CN114367304A - 一种复合分子筛、其制备方法及其应用 - Google Patents
一种复合分子筛、其制备方法及其应用 Download PDFInfo
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- CN114367304A CN114367304A CN202111629756.9A CN202111629756A CN114367304A CN 114367304 A CN114367304 A CN 114367304A CN 202111629756 A CN202111629756 A CN 202111629756A CN 114367304 A CN114367304 A CN 114367304A
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- Prior art keywords
- molecular sieve
- composite molecular
- transition metal
- salt
- low
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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 66
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 150000003624 transition metals Chemical class 0.000 claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- -1 transition metal salt Chemical class 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 239000004964 aerogel Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 150000003657 tungsten Chemical class 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002905 metal composite material Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 1
- 229910019167 CoC2 Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000047 product Substances 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
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 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
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
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Classifications
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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
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
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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
- B01J29/06—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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7676—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/04—Ethylene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/06—Propene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
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Abstract
本发明提供了一种复合分子筛，由过渡金属和分子筛组成，所述过渡金属以单分散的四面体配位形式存在于所述分子筛骨架中。本发明提供的复合分子筛是一种含单一位点骨架限域的过渡金属的复合分子筛。本发明还提供了低碳烯烃的制备方法，是将低碳烷烃在催化剂上脱氢生成低碳烯烃和氢气。实验证明，本发明的方法制备低碳烯烃，低碳烯烃选择性可达99.9％。本发明方法工艺简单，反应设备简便；复合分子筛催化剂耐酸碱、耐氧硫、耐水、抗积碳，寿命长，反应活性和产物选择性高，适用于工业生产。
Description
技术领域
本发明涉及烯烃制备技术领域，尤其涉及一种复合分子筛、其制备方法及其应用。
背景技术
低碳烯烃是现代化工最重要的原料之一。例如：乙烯是合成纤维、合成橡胶、合成塑料(聚乙烯及聚氯乙烯)、合成乙醇(酒精)的基本化工原料，也用于制造氯乙烯、苯乙烯、环氧乙烷、醋酸、乙醛和炸药等，还可用作水果和蔬菜的催熟剂；丙烯可用于生产聚丙烯、塑料或纤维、丙烯腈、环氧丙烷等数十种有价值的精细化工中间体；正丁烯主要可用于制造丁二烯，其次用于制造甲基乙基酮、仲丁醇、环氧丁烷及丁烯聚合物和共聚物；异丁烯主要可用于制造丁基橡胶、聚异丁烯橡胶及各种塑料。
当下，低碳烯烃主要来源于石脑油、轻柴油等的裂解，然而这一过程能耗高，产物分离困难，并且随着社会的快速发展，石油资源的消耗日益增加，所以通过传统的烃类蒸汽裂解已不能满足对低碳烯烃的巨大需求。相比之下，通过低碳烷烃脱氢来制备低碳烯烃具有原料来源广泛，成本低廉，低碳烯烃选择性高，操作简单等优点，是一种较好的替代方法。
目前，一般用于低碳烷烃脱氢的金属催化剂活性较低，在高温下金属颗粒易团聚，导致有效活性表面积小，原子利用率低，并且容易生成积炭，循环性能差。
发明内容
本发明解决的技术问题在于提供一种复合分子筛，该复合分子筛作为低碳烷烃脱氢的催化剂，实现了低碳烷烃稳定、高效和高选择性转化。
有鉴于此，本申请提供了一种复合分子筛，由过渡金属和分子筛组成，所述过渡金属以单分散的四面体配位形式存在于所述分子筛骨架中。
优选的，所述过渡金属选自Fe、Co、Ni、Cu、Ti、Mo和W中的一种或多种。
优选的，所述分子筛选自MFI、CHA、FER、MOR、MWW、FAU和*BEA中的一种。
优选的，所述过渡金属为所述复合分子筛的0.01～50wt％。
本申请还提供了所述的复合分子筛的制备方法，包括以下步骤：
将结构导向剂、硅源和水混合，加热，得到初始溶胶；
将所述初始溶胶、过渡金属盐和矿化剂进行晶化，得到固体产物；
将所述固体产物进行煅烧，得到复合分子筛。
优选的，所述结构导向剂选自含叔胺或季铵中心的含氮有机化合物；所述硅源选自硅溶胶、硅胶、气凝胶二氧化硅、硅酸钠和正硅酸乙酯中的一种或多种；所述过渡金属盐选自铁盐、钴盐、镍盐、铜盐、钛盐、钼盐和钨盐中的一种或多种；所述矿化剂选自NaOH、KOH、NaF、KF、NaCl和KCl中的一种或多种。
优选的，所述加热的温度为40～100℃，时间为5～20h；所述初始溶胶中，所述结构导向剂的含量为10～40wt％，所述硅源的含量为20～60wt％，所述水的含量为20～60wt％。
优选的，所述水热反应的温度为30～300℃，时间为3～240h。
优选的，所述煅烧的温度为200～800℃，时间为0.5～24h。
本申请还提供了一种制备低碳烯烃的方法，包括：
将催化剂和低碳烷烃混合于氢气气氛下反应，得到低碳烯烃，所述催化剂为上述方案所述的复合分子筛或所述的制备方法所制备的复合分子筛。
本申请提供了一种复合分子筛，其由过渡金属和分子筛组成，所述过渡金属以单分散的四面体配位形式存在于所述分子筛骨架中。本申请提供的复合分子筛利用分子筛的骨架和孔道实现了过渡金属的高度分散，增大了其作为催化剂的活性表面积，提高了催化剂的转化效率；同时，分子筛的骨架和孔道限制还可以避免在高温下催化剂的烧结，保证了催化剂的稳定性和良好的可再生性。
附图说明
图1为本发明实施例1制备的复合分子筛的EXAFS结果(虚线)与理论计算拟合结果(实线)对比曲线图；
图2为本发明实施例1制备的复合分子筛的球差电镜图片；
图3为本发明复合分子筛的结构示意图。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
鉴于现有技术中用于低碳烷烃的金属催化剂活性低、易团聚，最终影响催化效果的问题，本发明提供了一种复合分子筛及其制备方法，其利用一步水热合成法，将过渡金属引入分子筛中，通过分子筛骨架的限域作用实现活性位点的高度分散，避免了传统浸渍法等方法合成的催化剂结构不均匀，分散性差，易团聚，活性表面积小的缺点，实现了低碳烷烃的稳定、高效、高选择性转化。具体的，本申请实施例公开了一种复合分子筛，由过渡金属和分子筛组成，所述过渡金属以单分散的四面体配位形式存在于所述分子筛骨架中(如图3的示意图所示)。
在本申请中，所述过渡金属具体选自Fe、Co、Ni、Cu、Ti、Mo和W中的一种或多种；更具体地，所述过渡金属选自Fe或Cu。所述分子筛选自MFI、CHA、FER、MOR、MWW、FAU和*BEA中的一种；更具体地，所述分子筛选自MFI、CHA或*BEA。
在本申请所述的复合分子筛中，所述过渡金属为所述复合分子筛的0.01～50wt％；更具体地，所述过渡金属为所述复合分子筛的5～40wt％。
本申请还提供了复合分子筛的制备方法，包括以下步骤：
将结构导向剂、硅源和水混合，加热，得到初始溶胶；
将所述初始溶胶、过渡金属盐和矿化剂进行晶化，得到固体产物；
将所述固体产物进行煅烧，得到复合分子筛。
在复合分子筛制备的过程中，本申请首先将结构导向剂、硅源和水混合，加热，得到初始溶胶；在此过程中，上述原料合成了分子筛前驱体。所述结构导向剂为含叔胺中心或季铵中心的含氮有机化合物；在具体实施例中，所述结构导向剂具体选自四丙基氢氧化铵、四丙基溴化铵或吡啶。所述硅源选自有机硅源和无机硅源中的一种或多种，具体选自硅溶胶、硅胶、气凝胶二氧化硅、硅酸钠和正硅酸乙酯中的一种或多种，在实施例中，所述硅源选自气凝胶二氧化硅、硅溶胶和正硅酸乙酯中的一种或多种。所述加热的温度为40～100℃，在具体实施例中，所述加热的温度为50～80℃；所述加热的时间为5～20h，在具体实施例中，所述加热的时间为10～14h。在此过程中，所述结构导向剂的含量为10～40wt％，所述硅源的含量为20～60wt％，所述H2O的含量为20～60wt％。在本申请中，为了使原料混合的更加均匀，优选将结构导向剂、硅源和水的混合物进行搅拌，所述搅拌的转速为10～1500r/min，更具体为300～500r/min。
本申请然后向初始溶胶中加入过渡金属盐和矿化剂，转移至水热釜中进行晶化，以生长出分子筛结构。在此过程中，所述过渡金属盐选自铁盐、钴盐、镍盐、铜盐、钛盐、钼盐和钨盐中的一种或多种；所述铁盐选自FeCl2·4H2O、FeCl3·6H2O、FeSO4·7H2O、FeCl3、Fe(NO3)3·9H2O、Fe(NO3)3和Fe2(SO4)3·9H2O中的一种或多种；所述钴盐选自CoSO4·7H2O、Co(NO3)2·6H2O、CoCl2·6H2O和CoC2O4·2H2O中的一种或多种；所述镍盐选自Ni(NO3)2·6H2O、NiSO4、NiSO4·7H2O、NiSO4·6H2O、Ni(CH3COO)2和NiCl2·6H2O中的一种或多种；所述铜盐选自Cu(NO3)2·3H2O、Cu(NO3)2·6H2O、CuSO4、CuSO4·5H2O、CuCl2·2H2O和Cu(CH3COO)2·H2O中的一种或多种；Zn盐选自Zn(NO3)2·6H2O、ZnSO4·7H2O、ZnCl2和Zn(CH3COO)2·2H2O中的一种或多种；所述Cr盐Cr(NO3)3·9H2O、Cr(NO3)3、Cr2(SO4)3·5H2O和CrCl2·6H2O中的一种或多种；所述Ti盐选自TiCl4和C16H36O4Ti中的一种或两种；所述Mo盐选自Na2MoO4·2H2O和(NH4)2MoO4·H2O中的一种或两种；所述W盐选自Na2WO4·2H2O和H28N6O41W12中的一种或两种。所述矿化剂选自碱金属无机盐或碱金属无机碱，具体选自NaOH、KOH、NaF、KF、NaCl和KCl中的一种或多种。所述晶化的温度为30～300℃，在具体实施例中，所述晶化的温度为150～200℃，所述晶化的时间为3-240h，在具体实施例中，所述晶化的时间为15-30h。
本申请优选将上述得到的固体产物清洗、干燥。所述清洗至洗液pH小于8；所述干燥的温度为60～120℃，在具体实施例中，所述干燥的温度为80～100℃，所述干燥的时间为5～20h，在具体实施例中，所述干燥的时间为10～14h。
按照本发明，最后将得到的固体产物进行煅烧，以去除结构导向剂，得到复合分子筛。所述煅烧的温度为200～800℃，在具体实施例中，所述煅烧的温度为500～600℃，所述煅烧的时间为0.5～24h，在具体实施例中，所述煅烧的时间为优选1～3h。
本申请还提供了一种制备低碳烯烃的方法，包括：
将催化剂和低碳烷烃混合于氢气气氛下反应，得到低碳烯烃，所述催化剂为上述方案所述的复合分子筛。
本申请复合分子筛用于低碳烷烃脱氢制低碳烯烃反应中，将复合分子筛放置于固定床反应器中，于氢气气氛下还原，惰性气体吹扫后开始反应，优选反应物为低碳烷烃(含2～4个碳原子)，优选乙烷和丙烷，反应的温度为200～1000℃，优选550～650℃；还原的温度为200～800℃，优选550～650℃；还原的时间为0.5～5h，优选1～2h。吹扫的时间为1～60min，优选5～15min。
原料低碳烷烃的浓度为0.1～99wt％，余下为惰性气体，反应中，质量空速为0.5～20h-1，优选5～10h-1。
在整个反应中，低碳烷烃脱氢主要生成相应的烷烃，副反应少，在合适条件下，低碳烷烃的转化率可达100％，对应低碳烯烃的选择性大于99％。
为了进一步理解本发明，下面结合实施例对本发明提供的复合分子筛、其制备方法及其应用进行详细说明，本发明的保护范围不受以下实施例的限制。
实施例1
称取3.22g四丙基氢氧化铵，4.91g正硅酸乙酯和4.55g H2O混合后，恒温50℃搅拌14h，转速350r/min，得到分子筛前驱体；称取0.23g Fe(NO3)3·9H2O加入前驱体中，转移至水热釜中160℃晶化28h；洗涤结晶样品至pH小于8，于80℃干燥14h；最后将样品500℃煅烧3h，得到Fe-MFI催化剂A。
图1为本实施例制备的复合分子筛的EXAFS结果(虚线)与理论计算拟合结果(实线)对比曲线图；图2为本实施例制备的复合分子筛的球差电镜图片(其中红色点为骨架Fe)；由图1和图2可以说明，复合分子筛Fe-MFI催化剂A中的过渡金属Fe以单分散的四面体配位形式存在于分子筛MFI中。
实施例2
称取4.05g四丙基溴化铵，5.32g气态二氧化硅和5.89g H2O混合后，恒温70℃搅拌12h，转速450r/min，得到分子筛前驱体；称取0.59g CuSO4·5H2O加入前驱体中，转移至水热釜中170℃晶化25h；洗涤结晶样品至pH小于8，于85℃干燥13h；最后将样品560℃煅烧2.5h，得到Cu-*BEA催化剂B。
实施例3
称取2.39g吡啶，5.32g硅酸钠和4.75g H2O混合后，恒温90℃搅拌10h，转速500r/min，得到分子筛前驱体；称取0.11gCoC2O4·2H2O加入前驱体中，转移至水热釜中200℃晶化15h；洗涤结晶样品至pH小于8，于100℃干燥10h；最后将样品600℃煅烧1h，得到Co-CHA催化剂C。
按照实施例1、2和3制备的催化剂，对其进行低碳烷烃脱氢性能评价；将300mg催化剂装入固定床反应器中，在550℃，氢气气氛下保持1h，然后使用高纯氮气吹扫15min；反应选用单一丙烷，丙烷/Ar＝1/1，反应温度为550-650℃，质量空速为5～10·h-1；反应结果见表1。
表1不同实施例反应条件与反应结果数据表
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (10)
1.一种复合分子筛，由过渡金属和分子筛组成，所述过渡金属以单分散的四面体配位形式存在于所述分子筛骨架中。
2.根据权利要求1所述的复合分子筛，其特征在于，所述过渡金属选自Fe、Co、Ni、Cu、Ti、Mo和W中的一种或多种。
3.根据权利要求1所述的复合分子筛，其特征在于，所述分子筛选自MFI、CHA、FER、MOR、MWW、FAU和*BEA中的一种。
4.根据权利要求1所述的复合分子筛，其特征在于，所述过渡金属为所述复合分子筛的0.01～50wt％。
5.权利要求1所述的复合分子筛的制备方法，包括以下步骤：
将结构导向剂、硅源和水混合，加热，得到初始溶胶；
将所述初始溶胶、过渡金属盐和矿化剂进行晶化，得到固体产物；
将所述固体产物进行煅烧，得到复合分子筛。
6.根据权利要求5所述的制备方法，其特征在于，所述结构导向剂选自含叔胺或季铵中心的含氮有机化合物；所述硅源选自硅溶胶、硅胶、气凝胶二氧化硅、硅酸钠和正硅酸乙酯中的一种或多种；所述过渡金属盐选自铁盐、钴盐、镍盐、铜盐、钛盐、钼盐和钨盐中的一种或多种；所述矿化剂选自NaOH、KOH、NaF、KF、NaCl和KCl中的一种或多种。
7.根据权利要求5所述的制备方法，其特征在于，所述加热的温度为40～100℃，时间为5～20h；所述初始溶胶中，所述结构导向剂的含量为10～40wt％，所述硅源的含量为20～60wt％，所述水的含量为20～60wt％。
8.根据权利要求5所述的制备方法，其特征在于，所述水热反应的温度为30～300℃，时间为3～240h。
9.根据权利要求5所述的制备方法，其特征在于，所述煅烧的温度为200～800℃，时间为0.5～24h。
10.一种制备低碳烯烃的方法，包括：
将催化剂和低碳烷烃混合于氢气气氛下反应，得到低碳烯烃，所述催化剂为权利要求1～4任一项所述的复合分子筛或权利要求5～9任一项所述的制备方法所制备的复合分子筛。
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