CN109081359B - 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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- CN109081359B CN109081359B CN201711060306.6A CN201711060306A CN109081359B CN 109081359 B CN109081359 B CN 109081359B CN 201711060306 A CN201711060306 A CN 201711060306A CN 109081359 B CN109081359 B CN 109081359B
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 144
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 81
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 39
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 39
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 39
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003463 adsorbent Substances 0.000 claims abstract description 4
- 229910008310 Si—Ge Inorganic materials 0.000 claims abstract 2
- 238000002441 X-ray diffraction Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 38
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 25
- 229910052732 germanium Inorganic materials 0.000 claims description 24
- 230000002194 synthesizing effect Effects 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- -1 halogen ion Chemical class 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-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
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical group C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910052718 tin 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
- 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 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-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
- 235000012239 silicon dioxide Nutrition 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
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 238000002447 crystallographic data Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000010457 zeolite Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 229910021536 Zeolite Inorganic materials 0.000 description 10
- 238000001354 calcination Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000009616 inductively coupled plasma Methods 0.000 description 9
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 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
- 230000003197 catalytic effect Effects 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-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
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000926 separation method Methods 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
- 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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 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
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229910003074 TiCl4 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
- 230000003213 activating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000005260 alpha ray Effects 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
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 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 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000003795 desorption 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
- 238000002050 diffraction method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001678 irradiating effect Effects 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
- 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
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 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
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 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
- 238000001179 sorption measurement Methods 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
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910001845 yogo sapphire 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- 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
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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
- B01J20/02—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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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- 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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- B01J29/86—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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- 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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Abstract
本发明涉及一种分子筛SCM‑15、其合成方法及其用途。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。所述分子筛具有独特的XRD衍射数据,可作为吸附剂或催化剂使用。
Description
技术领域
本发明涉及一种分子筛SCM-15、其合成方法及其用途。
背景技术
在工业上,多孔无机材料被广泛用作催化剂和催化剂载体。多孔材料具有相对较高的比表面和畅通的孔道结构,因此是良好的催化材料或催化剂载体。多孔材料大致可以包括:无定型多孔材料、结晶分子筛以及改性的层状材料等。这些材料结构的细微差别,预示着它们本身在材料的催化和吸附性能等方面的重大差异,以及在用来表征它们的各种可观察性能中的差异,如它们的形貌、比表面积、空隙尺寸和这些尺寸的可变性。
结晶微孔沸石的基本骨架结构是基于刚性的三维TO4(SiO4,AlO4等)单元结构;在此结构中TO4是以四面体方式共享氧原子,骨架四面体如AlO4的电荷平衡是通过表面阳离子如Na+、H+的存在保持的。由此可见通过阳离子交换方式可以改变沸石的骨架性质。同时,在沸石的结构中存在着丰富的、孔径一定的孔道体系,这些孔道相互交错形成三维网状结构,且孔道中的水或有机物被去除后其骨架仍能稳定存在(US 4439409)。正是基于上述结构,沸石不但对多种有机反应具有良好催化活性、优良的择形性、并通过改性可实现良好的选择性(US 6162416,US 4954325,US 5362697)。
分子筛的特定结构是由X-射线衍射谱图(XRD)确定的,X-射线衍射谱图(XRD)由X-射线粉末衍射仪测定,使用Cu-Kα射线源、镍滤光片。不同的沸石分子筛,其XRD谱图特征不同。已有的分子筛,如A型沸石(US2882243)、Y型沸石(US3130007)、PSH-3分子筛(US4439409)、ZSM-11分子筛(US3709979)、ZSM-12分子筛(US3832449)、ZSM-23分子筛(US4076842)、ZSM-35分子筛(US4016245)、MCM-22分子筛(US4954325)等等均具有各自特点的XRD谱图。
同时,具有相同XRD谱图特征,但骨架元素种类不同,也是不同分子筛。如TS-1分子筛(US4410501)与ZSM-5分子筛(US3702886),它们二者具有相同的XRD谱图特征,但骨架元素不同。具体来说,TS-1分子筛骨架元素为Si和Ti,具有催化氧化功能,而ZSM-5分子筛骨架元素为Si和Al,具有酸催化功能。
另外,具有相同XRD谱图特征,骨架元素种类也相同,但是是骨架元素的相对含量不同,属于不同分子筛。如X沸石(US2882244)与Y沸石(US3130007),二者具有相同的XRD谱图特征,骨架元素均为Si和Al,但Si和Al的相对含量不同。具体来说,X沸石Si/Al摩尔比低于1.5,而Y沸石Si/Al摩尔比高于1.5。
发明内容
本发明人在现有技术的基础上经过刻苦的研究,发现了一种新型分子筛SCM-15,并进一步发现了其具有有益性能。
具体而言,本发明涉及一种分子筛SCM-15,其特征在于,所述分子筛具有基本上如下表所示的X-射线衍射图谱。
a=±0.3°。
本发明还提供一种分子筛SCM-15的合成方法。
技术效果
根据本发明,所涉及的SCM-15分子筛,其骨架结构是本领域之前从未获得过的。
附图说明
图1为实施例1中所得分子筛(合成态形式)的X射线衍射谱图(XRD)。
图2为实施例8中所得分子筛(合成态形式)的X射线衍射谱图(XRD)。
图3为实施例8中所得分子筛(焙烧后形式)的X射线衍射谱图(XRD)。
具体实施方式
下面对本发明的具体实施方式进行详细说明,但是需要指出的是,本发明的保护范围并不受这些具体实施方式的限制,而是由附录的权利要求书来确定。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都引于此供参考。除非另有定义,本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下,以本说明书的定义为准。
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时,该词头导出的对象涵盖本申请提出时本领域常规使用的那些,但也包括目前还不常用,却将变成本领域公认为适用于类似目的的那些。
在本说明书的上下文中,所谓比表面积,是指单位质量样品所具有的总面积,包括内表面积和外表面积。非孔性样品只具有外表面积,如硅酸盐水泥、一些粘土矿物粉粒等;有孔和多孔样品具有外表面积和内表面积,如石棉纤维、硅藻土和分子筛等。有孔和多孔样品中孔径小于2nm的孔的表面积是内表面积,扣除内表面积后的表面积称为外表面积,单位质量样品具有的外表面积即外比表面积。
在本说明书的上下文中,所谓孔容,指单位质量多孔材料所具有的孔的容积。所谓总孔容,是指单位质量分子筛所具有的全部孔(一般仅计入孔道直径小于50nm的孔)的容积。所谓微孔孔容,是指单位质量分子筛所具有的全部微孔(一般指的是孔道直径小于2nm的孔)的容积。
在本说明书的上下文中,在分子筛的XRD数据中,w、m、s、vs代表衍射峰强度,w为弱,m为中等,s为强,vs为非常强,这为本领域技术人员所熟知的。一般而言,w为小于20;m为20-40;s为40-70;vs为大于70。
在本说明书的上下文中,分子筛的结构是由X-射线衍射谱图(XRD)确定的,而所述分子筛的X-射线衍射谱图(XRD)由X-射线粉末衍射仪测定,使用Cu-Kα射线源,Kα1波长λ=1.5405980埃镍滤光片。
在本说明书的上下文中,所谓合成态、合成态形式或者合成态分子筛,是指所述分子筛在合成结束之后的状态。作为所述合成状态,具体举例而言,可能是合成结束之后直接呈现的状态(一般称为分子筛前躯体),也可能是通过除了焙烧以外的方法进一步脱除其孔道中可能存在的有机物(特别是有机模板剂)之后而呈现的状态。鉴于此,在所述合成状态下,所述分子筛可能含有水、可能含有有机物、可能不含水或者可能不含有机物。
在本说明书的上下文中,所谓焙烧后、焙烧后形式或者焙烧后分子筛,是指所述分子筛在焙烧之后的状态。作为所述焙烧状态,具体举例而言,可能是将合成态分子筛通过焙烧而进一步脱除其孔道中可能存在的有机物(特别是有机模板剂)和水等之后而呈现的状态。在此,所述焙烧的条件特别包括:在550℃空气气氛下焙烧6小时。
需要特别说明的是,在本说明书的上下文中公开的两个或多个方面(或实施方式)可以彼此任意组合,由此而形成的技术方案(比如方法或系统)属于本说明书原始公开内容的一部分,同时也落入本发明的保护范围之内。
在没有明确指明的情况下,本说明书内所提到的所有百分数、份数、比率等都是以重量为基准的,除非以重量为基准时不符合本领域技术人员的常规认识。
根据本发明的一个方面,涉及一种分子筛SCM-15。所述分子筛(特别是在其合成态的形式或者其焙烧后的形式中)具有基本上如下表A-1或表A-2所示的X-射线衍射图谱。
表A-1
(a)=±0.3°,(b)随2θ变化。
表A-2
a=±0.3°。
根据本发明的一个方面,所述X射线衍射图案还可以包括基本上如下表B-1或表B-2所示的X射线衍射峰。
表B-1
(a)=±0.3°,(b)随2θ变化。
表B-2
(a)=±0.3°。
根据本发明的一个方面,所述X-射线衍射图谱还任选进一步包括基本上如下表所示的X-射线衍射峰,
(a)=±0.3°。
根据本发明的一个方面,所述分子筛SCM-15具有如式“SiO2·GeO2”所示的示意性化学组成。已知的是,分子筛中有时会(尤其是在刚合成之后)含有一定量的水分和有机物(特别是有机模板剂),但本发明认为并没有必要对该水分和有机物的量进行特定,因为该水分和有机物的存在与否并不会实质上影响该分子筛的XRD谱图。鉴于此,该示意性化学组成实际上代表的是该分子筛的无水、无有机物的化学组成。而且,显然的是,该示意性化学组成代表的是该SCM-15分子筛的骨架化学组成,或者也可以代表该SCM-15分子筛的焙烧后示意性化学组成。
根据本发明的一个方面,在所述分子筛SCM-15中,所述硅锗摩尔SiO2/GeO2≥1,优选1≤SiO2/GeO2≤15,优选2≤SiO2/GeO2≤10,优选2.5≤SiO2/GeO2≤5。
根据本发明的一个方面,在所述分子筛SCM-15中,骨架锗可以部分被非硅和锗的三价或四价元素替代,替代率不超过10%。在此,该参数“替代率”无量纲。锗被三价元素,例如硼、铝替代时,替代率=2X2O3/(2X2O3+GeO2)×100%,其中X为三价元素;锗被四价元素,例如锡、锆、钛替代时,替代率=YO2/(YO2+GeO2)×100%,其中Y为四价元素。在计算替代率时,使用相应氧化物的摩尔数。
根据本发明的一个方面,所述分子筛SCM-15的比表面积(BET法)为100-600米2/克,优选130-500米2/克,更优选200-400米2/克。
根据本发明的一个方面,所述分子筛SCM-15的微孔孔容(t-plot法)为0.04-0.25厘米3/克,优选0.05-0.20厘米3/克,更优选0.09-0.18厘米3/克。
根据本发明的一个方面,所述分子筛SCM-15可以通过如下的方法进行合成。鉴于此,本发明还涉及一种分子筛SCM-15的合成方法,包括使包含硅源、锗源、氟源、有机模板剂和水或者由硅源、锗源、氟源、有机模板剂和水形成的混合物(以下统称为混合物)晶化以获得所述分子筛的步骤。
根据本发明的一个方面,在所述分子筛的合成方法中,所述有机模板剂选自4-吡咯烷基吡啶、或者结构式(A-1)、结构式(A-2)或结构式(A-3)所示的季铵形式,优选4-吡咯烷基吡啶。这些有机模板剂可以单独使用一种,或者以需要的比例组合使用多种。
在各式中,R1和R2各自独立地为H或者C1-8烷基,优选C1-4烷基,更优选C1-2烷基,X-各自独立为卤素离子(比如Cl-、Br-和I-)和氢氧根离子(OH-),优选氢氧根离子(OH-)。
根据本发明的一个方面,在所述分子筛的合成方法中,所述晶化步骤可以按照本领域常规已知的任何方式进行,比如可以举出使所述硅源、所述锗源、所述氟源、所述有机模板剂和水按照预定的比例混合,并使所获得的混合物在所述晶化条件下水热晶化的方法。可以根据需要在搅拌的存在下。
根据本发明的一个方面,在所述分子筛的合成方法中,作为所述硅源,可以使用本领域为此目的而常规使用的任何硅源。比如可以举出硅酸、硅胶、硅溶胶、硅酸四烷基酯或者水玻璃等。这些硅源可以单独使用一种,或者以需要的比例组合使用多种。
根据本发明的一个方面,在所述分子筛的合成方法中,作为所述锗源,可以使用本领域为此目的而常规使用的任何锗源,包括但不限于氧化锗、硝酸锗和四烷氧基锗。
根据本发明的一个方面,在所述分子筛的合成方法中,作为所述氟源,可以使用本领域为此目的而常规使用的任何氟源,比如可以举出氟化物或其水溶液,特别是氢氟酸等。
根据本发明的一个方面,在所述分子筛的合成方法中,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一般为1∶(0至1)∶(0.1至2.0)∶(0.1至2.0)∶(3至30);优选1∶(1/15至1.5)∶(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)。
根据本发明的一个方面,在所述分子筛的合成方法中,所述晶化条件包括: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。
根据本发明的一个方面,在所述分子筛的合成方法中,包括在晶化之前进行的老化步骤,老化条件包括:老化温度50至90℃,老化时间2小时至2天。
根据本发明的一个方面,在所述分子筛的合成方法中,当采用三价或四价非硅和锗的元素替代锗原子时,需向所述混合物中加入非硅和锗的三价或四价元素源,优选非硅和锗的三价或四价元素的氧化物源。作为所述氧化物源,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。作为所述氧化铝源,具体比如可以举出选自由氢氧化铝、铝酸钠、铝盐、高岭土和蒙脱土组成的组中的至少一种。作为所述氧化硼源,具体比如可以举出选自由氧化硼、硼砂、偏硼酸钠和硼酸组成的组中的至少一种。作为所述氧化锡源,具体比如可以举出选自由四氯化锡、氯化亚锡、烷基锡、烷氧基锡和有机锡酸酯组成的组中的至少一种。作为所述氧化锆源,具体比如可以举出选自由锆盐(如硝酸锆、硫酸锆)、烷基锆、烷氧基锆和有机锆酸酯组成的组中的至少一种。作为所述氧化钛源,具体比如可以举出选自四烷基钛酸酯(如钛酸四甲酯、钛酸四乙酯、钛酸四丙酯、钛酸四正丁酯)、TiCl4、六氟钛酸、Ti(SO4)2以及它们的水解产物中的一种或多种。
根据本发明的一个方面,在所述分子筛的合成方法中,在使用时,所述氧化物源(以相应的氧化物为计)与所述锗源(以GeO2为计)的摩尔比一般为(0.01至0.1)∶1,优选(0.02至0.08)∶1。
根据本发明的一个方面,在所述分子筛的合成方法中,在所述晶化完成之后,可以通过常规已知的任何分离方式从所获得的反应混合物中分离出分子筛作为产品,由此获得分子筛SCM-15,或者也称为合成态形式的分子筛SCM-15。作为所述分离方式,比如可以举出对所述获得的反应混合物进行过滤、洗涤和干燥的方法。
根据本发明的一个方面,在所述分子筛的合成方法中,所述过滤、洗涤和干燥可以按照本领域常规已知的任何方式进行。具体举例而言,作为所述过滤,比如可以简单地抽滤所述获得的反应混合物。作为所述洗涤,比如可以举出使用去离子水进行洗涤。作为所述干燥温度,比如可以举出40至250℃,优选60至150℃,作为所述干燥的时间,比如可以举出8至30小时,优选10至20小时。该干燥可以在常压下进行,也可以在减压下进行。
根据本发明的一个方面,在所述分子筛的合成方法中,所述分子筛SCM-15可以不进行焙烧。虽然如此,根据需要,可以将所述分子筛中可能存在的有机物(特别是所述有机模板剂)通过紫外/臭氧法进行脱除,由此获得不含有机物的分子筛。这种分子筛同样属于本发明的分子筛SCM-15,或者也称为合成态形式的分子筛SCM-15。所述紫外/臭氧法在本领域是已知的,具体比如可以举出将分子筛置于距离紫外灯2~3毫米处,紫外光照灯波长范围为184~257纳米,照射12~48小时的方法。在此,所述紫外光可使用由密闭在箱体中的低、中压汞灯(10~20mW·cm-2)产生。
根据本发明的一个方面,在所述分子筛的合成方法中,根据需要,也可以将晶化获得的分子筛进行焙烧,以脱除所述有机模板剂和可能存在的水分等,由此获得焙烧后的分子筛,也称为焙烧后形式的分子筛SCM-15。所述焙烧可以按照本领域常规已知的任何方式进行,比如焙烧温度一般为从300℃至750℃,优选从400℃至600℃,而焙烧时间一般为从1小时至10小时,优选从3小时至6小时。另外,所述焙烧一般在含氧气氛下进行,比如空气或者氧气气氛下。
根据本发明的一个方面,所述分子筛SCM-15可以呈现为任何的物理形式,比如粉末状、颗粒状或者模制品状(比如条状、三叶草状等)。可以按照本领域常规已知的任何方式获得这些物理形式,并没有特别的限定。
根据本发明的一个方面,所述分子筛SCM-15可以与其他材料复合使用,由此获得分子筛组合物。作为这些其他材料,比如可以举出活性材料和非活性材料。作为所述活性材料,比如可以举出合成沸石和天然沸石等,作为所述非活性材料(一般称为粘结剂),比如可以举出粘土、白土、硅胶和氧化铝等。这些其他材料可以单独使用一种,或者以任意的比例组合使用多种。作为所述其他材料的用量,可以直接参照本领域的常规用量,并没有特别的限制。
根据本发明的一个方面,所述分子筛SCM-15或所述分子筛组合物可用作吸附剂,例如用来在气相或液相中从多种组分的混合物中分离出至少一种组分。所以,至少一种组分可以部分或基本全部从各种组分的混合物中分离出来,方式是让混合物与所述分子筛SCM-15或所述分子筛组合物相接触,有选择的吸附这一组分。
根据本发明的一个方面,所述分子筛SCM-15或所述分子筛组合物还可直接或者经过本领域常规针对分子筛进行的必要处理或转化(比如离子交换等)之后用作催化剂(或作为其催化活性组分)。为此,根据本发明的一个方面,比如可以使反应物(比如烃类)在所述催化剂的存在下进行预定反应,并由此获得目标产物。
实施例
以下采用实施例进一步详细地说明本发明,但本发明并不限于这些实施例。
实施例1
将43.2g去离子水、42.63g有机模板剂4-吡咯烷基吡啶(98重量%)、8.37g氧化锗(99重量%)、14.0g氢氟酸(40重量%)、60.0g硅溶胶(SiO240重量%)混合均匀,制得反应混合物,反应混合物的物料配比(摩尔比)为:
SiO2/GeO2=5
模板剂/SiO2=0.70
F/SiO2=0.70
H2O/SiO2=12
混合均匀后,装入不锈钢反应釜中,在80℃水浴中老化2小时,然后在搅拌的情况下于170℃晶化5天。晶化结束后过滤、洗涤、120℃干燥12小时,得到分子筛。
产品分子筛(合成态形式)的XRD谱图数据如表1所示,XRD谱图如图1所示。
采用电感耦合等离子体原子发射光谱(ICP)测得产品分子筛的SiO2/GeO2=5.1。
表1
实施例2
同实施例1,只是反应混合物的物料配比(摩尔比)为:
SiO2/GeO2=4
模板剂/SiO2=0.60
F/SiO2=0.60
H2O/SiO2=10
混合均匀后,装入不锈钢反应釜中,在80℃水浴中老化3小时,然后在搅拌的情况下于165℃晶化4天。
产品(合成态形式)的XRD谱图数据如表2所示,XRD谱图与图1相似。
采用电感耦合等离子体原子发射光谱(ICP)测得产品分子筛的SiO2/GeO2=4.2。
表2
实施例3
同实施例1,只是反应混合物的物料配比(摩尔比)为:
SiO2/GeO2=4
模板剂/SiO2=0.66
F/SiO2=0.66
H2O/SiO2=8
混合均匀后,装入不锈钢反应釜中,在搅拌情况下于170℃晶化5天。
产品(合成态形式)的XRD谱图数据如表3所示,XRD谱图与图1相似。
采用电感耦合等离子体原子发射光谱(ICP)测得产品分子筛的SiO2/GeO2=4.4。
表3
实施例4
同实施例1,只是反应混合物的物料配比(摩尔比)为:
SiO2/GeO2=5
模板剂/SiO2=0.60
F/SiO2=0.60
H2O/SiO2=12
混合均匀后,装入不锈钢反应釜中,在搅拌情况下于150℃晶化5天。
产品(合成态形式)的XRD谱图数据如表4所示,XRD谱图与图1相似。
采用电感耦合等离子体原子发射光谱(ICP)测得产品分子筛的SiO2/GeO2=5.3。
表4
实施例5
同实施例1,只是反应混合物的物料配比(摩尔比)为:
SiO2/GeO2=3.5
模板剂/SiO2=0.72
F/SiO2=0.72
H2O/SiO2=9
混合均匀后,装入不锈钢反应釜中,在搅拌情况下于150℃晶化5天。
产品(合成态形式)的XRD谱图数据如表5所示,XRD谱图与图1相似。
采用电感耦合等离子体原子发射光谱(ICP)测得产品分子筛的SiO2/GeO2=3.9。
表5
实施例6
同实施例1,只是向体系中加入硼酸作为硼源,替代部分的锗源,替代率1%。
产品(合成态形式)的XRD谱图数据如表6所示,XRD谱图与图1相似。
采用电感耦合等离子体原子发射光谱(ICP)测得产品分子筛的SiO2/GeO2=5.4,SiO2/B2O3=991.3。
表6
实施例7
同实施例1,只是向体系中加入钛酸四正丁酯作为钛源,替代部分的锗源,替代率2%。
产品(合成态形式)的XRD谱图数据如表7所示,XRD谱图与图1相似。
采用电感耦合等离子体原子发射光谱(ICP)测得产品分子筛的SiO2/GeO2=5.2,SiO2/TiO2=197.2。
表7
实施例8
同实施例1,只是反应混合物的物料配比(摩尔比)为:
SiO2/GeO2=4
模板剂/SiO2=0.9
F/SiO2=0.9
H2O/SiO2=11
混合均匀后,装入不锈钢反应釜中,在搅拌情况下于170℃晶化6天。
产品(合成态形式)的XRD谱图数据如表8所示,XRD谱图如图2所示。
采用电感耦合等离子体原子发射光谱(ICP)测得产品分子筛的SiO2/GeO2=4.2。
表8
产品在550℃空气气氛下焙烧6小时,所得样品(焙烧后形式)的XRD谱图如图3所示,谱图数据如表9所示。采用氮气物理吸脱附测得焙烧后样品的比表面积(BET法)为337.4米2/克,微孔孔容(t-plot法)为0.14厘米3/克。
表9
实施例9
将实施例8中得到的焙烧后分子筛与0.7质量%的Al(NO)3溶液按照分子筛∶Al(NO3)3溶液=1∶50的质量配比投入三口烧瓶中,在80℃油浴中搅拌下反应6小时,反应结束后固体样品经离心、洗涤后,放于100℃烘箱中过夜干燥。再将干燥后的样品与浓度0.01摩尔/升的HCl溶液按照分子筛∶HCl溶液=1∶50的质量配比在室温下搅拌反应6小时,反应结束后固体样品经离心、洗涤后,放于100℃烘箱中过夜干燥,获得粉末。采用电感耦合等离子体原子发射光谱(ICP)测得产品的SiO2/GeO2=5.8,SiO2/Al2O3=112.5。
实施例10
取3克实施例9合成的粉末样品,与2克氧化铝、0.3克田菁粉充分混合,加入5重量%硝酸捏合、挤条成型为毫米的条状物,然后在110℃烘干,在550℃空气气氛下焙烧6小时脱除有机物,制备成需要的分子筛组合物。该分子筛组合物可作为吸附剂或催化剂使用。
实施例11
将实施例10制备的分子筛组合物破碎、过筛,取30毫克粒径20~40目之间的颗粒,装填在脉冲固定床反应器中,在300℃氮气氛围活化1h后降温至反应温度250℃。采用脉冲进样方式,将0.4微升异丙苯一次性瞬间注入反应器,异丙苯经过分子筛组合物床层发生裂解反应,反应后的混合物直接进入气相色谱分析,得异丙苯转化率为33.7%,主产物为丙烯和苯。
Claims (17)
3.根据权利要求1所述的分子筛SCM-15,其特征在于,硅锗摩尔比1≤SiO2/GeO2≤15。
4.根据权利要求1所述的分子筛SCM-15,其特征在于,硅锗摩尔比为2.5≤SiO2/GeO2≤5。
5.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。
6.根据权利要求5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。
8.根据权利要求7所述分子筛SCM-15的合成方法,其特征在于,在各式中,R1和R2各自独立地为C1-2烷基,X-各自独立为氢氧根离子(OH-)。
9.根据权利要求7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;
以SiO2为计的所述硅源、以GeO2为计的所述锗源、以F为计的所述氟源、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)。
10.根据权利要求7所述分子筛SCM-15的合成方法,其特征在于,以SiO2为计的所述硅源、以GeO2为计的所述锗源、以F为计的所述氟源、所述有机模板剂和水的摩尔比为1:(0.2至0.4):(0.6至1.0):(0.6至1.0):(5至15)。
11.根据权利要求7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℃;晶化时间1至20天。
12.根据权利要求7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160至180℃;晶化时间2至7天。
13.根据权利要求7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。
14.根据权利要求7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选自由硼源、铝源、锡源、锆源和钛源组成的组中的至少一种;
以相应的氧化物为计的所述氧化物源与以GeO2为计的所述锗源的摩尔比为(0.01至0.1):1。
15.根据权利要求7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;
以相应的氧化物为计的所述氧化物源与所述以GeO2为计的锗源的摩尔比为(0.02至0.08):1。
16.一种分子筛组合物,包含权利要求1至6任一所述的分子筛SCM-15或者按照权利要求7至15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。
17.权利要求1至6任一所述的分子筛SCM-15、按照权利要求7至15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16所述分子筛组合物作为吸附剂或催化剂的应用。
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US10974967B2 (en) | 2021-04-13 |
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