WO2018227850A1 - 分子筛scm-15、其合成方法及其用途 - Google Patents
分子筛scm-15、其合成方法及其用途 Download PDFInfo
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- WO2018227850A1 WO2018227850A1 PCT/CN2017/108462 CN2017108462W WO2018227850A1 WO 2018227850 A1 WO2018227850 A1 WO 2018227850A1 CN 2017108462 W CN2017108462 W CN 2017108462W WO 2018227850 A1 WO2018227850 A1 WO 2018227850A1
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- molecular sieve
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- scm
- sio
- sieve scm
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 130
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 12
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 49
- 238000002441 X-ray diffraction Methods 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 31
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 230000002194 synthesizing effect Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- -1 halogen ion Chemical class 0.000 claims description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical group C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 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
- 238000001179 sorption measurement Methods 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 2
- 239000003463 adsorbent Substances 0.000 abstract description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 abstract 4
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 238000002447 crystallographic data Methods 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 28
- 239000011148 porous material Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 13
- 238000001354 calcination Methods 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000009616 inductively coupled plasma Methods 0.000 description 9
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229960002050 hydrofluoric acid Drugs 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 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
- 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 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
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 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
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- 238000003776 cleavage reaction Methods 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
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- 238000002347 injection Methods 0.000 description 1
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- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 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
- 230000004048 modification Effects 0.000 description 1
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- 229910052901 montmorillonite Inorganic materials 0.000 description 1
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- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 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
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
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- 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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- B01J20/30—Processes for preparing, regenerating, or reactivating
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- B01J29/047—Germanosilicates; Aluminogermanosilicates
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- B01J29/86—Borosilicates; Aluminoborosilicates
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- C—CHEMISTRY; METALLURGY
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Definitions
- the invention relates to a molecular sieve SCM-15, a synthesis method thereof and use thereof.
- porous inorganic materials are widely used as catalysts and catalyst supports. Porous materials have a relatively high specific surface area and a clear channel structure and are therefore good catalytic materials or catalyst supports.
- the porous material may generally include: an amorphous porous material, a crystalline molecular sieve, a modified layered material, and the like. The subtle differences in the structure of these materials are indicative of significant differences in their catalytic and adsorption properties, as well as differences in the various observable properties used to characterize them, such as their morphology, specific surface area, and voids. Size and variability of these dimensions.
- the basic skeleton structure of crystalline microporous zeolite is based on a rigid three-dimensional TO 4 (SiO 4 , AlO 4 , etc.) unit structure; in this structure, TO 4 shares oxygen atoms in a tetrahedral manner, and charge balance of a skeleton tetrahedron such as AlO 4 It is maintained by the presence of surface cations such as Na + , H + . It can be seen that the skeletal properties of the zeolite can be altered by cation exchange. At the same time, there are abundant pore-porosity systems in the structure of zeolite.
- zeolite not only has good catalytic activity for various organic reactions, excellent shape-selection, but also good selectivity by modification (US Pat. No. 6,162,416, US Pat. No. 4,954,325, US Pat. No. 5,362,697).
- the specific structure of the molecular sieve is determined by an X-ray diffraction spectrum (XRD), and the X-ray diffraction spectrum (XRD) is measured by an X-ray powder diffractometer using a Cu-K ⁇ ray source, a nickel filter. Different zeolite molecular sieves have different XRD patterns.
- TS-1 molecular sieve US4410501
- ZSM-5 molecular sieve US3702886
- the TS-1 molecular sieve skeleton elements are Si and Ti, which have catalytic oxidation function
- ZSM-5 molecular sieve skeleton element It is known as Si and Al and has an acid catalyzing function.
- X zeolite US2882244
- Y zeolite US3130007
- the skeleton elements are both Si and Al, but the relative contents of Si and Al are different.
- the X zeolite Si/Al molar ratio is less than 1.5
- the Y zeolite Si/Al molar ratio is higher than 1.5.
- the inventors have studied hard on the basis of the prior art and found a novel molecular sieve SCM-15, and further found that it has beneficial properties.
- the present invention relates to a molecular sieve SCM-15 characterized in that the molecular sieve has an X-ray diffraction pattern substantially as shown in the following table.
- the invention also provides a method for synthesizing molecular sieve SCM-15.
- the SCM-15 molecular sieve involved has a skeleton structure which has never been obtained before in the art.
- Figure 1 is an X-ray diffraction spectrum (XRD) of the molecular sieve (synthesized form) obtained in Example 1.
- Example 2 is an X-ray diffraction spectrum (XRD) of the molecular sieve (synthesized form) obtained in Example 8.
- Figure 3 is an X-ray diffraction spectrum of the molecular sieve obtained in Example 8 (form after calcination) (XRD).
- the term "specific surface area” refers to the total area of a unit mass sample, including internal surface area and external surface area.
- Non-porous samples have only external surface areas, such as Portland cement , some clay mineral particles, etc.; porous and porous samples have external surface area and internal surface area, such as asbestos fibers, diatomaceous earth and molecular sieves.
- the surface area of pores having pore diameters less than 2 nm in porous and porous samples is the internal surface area, the surface area after deducting the internal surface area is referred to as the external surface area, and the external surface area per unit mass of sample is the external specific surface area.
- pore volume refers to the volume of a pore per unit mass of porous material.
- the total pore volume refers to the volume of all the pores (generally only the pores having a pore diameter of less than 50 nm) per unit mass of the molecular sieve.
- microporous pore volume refers to the volume of all micropores (generally referred to as pores having a pore diameter of less than 2 nm) per unit mass of molecular sieve.
- w, m, s, vs represent the intensity of the diffraction peak, w is weak, m is medium, s is strong, and vs is very strong, which is known to those skilled in the art.
- w is less than 20; m is 20-40; s is 40-70; vs is greater than 70.
- XRD X-ray diffraction spectrum
- the so-called synthetic state, synthetic form or synthetic molecular sieve refers to the state of the molecular sieve after the end of the synthesis.
- the synthesis state for example, it may be a state directly presented after the end of synthesis (generally referred to as a molecular sieve precursor), or may be further removed by a method other than baking to remove organic substances (especially in the pores thereof). It is the state that is present after the organic templating agent).
- the molecular sieve may contain water, may contain organic matter, may not contain water or may be free of organic matter.
- the term "calcined after calcination, after calcination or after calcination” refers to the state of the molecular sieve after calcination.
- the calcination state specifically, for example, a state in which the synthetic molecular sieve is further removed by calcination to remove an organic substance (particularly an organic templating agent) which may exist in the pores, water, or the like may be employed.
- the firing conditions specifically include: baking at 550 ° C for 6 hours in an air atmosphere.
- a molecular sieve SCM-15 is contemplated.
- the molecular sieve (especially in its as-synthesized form or its calcined form) has an X-ray diffraction pattern substantially as shown in Table A-1 or Table A-2 below.
- the X-ray diffraction pattern may further include an X-ray diffraction peak substantially as shown in Table B-1 or Table B-2 below.
- the X-ray diffraction pattern further optionally further comprises an X-ray diffraction peak substantially as shown in the following table,
- the molecular sieve SCM-15 has the schematic chemical composition as shown by the formula "SiO 2 ⁇ GeO 2 ". It is known that molecular sieves sometimes contain a certain amount of moisture and organic matter (especially after the synthesis), but the present invention does not consider it necessary to specify the amount of water and organic matter because The presence or absence of this moisture and organic matter does not substantially affect the XRD spectrum of the molecular sieve. In view of this, the schematic chemical composition actually represents the anhydrous, organic-free chemical composition of the molecular sieve. Moreover, it is apparent that the schematic chemical composition represents the framework chemical composition of the SCM-15 molecular sieve or may also represent the post-fired schematic chemical composition of the SCM-15 molecular sieve.
- the molecular sieve SCM-15 the silicon germanium molar SiO 2 / GeO 2 ⁇ 1, preferably 1 ⁇ SiO 2 / GeO 2 ⁇ 15, preferably 2 ⁇ SiO 2 / GeO 2 ⁇ 10 Preferably, 2.5 ⁇ SiO 2 /GeO 2 ⁇ 5.
- the skeleton ruthenium in the molecular sieve SCM-15, may be partially replaced by a trivalent or tetravalent element other than silicon and germanium, and the substitution rate is not more than 10%.
- the parameter "replacement rate" is dimensionless.
- the substitution rate is 2X 2 O 3 /(2X 2 O 3 +GeO 2 ) ⁇ 100%, where X is a trivalent element; ⁇ is a tetravalent element such as tin,
- the substitution rate is YO 2 /(YO 2 +GeO 2 ) ⁇ 100%, where Y is a tetravalent element. In calculating the substitution rate, the number of moles of the corresponding oxide is used.
- the molecular sieve SCM-15 specific surface area of 100-600 m 2 / g, preferably 130-500 m 2 / g, more preferably 200-400 m 2 / g.
- the micropore volume of the molecular sieve of SCM-15 (t-plot method) of 0.04 to 0.25 cm 3 / g, preferably from 0.05 to 0.20 cm 3 / g, more preferably 0.09-0.18 cm 3 / Gram.
- the molecular sieve SCM-15 can be obtained by the following method Perform the synthesis.
- the present invention also relates to a method for synthesizing molecular sieve SCM-15, comprising comprising a silicon source, a cerium source, a fluorine source, an organic templating agent and water or a silicon source, a cerium source, a fluorine source, an organic templating agent and water.
- the resulting mixture (hereinafter collectively referred to as a mixture) is crystallized to obtain the molecular sieve.
- the organic templating agent in the method for synthesizing the molecular sieve, is selected from the group consisting of 4-pyrrolidinopyridine, or the structural formula (A-1), the structural formula (A-2) or the structural formula (A-3).
- the quaternary ammonium form shown is preferably 4-pyrrolidinopyridine.
- R 1 and R 2 are each independently H or C 1-8 alkyl, preferably C 1-4 alkyl, more preferably C 1-2 alkyl, X - is independently a halogen ion (such as Cl - , Br - and I - ) and hydroxide ions (OH - ), preferably hydroxide ions (OH - ).
- X - is independently a halogen ion (such as Cl - , Br - and I - ) and hydroxide ions (OH - ), preferably hydroxide ions (OH - ).
- the crystallization step may be carried out in any manner conventionally known in the art, such as exemplifying A method of mixing the source, the source of the fluorine, the source of the fluorine, the organic templating agent and water in a predetermined ratio, and hydrothermally crystallizing the obtained mixture under the crystallization conditions. It can be in the presence of agitation as needed.
- any silicon source conventionally used for this purpose in the art can be used.
- silicic acid, silica gel, silica sol, tetraalkyl silicate or water glass can be mentioned.
- These silicon sources may be used singly or in combination of a plurality of them in a desired ratio.
- any ruthenium source conventionally used for this purpose in the art may be used, including but not limited to ruthenium oxide, ruthenium nitrate and tetraalkoxy. Basic.
- any fluorine source conventionally used for this purpose in the art may be used, and for example, a fluoride or an aqueous solution thereof, particularly hydrogen, may be mentioned. Fluoric acid, etc.
- the silicon source in terms of SiO 2
- the source of germanium in terms of GeO 2
- the source of fluorine in terms of F
- the molar ratio of the organic templating agent to water is generally 1: (0 to 1): (0.1 to 2.0): (0.1 to 2.0): (3 to 30); preferably 1: (1/15 to 1.5): (0.2 to 1.5): (0.2 to 1.5): (4 to 25); more preferably 1: (0.1 to 0.5): (0.4 to 1.2): (0.4 to 1.2): (5 to 20); more preferably 1: (0.2 to 0.4): (0.6 to 1.0): (0.6 to 1.0): (5 to 15).
- the crystallization conditions include: a crystallization temperature of 131 to 210 ° C, preferably 150 to 190 ° C, more preferably 160 to 180 ° C; and a crystallization time of 1 to 20 Days, preferably 2 to 10 days, more preferably 2 to 7 days.
- an aging step performed before crystallization is included, and the aging conditions include an aging temperature of 50 to 90 ° C and an aging time of 2 hours to 2 days.
- a source of valence elements preferably an oxide source of a trivalent or tetravalent element other than silicon and germanium.
- the oxide source at least one selected from the group consisting of a boron oxide source, an alumina source, a tin oxide source, a zirconia source, and a titanium oxide source is preferable.
- alumina source include at least one selected from the group consisting of aluminum hydroxide, sodium aluminate, aluminum salt, kaolin, and montmorillonite.
- boron oxide source include at least one selected from the group consisting of boron oxide, borax, sodium metaborate, and boric acid.
- tin oxide source include at least one selected from the group consisting of tin tetrachloride, stannous chloride, alkyl tin, alkoxy tin, and an organic stannate.
- zirconia source examples include at least one selected from the group consisting of zirconium salts (e.g., zirconium nitrate, zirconium sulfate), alkyl zirconium, zirconium alkoxide, and organic zirconate.
- zirconium salts e.g., zirconium nitrate, zirconium sulfate
- titanium oxide source include a tetraalkyl titanate (such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetra-n-butyl titanate), and TiCl 4 .
- Ti(SO 4 ) 2 One or more of hexafluorotitanate, Ti(SO 4 ) 2 and their hydrolysis products.
- the molar ratio of the oxide source (in terms of the corresponding oxide) to the source of germanium (in terms of GeO 2 ) is generally used. It is (0.01 to 0.1): 1, preferably (0.02 to 0.08): 1.
- the molecular sieve in the synthesis 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 separation method conventionally known, thereby obtaining a molecular sieve.
- SCM-15 or molecular sieve SCM-15, also known as the synthetic form.
- the separation method for example, a method of filtering, washing, and drying the obtained reaction mixture can be mentioned.
- the filtration, washing and drying can be carried out in any manner conventionally known in the art.
- the filtration for example, the obtained reaction mixture can be simply suction filtered.
- washing for example, washing with deionized water can be mentioned.
- the drying temperature for example, 40 to 250 ° C, preferably 60 to 150 ° C can be mentioned, and as the drying time, for example, 8 to 30 hours, preferably 10 to 20 hours can be mentioned.
- the drying can be carried out under normal pressure or under reduced pressure.
- the molecular sieve SCM-15 may not be calcined. Nonetheless, the organic substances (particularly the organic templating agent) which may be present in the molecular sieve may be removed by an ultraviolet/ozone method as needed, thereby obtaining an organic-free molecular sieve.
- Such molecular sieves are also of the molecular sieve SCM-15 of the invention, or molecular sieve SCM-15, also known as the synthetic form.
- the ultraviolet/ozone method is known in the art, and specifically, for example, a method of placing a molecular sieve at a distance of 2 to 3 mm from an ultraviolet lamp, and a wavelength range of 184 to 257 nm for an ultraviolet light lamp, and irradiating for 12 to 48 hours .
- the ultraviolet light can be generated by using a low- and medium-pressure mercury lamp (10 to 20 mW ⁇ cm -2 ) sealed in a casing.
- the molecular sieve obtained by crystallization may also be calcined to remove the organic templating agent and moisture or the like which may be present, thereby obtaining a calcined molecular sieve, which is also referred to as a molecular sieve SCM-15 in a calcined form.
- the calcination can be carried out in any manner conventionally known in the art, such as a calcination temperature generally from 300 ° C to 750 ° C, preferably from 400 ° C to 600 ° C, and a calcination time of generally from 1 hour to 10 hours, preferably from 3 Hours to 6 hours.
- the calcination is generally carried out under an oxygen-containing atmosphere, such as an air or oxygen atmosphere.
- the molecular sieve SCM-15 may be in any physical form, such as in the form of a powder, granules or a molded article (such as a strip, clover, etc.). These physical forms can be obtained in any manner conventionally known in the art, and are not particularly limited.
- the molecular sieve SCM-15 can be used in combination with other materials, thereby obtaining a molecular sieve composition.
- other materials for example, an active material and an inactive material can be mentioned.
- the active material include synthetic zeolite and natural zeolite.
- the inactive material (generally referred to as a binder) include clay, clay, silica gel, and alumina. These other materials may be used alone or in combination of any ones in any ratio.
- the amount of the other materials the conventional amounts in the art can be directly referred to, and are not particularly limited.
- the molecular sieve SCM-15 or the molecular sieve composition can be used as an adsorbent, for example to separate at least one component from a mixture of components in a gas phase or a liquid phase. Therefore, at least one component may be partially or substantially completely separated from the mixture of the various components by contacting the mixture with the molecular sieve SCM-15 or the molecular sieve composition, and selectively adsorbing the group. Minute.
- the molecular sieve SCM-15 or the molecular sieve composition may also be used as a catalyst (or as a catalyst) either directly or after necessary treatment or conversion (such as ion exchange, etc.) conventionally performed in the art for molecular sieves.
- Active component for example, a reactant (such as a hydrocarbon) can be subjected to a predetermined reaction in the presence of the catalyst, and thereby the target product can be obtained.
- the SiO 2 /GeO 2 5.1 of the product molecular sieve was measured by inductively coupled plasma atomic emission spectroscopy (ICP).
- the SiO 2 /GeO 2 4.2 of the product molecular sieve was measured by inductively coupled plasma atomic emission spectroscopy (ICP).
- the SiO 2 /GeO 2 4.4 of the product molecular sieve was measured by inductively coupled plasma atomic emission spectroscopy (ICP).
- the SiO 2 /GeO 2 5.3 of the product molecular sieve was measured by inductively coupled plasma atomic emission spectroscopy (ICP).
- the SiO 2 /GeO 2 3.9 of the product molecular sieve was measured by inductively coupled plasma atomic emission spectroscopy (ICP).
- boric acid was added as a boron source to the system, and a part of the niobium source was replaced, and the substitution rate was 1%.
- ICP inductively coupled plasma atomic emission spectroscopy
- the SiO 2 /GeO 2 4.2 of the product molecular sieve was measured by inductively coupled plasma atomic emission spectroscopy (ICP).
- the product was fired in an air atmosphere at 550 ° C for 6 hours, and the XRD spectrum of the obtained sample (form after calcination) is shown in Fig. 3, and the spectrum data is shown in Table 9.
- the specific surface area (BET method) of the calcined sample was 337.4 m 2 /g and the micropore volume (t-plot method) was 0.14 cm 3 /g.
- the solid sample is centrifuged, washed, and placed at 100. Dry overnight in a °C oven to obtain a powder.
- 3 g of the powder sample synthesized in Example 9 was thoroughly mixed with 2 g of alumina and 0.3 g of phthalocyanine powder, kneaded with 5 wt% of nitric acid, and extruded into a strip. The strips of millimeters were then dried at 110 ° C and calcined at 550 ° C for 6 hours to remove organics to prepare the desired molecular sieve composition.
- the molecular sieve composition can be used as an adsorbent or a catalyst.
- the molecular sieve composition prepared in Example 10 was crushed and sieved, and 30 mg of particles having a particle diameter of 20 to 40 mesh were taken, packed in a pulse fixed bed reactor, and cooled to a reaction temperature of 250 after activation at 300 ° C for 1 h in a nitrogen atmosphere. °C.
- 0.4 ⁇ l of cumene was injected into the reactor at one time, and cumene was subjected to cleavage reaction through the bed of the molecular sieve composition.
- the reacted mixture was directly subjected to gas chromatography analysis, and the conversion of cumene was obtained. 33.7%, the main products are propylene and benzene.
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Abstract
Description
Claims (12)
- 根据权利要求1所述的分子筛SCM-15,其特征在于,所述分子筛具有如式“SiO2·GeO2”所示的示意性化学组成,其中硅锗摩尔比SiO2/GeO2≥1,优选1≤SiO2/GeO2≤15,更优选2≤SiO2/GeO2≤10,更优选2.5≤SiO2/GeO2≤5。
- 根据权利要求3所述的分子筛SCM-15,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。
- 根据权利要求4所述的分子筛SCM-15,其特征在于,所述非硅和锗的元素选自由硼、铝、锡、锆和钛组成的组中的至少一种。
- 根据权利要求6所述分子筛SCM-15的合成方法,其特征在于,所述硅源选自由硅酸、硅胶、硅溶胶、硅酸四烷基酯和水玻璃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;所述硅源(以SiO2为计)、所述锗源(以GeO2为计)、所述氟源(以F为计)、所述有机模板剂和水的摩尔比为1∶(0至1)∶(0.1至2.0)∶(0.1至2.0)∶(3至30);优选1∶(1/15至1)∶(0.2至1.5)∶(0.2至1.5)∶(4至25);更优选1∶(0.1至0.5)∶(0.4至1.2)∶(0.4至1.2)∶(5至20);更优选1∶(0.2至0.4)∶(0.6至1.0)∶(0.6至1.0)∶(5至15)。
- 根据权利要求6所述分子筛SCM-15的合成方法,其特征在于,所述晶化的条件包括:晶化温度131至210℃,优选150至190℃,更优选160至180℃;晶化时间1至20天,优选2至10天,更优选2至7天。
- 根据权利要求6所述分子筛SCM-15的合成方法,其特征在于,所述方法包括晶化前的老化步骤;老化条件包括:老化温度50至90℃,老化时间2小时至2天。
- 根据权利要求6所述分子筛SCM-15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、锡源、锆源和钛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、氧化锡源、氧化锆源和氧化钛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GeO2为计)的摩尔比为(0.01至0.1)∶1,优选(0.02至0.08)∶1。
- 一种分子筛组合物,包含权利要求1至5任一所述的分子筛SCM-15或者按照权利要求6至10任一所述分子筛SCM-15的合成方法合成的分子筛SCM-15,以及粘结剂。
- 权利要求1至5任一所述的分子筛SCM-15、按照权利要求6至10任一所述分子筛SCM-15的合成方法合成的分子筛SCM-15、或者权利要求11所述分子筛组合物作为吸附剂或催化剂的应用。
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