≤n≤20,更优选0.5≤n≤15,更优选1≤n≤5。
- 前述权利要求中任一项的分子筛,其特征在于,所述分子筛合成态的形式中具有如式“kF·mQ·SiO 2·1/nGeO 2·pH 2O”所示的示意性化学组成,其中,硅锗摩尔比0.1≤n≤30,优选0.25≤n≤20,更优选0.5≤n≤15,更优选1≤n≤5;0.05≤k≤1.0,优选0.05≤k≤0.5,更优选0.1≤k≤0.5,更优选0.1≤k≤0.4;Q为有机模板剂,0.01≤m≤1.0,优选0.02≤m≤0.5,更优选0.05≤m≤0.5,更优选0.05≤m≤0.3;所述有机模板剂选自含1,1,3,5-四烷基哌啶鎓离子或者如下结构式所示的季铵形式,优选1,1,3,5-四甲基哌啶氢氧化物;在上式中,R 1-R 4各自独立地为H或者C 1-4烷基,优选C 1-2烷基,更优选-CH 3,X -为卤素离子(比如Cl -、Br -和I -)和氢氧根离子(OH -),优选氢氧根离子(OH -);0.005≤p≤0.5,优选0.01≤p≤0.4,更优选0.01≤p≤0.3,更优选0.02≤p≤0.2。
- 前述权利要求中任一项的分子筛,其特征在于,所述分子筛中不超过10%的Ge原子被至少一种非硅和锗的元素的原子取代。
- 前述权利要求中任一项的分子筛,其特征在于,所述非硅和锗的元素选自由硼、铝、镓、钛、锆、铪、锡、锌、铁、铬和铟组成的组中的至少一种,优选选自由铝和钛组成的组中的至少一种。
- 根据权利要求12所述分子筛的合成方法,其特征在于,所述硅源选自由水玻璃、硅溶胶、固体硅胶、气相白炭黑、无定形二氧化硅、硅藻土、沸石、正硅酸四乙酯组成的组中的至少一种;所述锗源选自由氧化锗、硝酸锗和四烷氧基锗组成的组中的至少一种,其中烷氧基是C 1-C 6烷氧基;所述有机模板剂Q、所述硅源(以SiO 2为计)、所述锗源(以GeO 2为计)、所述氟源(以F为计)和水的摩尔比为Q:SiO 2:GeO 2:F:H 2O=0.15-4:1:0.033-10:0.2-4:0.5-50,优选Q:SiO 2:GeO 2:F:H 2O=0.25-3.5:1:0.05-4:0.35-3.5:1-35,更优选Q:SiO 2:GeO 2:F:H 2O=0.3-2.5:1:0.067-2:0.4-2.5:1.5-25,更优选Q:SiO 2:GeO 2:F:H 2O=0.35-1.5:1:0.2-1:0.45-2:2-15。
- 根据权利要求12所述分子筛的合成方法,其特征在于,所述氟源包括选自由氢氟酸、氟化铵、氟化钠、氟化钾组成的组中的至少一种,优选为氢氟酸、氟化铵组成的组中的至少一种。
- 根据权利要求12所述的分子筛的合成方法,其特征在于,所述晶化条件包括在100-200℃晶化30-400小时;优选110-190℃晶化48-360小时;更优选120-180℃晶化72-320小时。
- 根据权利要求12所述分子筛的合成方法,其特征在于,所述混合物中还包括含非硅和锗的元素源,优选选自由硼源、铝源、镓源、钛源、锆源、铪源、锡源、锌源、铁源、铬源和铟源组成的组中的至少一种;更优选选自由氧化硼源、氧化铝源、氧化镓源、氧化钛源、氧化锆源、氧化铪源、氧化锡源、氧化锌源、氧化铁源、氧化铬源和氧化铟源组成的组中的至少一种氧化物源;所述氧化物源(以相应的氧化物为计)与所述锗源(以GeO 2为计)的摩尔比为(0.01-0.1):1,优选(0.015-0.08):1。
- 一种分子筛组合物,包含权利要求1至11任一所述的分子筛或者按照权利要求12至16任一所述分子筛的合成方法合成的分子筛,以及粘结剂。
- 权利要求1至11任一所述的分子筛、按照权利要求12至16任一所 述分子筛的合成方法合成的分子筛、或者权利要求17所述分子筛组合物作为吸附剂或催化剂的应用。
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