CN115707654A - All-silicon molecular sieve and preparation method and application thereof - Google Patents
All-silicon molecular sieve and preparation method and application thereof Download PDFInfo
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- CN115707654A CN115707654A CN202110955353.7A CN202110955353A CN115707654A CN 115707654 A CN115707654 A CN 115707654A CN 202110955353 A CN202110955353 A CN 202110955353A CN 115707654 A CN115707654 A CN 115707654A
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 84
- 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 84
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 80
- 239000010703 silicon Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000007790 solid phase Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- 239000000741 silica gel Substances 0.000 claims description 13
- 229910002027 silica gel Inorganic materials 0.000 claims description 13
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- -1 aliphatic diamine Chemical class 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- 238000006392 deoxygenation reaction Methods 0.000 claims description 9
- 238000005342 ion exchange Methods 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000008282 halocarbons Chemical class 0.000 claims description 6
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 3
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical group CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- QLIMAARBRDAYGQ-UHFFFAOYSA-N 1,6-diiodohexane Chemical compound ICCCCCCI QLIMAARBRDAYGQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000010453 quartz Substances 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
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000002149 hierarchical pore Chemical group 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- 239000000243 solution Substances 0.000 description 27
- 238000001035 drying Methods 0.000 description 21
- 238000005470 impregnation Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 230000032683 aging Effects 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000012265 solid product Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000002390 rotary evaporation Methods 0.000 description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 8
- 239000003957 anion exchange resin Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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Abstract
The invention relates to the technical field of oxygen removal, and discloses an all-silicon molecular sieve and a preparation method and application thereof. The invention discloses a method for preparing an all-silicon molecular sieve, which comprises the following steps: mixing a silicon source, an alkali source and the template agent, and then sequentially carrying out solid phase crystallization and first roasting on the obtained mixture; wherein the template agent contains at least one of the compounds shown in the formula (1). The invention also discloses a catalyst with a deoxidation function, which comprises a carrier and an active component loaded on the carrier, wherein the carrier comprises an all-silicon molecular sieve; the active component comprises group VIII goldA metal of the genus and/or group IB. The carrier is an all-silicon molecular sieve with an MFI structure and a hierarchical pore structure. The catalyst with the deoxidation function has longer service life when used for deoxidation reaction.
Description
Technical Field
The invention relates to the technical field of oxygen removal, in particular to an all-silicon molecular sieve and a preparation method and application thereof.
Background
Oxygen is a colorless and tasteless gas with combustion-supporting property and oxidizing property, and participates in various chemical processes such as respiration, combustion and the like. However, for chemical processes in which oxygen or an oxidizing agent is present, the reaction organic tail gas often contains a certain amount of oxygen. If the oxygen content is not effectively controlled, the explosion risk is generated. SH 3009-2013 'design code of combustible gas discharge system for petrochemical industry' also stipulates that combustible gas with oxygen content of more than 2v% should not be discharged into the combustible gas discharge system of whole plant, such as torch, incinerator, etc. Has important practical significance for carrying out the deoxidization treatment on the organic gas containing oxygen or the chemical tail gas.
The catalytic method for deoxidizing utilizes the chemical reaction of oxygen and a sacrificial agent on the surface of the catalyst to remove the oxygen, has the comprehensive advantages of convenient operation, high oxygen removal rate and recyclable materials compared with the adsorption method and the combustion method, and is considered as a promising chemical tail gas and circulating organic gas deoxidizing mode.
CN 11056538 discloses a propylene gas catalytic deoxidation reaction device and a deoxidation method, wherein raw material propylene tail gas is heated to a reaction operation temperature by an electric heater and then enters a deoxidation reactor, gas after deoxidation reaction exchanges heat with raw material gas, the gas is cooled by an air condenser and enters a gas-liquid separation tank, a gas phase is pressurized by a compressor and then enters a noncondensable gas separation tower, and noncondensable gas and a liquid phase are separated from the gas phase to finally obtain pure propylene.
CN105268449B discloses a hydrogenation catalyst and its application in hydrodeoxygenation, wherein the catalyst is prepared by using alumina carrier loaded with auxiliary agent of metal elements of groups IA, IIA and IVB and molybdenum, tungsten and other active components loaded on VIB on the carrier through the processes of forming, drying and roasting.
CN106607057B discloses a medium coal bed methane deoxidation catalyst and a preparation method thereof, wherein the catalyst is prepared by drying and forming by using a Raney alloy as an active component and silicon dioxide as a carrier.
The existing deoxygenation catalyst can have excellent oxygen removal rate, but the catalyst has side reactions such as severe coking and carbon deposition in the use process, so that the catalyst is inactivated, has short service life, often has more side reactions, and causes the loss of raw material gas.
Disclosure of Invention
In order to overcome the technical problems, the invention provides an all-silicon molecular sieve and a preparation method and application thereof.
In the synthesis process of the all-silicon molecular sieve, tetrapropylammonium hydroxide (or tetrapropylquaternary ammonium base) is generally required to be introduced as a template agent, is positioned in the pore channels or cages of the molecular sieve, and plays a role in generating a specific pore channel or cage structure (MFI structure): (1) space filling effect; and (2) structure guiding function. However, the all-silicon molecular sieve synthesized by tetrapropylammonium hydroxide and inorganic matters only has a micropore structure and does not have a mesopore structure. In the process of synthesizing mesoporous materials, the mesoporous materials are usually synthesized by the combined action of a mesoporous template and raw materials, but the conventional surfactant cannot guide the formation of an MFI structure. It is a conventional understanding of those skilled in the art that if the molecular size of the templating agent is changed, the structural influence on the finally prepared molecular sieve is unpredictable, and sometimes even a molecular sieve with a specific structure cannot be obtained (r.r.xu, w.q.pang, j.h.yu, q.s.huo and j.s.chen, chemistry of zeolite and Related Materials, wiley, singapore, 2007.), and there is no existing technology for synthesizing a whole silica molecular sieve with MFI structure, both with microporous and mesoporous structure, by using one templating agent. However, in the research process, the inventor finds that when the template agent synthesized by the invention and having a molecular size larger than that of tetrapropylammonium hydroxide is combined with a solid phase method, the prepared molecular sieve not only has an MFI structure, but also contains a micropore and a mesopore structure, namely the all-silicon molecular sieve with a hierarchical pore structure is prepared.
In a first aspect, the present invention provides a method for preparing an all-silicon molecular sieve, the method comprising: mixing a silicon source, an alkali source and the template agent, and then sequentially carrying out solid phase crystallization and first roasting on the obtained mixture; wherein the template agent contains at least one of the compounds shown in the formula (1),
wherein R is 1 Is C 2 -C 6 Alkylene of (3), preferably linear alkylene, R 2 Is C 3 -C 5 The linear alkyl group of (1) is preferably propyl.
The solid-phase crystallization is relative to the hydrothermal crystallization in the synthesis of the molecular sieve by a hydrothermal method, and the solid-phase crystallization is prepared from the all-silicon molecular sieve by the solid-phase method, namely, no additional water is required in the process of preparing the all-silicon molecular sieve.
In a second aspect, the invention provides an all-silicon molecular sieve prepared by the method.
The third aspect of the invention provides a catalyst with a deoxygenation function, which comprises a carrier and an active component loaded on the carrier, wherein the carrier comprises the all-silicon molecular sieve; the active component comprises a group VIII metal and/or a group IB metal.
The fourth aspect of the present invention provides a method for preparing the catalyst, which comprises: loading an active component precursor on a carrier, and then carrying out second roasting, wherein the active component precursor comprises a VIII family metal precursor and/or IB family metal precursor, and the carrier comprises the all-silicon molecular sieve.
The fifth aspect of the invention provides an application of the above all-silicon molecular sieve and the catalyst in a deoxygenation reaction.
Through the technical scheme, the invention has the following beneficial effects:
the template agent prepared by the method is mixed with a silicon source and an alkali source, and the hierarchical pore all-silicon molecular sieve is prepared under the condition of not adding a solvent and a mesoporous template agent, wherein the average grain size of the molecular sieve is 80-150nm, the average pore diameter of the mesopores is 10-20nm, and the specific surface area is 380-420m 2 The total pore volume is 0.2-0.4mL/g, the pore volume of the mesopores is 0.15-0.25mL/g, and the pore volume of the micropores is 0.09-0.15mL/g.
The preparation process of the hierarchical pore all-silicon molecular sieve does not need to add water solvent, and the preparation method is simple, low in energy consumption and capable of reducing pollution to the environment. And an expensive mesoporous template agent (such as hexadecyl trimethyl ammonium bromide) is not required to be added, so that the production cost of the hierarchical pore all-silicon molecular sieve is reduced.
When the catalyst with the deoxidation function is used for the deoxidation reaction, the catalyst has higher oxygen removal rate and longer service life.
Drawings
FIG. 1 is an XRD pattern of a multiwell, all-silica molecular sieve prepared in preparation 1;
FIG. 2 is an SEM image of a multi-stage pore all-silica molecular sieve prepared in preparation example 1;
FIG. 3 is an SEM image of a multiwell, all-silica molecular sieve prepared in preparation 1;
fig. 4 is a TEM image of the hierarchical pore all-silica molecular sieve prepared in preparation example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a method for preparing an all-silicon molecular sieve, the method comprising: mixing a silicon source, an alkali source and the template agent, and then sequentially carrying out solid phase crystallization and first roasting on the obtained mixture; wherein the template agent contains at least one of the compounds shown in the formula (1),
wherein R is 1 Is C 2 -C 6 Alkylene of (3), preferably linear alkylene, R 2 Is C 3 -C 5 The linear alkyl group of (1) is preferably propyl.
In the present invention, C 2 -C 6 The alkylene group of (a) may be, for example, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isopropylene group, a pentylene group, or a hexylene group.
In the present invention, C 3 -C 5 The straight-chain alkyl group of (2) may be, for example, n-propyl, n-butyl, n-pentyl.
According to a preferred embodiment of the invention, the templating agent is only at least one of the compounds of formula (1).
According to the present invention, preferably, the preparation method of the template is: under the condition of nucleophilic substitution reaction, organic amine is contacted with halohydrocarbon in solvent, and the reaction product obtained by contact is subjected to OH - And (4) ion exchange. That is, the method may further includeThe procedure for the preparation of the templating agent was as follows.
According to the present invention, preferably, the templating agent does not include tetrapropyl quaternary ammonium salt, tetrapropyl quaternary ammonium base, cetyl trimethyl quaternary ammonium salt.
According to the present invention, the kind of the organic amine and the halogenated hydrocarbon is not particularly limited, and preferably, the organic amine is a monohydric aliphatic amine and the halogenated hydrocarbon is a dihalo-hydrocarbon.
According to the present invention, the amounts of the dihalo-hydrocarbon and the monohydric aliphatic amine to be used are not particularly limited as long as the amounts required for the template reaction are satisfied. Preferably, the molar ratio of the dihalo-hydrocarbon to the mono-aliphatic amine is from 0.5 to 1:1.
according to the invention, preferably, the mono-aliphatic amine is C 6 -C 12 The dihalohydrocarbon is C 2 -C 6 A dihalo-hydrocarbon of (2).
According to the invention, preferably, the monohydric aliphatic amine is tri-n-propylamine and the dihalogenated hydrocarbon is 1, 6-dibromohexane and/or 1, 6-diiodohexane.
According to the present invention, the kinds of the organic amine and the halogenated hydrocarbon are not particularly limited, and preferably, the organic amine is a divalent aliphatic amine and the halogenated hydrocarbon is a monohalogenated hydrocarbon.
According to the present invention, the amounts of the monohalogenated hydrocarbon and the aliphatic diamine are not particularly limited as long as the amounts required for the reaction of the templating agent are satisfied. Preferably, the molar ratio of the monohalogenated hydrocarbon to the aliphatic diamine is 5-10:1.
according to the invention, preferably, the aliphatic diamine is C 2 -C 6 The monohalogenated hydrocarbon is C 3 -C 5 The monohalogenated hydrocarbon of (2).
According to the invention, preferably, the monohalogenated hydrocarbon is bromopropane and/or iodopropane and the diamine is ethylenediamine and/or hexamethylenediamine.
According to the present invention, the amount of the solvent and the organic amine is not particularly limited as long as the amount required for the reaction of the templating agent is satisfied.
According to the present invention, the reaction conditions of the contacting are not particularly limited, and preferably, the contacting temperature is 80 to 100 ℃ and the time is 12 to 36 hours.
According to the invention, preferably, the solvent is C 1 -C 5 The monohydric alcohol of (a) is preferably methanol and/or ethanol.
According to the present invention, preferably, the solvent is an anhydrous alcoholic solvent.
According to the present invention, in order to avoid the influence of water on the structure of the templating agent, anhydrous potassium carbonate is preferably added to the solvent at the time of preparing the templating agent to adsorb water in the solvent.
According to the invention, in order to improve the purity of the template agent, the preparation process of the template agent also comprises the steps of carrying out rotary evaporation and washing on a reaction product obtained by contacting organic amine and halogenated hydrocarbon. And obtaining a solid product after rotary evaporation and washing, and then carrying out vacuum drying on the solid product by using a vacuum drier. The washing conditions are not particularly limited, and preferably, the solvent for washing is ethyl acetate and/or diethyl ether, and the number of washing is 3 to 5.
According to the invention, the OH - Ion exchange may be a method commonly used in the art, preferably, the OH group - The specific process of ion exchange is as follows: and mixing and dissolving the solid product with a proper amount of water, then carrying out ion exchange with strongly basic anion exchange resin, and carrying out rotary evaporation and concentration to obtain the template agent, wherein the water content in the template agent is 50-85 wt%.
According to the present invention, preferably, the strongly basic anion exchange resin is a 717 strongly basic anion exchange resin.
According to the present invention, the amount of the silicon source is not particularly limited as long as it can satisfy the requirements for molecular sieve production. Preferably, the silicon source is used in an amount of 0.1 to 2g, relative to 1g of the template.
According to the present invention, the amount of the alkali source is not particularly limited as long as it can satisfy the requirements for molecular sieve production. Preferably, the alkali source is used in an amount of 0.05 to 0.2g, relative to 1g of the template.
According to the present invention, the type of the silicon source is not particularly limited, and may be a silicon source commonly used in the art. Preferably, the silicon source is an organic silicon source and/or an inorganic silicon source, and more preferably at least one of silica gel, white carbon black, quartz and sodium silicate; further preferred is silica gel.
According to the present invention, in order to make the performance of the prepared all-silica molecular sieve better, it is preferable that the silica gel has an average pore diameter of 5 to 10nm and a specific surface area of 100 to 300m 2 /g。
According to the present invention, the type of the alkali source is not particularly limited, and may be an alkali source commonly used in the art. Preferably, the alkali source is an inorganic alkali, preferably sodium hydroxide and/or potassium hydroxide.
According to the invention, the conditions for the solid phase crystallization can be selected within a wide range. Preferably, the temperature of the solid phase crystallization is 160-200 ℃, and the time is 3-10h. The invention does not need additional water in the process of preparing the ZSM-5 molecular sieve, namely, the solid phase crystallization process in the method is carried out under the condition of basically no water (the water content in a crystallization system is below 50 weight percent).
According to the invention, the conditions of the first drying can be selected within a wide range. Preferably, the drying temperature is 80-150 ℃ and the drying time is 5-10h.
According to the invention, the conditions of the first calcination can be selected within a wide range. Preferably, the roasting temperature is 500-550 ℃ and the roasting time is 3-7h.
According to the invention, in order to mix the raw materials sufficiently and uniformly, the method also comprises the step of mixing a silicon source, an alkali source and the template agent and then grinding. The grinding conditions are not particularly limited, and the grinding time is 5 to 20min.
According to the present invention, the method for polishing is not particularly limited, and the polishing may be performed by a manual polishing method or a mechanical polishing method as long as the silicon source, the alkali source, and the template are sufficiently mixed.
The invention provides an all-silicon molecular sieve prepared by the method.
The third aspect of the invention provides a catalyst with a deoxygenation function, which comprises a carrier and an active component loaded on the carrier, wherein the carrier comprises the all-silicon molecular sieve; the active component comprises a group VIII metal and/or a group IB metal.
According to the present invention, preferably, the active component is at least one of platinum, palladium, gold, ruthenium, nickel, and cobalt.
According to the present invention, it is preferable that the active component is contained in an amount of 0.01 to 2g in terms of metal element with respect to 100g of the all-silicon molecular sieve.
According to the invention, the catalyst can be directly used for deoxidation reaction, and can also be used for deoxidation reaction after reducing metal elements in the catalyst into metal simple substances.
The fourth aspect of the present invention provides a method for preparing the above catalyst, which comprises: loading an active component precursor on a carrier, and then carrying out second roasting, wherein the active component precursor comprises a VIII family metal precursor and/or IB family metal precursor, and the carrier comprises the all-silicon molecular sieve.
According to the present invention, it is preferable that the active component precursor is used in an amount such that the content of the active component in terms of metal element in the resulting catalyst is 0.01 to 2g, relative to 100g of the all-silicon molecular sieve.
According to the invention, preferably, the preparation method further comprises secondary drying, wherein the temperature of the secondary drying is 100-150 ℃ and the time is 3-5h.
According to the invention, the temperature of the second roasting is preferably 450-600 ℃ and the time is 3-9h.
According to the present invention, preferably, the active component precursor is at least one of a platinum element-containing compound, a gold element-containing compound, a palladium element-containing compound, a nickel element-containing compound, a ruthenium element-containing compound, and a cobalt element-containing compound.
According to the present invention, preferably, the active component precursor is at least one of sodium chloroplatinate, chloroplatinic acid, nickel nitrate, nickel sulfate, cobalt nitrate, cobalt sulfate, chloroauric acid, gold chloride, palladium nitrate and palladium chloride.
According to the present invention, the supporting means may be a means commonly used in the art as long as it is capable of supporting the active component on the carrier, and may be, for example, an impregnation method, a spraying method, a chemical vapor deposition method, or the like. Preferably, the supporting mode is a dipping method. Further preferably, the process of the load is: soaking the water solution containing the active component precursor at room temperature for 5-10h, then continuing aging for 8-12h, stirring at 50-150 ℃, evaporating the water in the aging product, and loading the active component precursor on the carrier.
In the present invention, the room temperature means 15 to 40 ℃.
According to a most preferred embodiment of the present invention, the method for preparing the catalyst comprises the steps of:
(1) Adding anhydrous potassium carbonate and anhydrous ethanol into a flask, stirring, and adding bromopropane and hexamethylenediamine into the flask, wherein the molar ratio of the bromopropane to the hexamethylenediamine is 7.2-8:1, then reacting for 22-24h under the condition of stirring at 85-90 ℃, after the reaction is finished, carrying out rotary evaporation on the material to semisolid, washing the semisolid for 3-5 times by using ethyl acetate, and then carrying out freeze vacuum drying to obtain a solid product. And then adding water into the solid product to dissolve the solid product, then carrying out ion exchange with 717 strongly basic anion exchange resin, and carrying out rotary evaporation and concentration to obtain a template agent, wherein the template agent contains a compound shown in the formula (I).
(2) Firstly, solid raw materials: grinding fine silica gel, a template agent and sodium hydroxide in a mortar for 10-20min, fully mixing, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 170-180 ℃ for 5-6h, cooling after crystallization, washing with deionized water to be neutral, drying at 100 ℃ for 3h, and finally roasting at 520-530 ℃ for 4-5h in an air atmosphere to obtain the all-silicon molecular sieve. The amount of fine silica gel is 0.6-0.8g and the amount of sodium hydroxide is 0.13-0.15g, relative to 1g of template agent.
(3) Dissolving palladium chloride in HCl solution, adding deionized water after completely dissolving to prepare impregnation liquid, then impregnating the all-silicon molecular sieve in the impregnation liquid at 15-40 ℃, impregnating for 8-9h, and then aging for 11-12h; stirring at 90-100 deg.C, evaporating water in the aged product to load active component precursor on the carrier; then drying at 110-120 ℃ for 3-4h, and then roasting at 580-600 ℃ for 4-5h to obtain the catalyst with the deoxidation function. The amount of palladium chloride used is 1.6-2g per 100g of all-silicon molecular sieve.
In a fifth aspect, the invention provides a use of the above catalyst in a deoxygenation reaction.
According to the present invention, preferably, the deoxidation reaction conditions include: the temperature of the deoxidation reaction is 100-450 ℃, the pressure of the deoxidation reaction is 0.1-1.5MPa, and the volume space velocity of the raw material gas is 1000-20000h -1 The oxygen content in the feed gas is from 0.1 to 10% by volume, preferably from 0.5 to 5% by volume.
According to the present invention, preferably, the raw material gas is a combustible gas, more preferably at least one of hydrogen, a hydrocarbon and a carbon-oxygen compound; further preferred is at least one of hydrogen, carbon monoxide, methane, ethylene, ethane, butene and butane.
In the invention, under the action of the catalyst, oxygen in the raw material gas is converted into carbon dioxide and/or carbon monoxide.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
room temperature is about 25 ℃;
the morphology and the grain size of the molecular sieve are characterized by adopting SEM with the instrument model of Hitachi SU1510;
the pore structure of the molecular sieve is characterized by BET and TEM, and an instrument adopted by BET testing is an ASAP2020 model of Mike corporation; the model of an instrument adopted by the TEM test is JEM-2100F;
the BET test method is: taking a certain amount of sample of about 0.10g, degassing for 6 hours under the vacuum condition of 200 ℃ and 1mmHg, and measuring the nitrogen absorption and desorption curve of the sample in liquid nitrogen (-196 ℃); then, the pore diameter and the distribution of the pore diameter distribution mesopores are calculated by adopting NLDFT. Specific surface areaThe product testing method comprises the following steps: taking a certain amount of sample of about 0.10g, vacuumizing at 30 deg.C for 10 hr<6.67×10 2 Pa and then the adsorption line data in the BET equation is used to calculate the specific surface area of the sample.
The test conditions of the TEM are as follows: the accelerating voltage is 200kV, the dot resolution of the instrument is 0.23nm, and the line resolution is 0.14nm. Before testing, a sample is crushed and ground to 300 meshes and placed in ethanol to form a suspension, ultrasonic dispersion is carried out for 5-10min at room temperature, then a dropper is used for sucking upper suspension liquid drops on a copper net, and HRTEM (high resolution transmission electron microscope) characterization is carried out after ethanol is volatilized.
The crystal form of the molecular sieve is characterized by XRD, and an instrument adopted by XRD testing is a SmartlabX ray diffractometer of Japan science company;
the content of oxygen is tested by adopting an Ampere oxygen tester;
the fine silica gel had an average pore diameter of 8nm and a specific surface area of 200m 2 /g；
Tetrapropylammonium hydroxide was purchased from Aladdin reagent Inc.;
the calculation formula of the silicon source conversion rate is as follows: the content of silicon element in the molecular sieve ÷ the content of silicon element in the silicon source x 100%.
The oxygen conversion is calculated as:
preparation example 1
(1) Adding 30g of anhydrous potassium carbonate and 200mL of anhydrous ethanol into a flask, fully stirring, adding 200g of bromopropane and 25g of hexamethylenediamine into the flask, reacting for 24 hours at 90 ℃ under a stirring condition, after the reaction is finished, performing rotary evaporation on the materials to form semisolid, washing the semisolid with ethyl acetate for 3 times, and performing freeze vacuum drying to obtain a solid product. Then adding water to the solid product to dissolve itPerforming ion exchange with 717 strongly basic anion exchange resin, and performing rotary evaporation and concentration to obtain template agent containing compound shown in formula (I) (wherein R is 1 Is hexamethylene, R 2 Is n-propyl); the water content in the template agent is 80 wt%.
(2) Firstly, solid raw materials: placing 0.8g of fine silica gel, 1g of template agent and 0.15g of sodium hydroxide in a mortar for grinding for 20min, fully mixing, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 180 ℃ for 5h, cooling at room temperature after crystallization is finished, washing to be neutral by using deionized water, drying at 100 ℃ for 3h, and finally roasting at 520 ℃ in an air atmosphere for 5h to obtain the all-silicon molecular sieve. The XRD characterization results are similar to those of fig. 1 and are not shown here. The silicon source conversion was 80 wt%.
XRD shows that characteristic peaks exist at positions with 2 theta of 8 degrees, 24 degrees and the like (shown in figure 1), and the molecular sieve prepared in the preparation example 1 is proved to be the all-silicon molecular sieve with an MFI structure, and the peak shape is relatively sharp, which indicates that the crystallinity of the all-silicon molecular sieve is high. Observing the all-silica molecular sieve obtained in preparation example 1 through SEM images (fig. 2 and 3), it can be seen that the average crystallite size of the all-silica molecular sieve is 112nm. It can be seen from TEM (fig. 4) that there are many mesopores inside the crystal of the all-silicon molecular sieve, the white circles in fig. 4 are relatively clear mesopores, and the pore diameter of the mesopores is in the range of 8-30 nm. The silicon source conversion was 84 wt%.
Preparation example 2
(1) Adding 30g of anhydrous potassium carbonate and 150mL of anhydrous ethanol into a flask, fully stirring, adding 160g of iodopropane and 25g of hexamethylenediamine into the flask, reacting for 24 hours at 50 ℃ under stirring, after the reaction is finished, performing rotary evaporation on the materials to form semisolid, washing the semisolid with diethyl ether for 5 times, and performing freeze vacuum drying to obtain a solid product. Then adding water into the solid product to dissolve the solid product, then carrying out ion exchange with 717 strongly basic anion exchange resin, and carrying out rotary evaporation and concentration to obtain a template agent, wherein the template agent contains a compound shown as a formula (I) (wherein R is 1 Is hexamethylene, R 2 Is n-propyl); the water content in the template agent is 70 wt%.
(2) Firstly, solid raw materials: placing 0.1g of fine silica gel, 1g of template agent and 0.05g of sodium hydroxide in a mortar for grinding for 5min, fully mixing, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing for 3h at 200 ℃, cooling at room temperature after crystallization is finished, washing to be neutral by using deionized water, drying for 5h at 100 ℃, and finally roasting for 3h at 550 ℃ in an air atmosphere to obtain the hierarchical pore all-silicon molecular sieve.
Preparation example 3
(1) Adding 30g of anhydrous potassium carbonate and 200mL of anhydrous ethanol into a flask, fully stirring, adding 90g of 1, 6-dibromohexane and 90g of tri-n-propylamine into the flask, reacting for 12 hours at 80 ℃ under stirring, after the reaction is finished, performing rotary evaporation on the materials to form semisolid, washing for 3 times by using ethyl acetate, and performing freeze vacuum drying to obtain a solid product. Then adding water into the solid product to dissolve the solid product, then carrying out ion exchange with 717 strongly basic anion exchange resin, and carrying out rotary evaporation and concentration to obtain a template agent, wherein the template agent contains a compound shown as a formula (I) (wherein R is 1 Is hexamethylene, R 2 Is n-propyl); the water content in the template agent is 80 wt%.
(2) Firstly, solid raw materials: placing 2g of fine silica gel, 1g of template agent and 0.2g of sodium hydroxide in a mortar for grinding for 10min, fully mixing, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 160 ℃ for 10h, cooling at room temperature after crystallization is finished, washing to be neutral by using deionized water, drying at 100 ℃ for 10h, and finally roasting at 550 ℃ in an air atmosphere for 3h to obtain the all-silicon molecular sieve. The XRD characterization results are similar to those of fig. 1 and are not shown here. The silicon source conversion was 87 wt%.
Comparative preparation example 1
Synthesizing a molecular sieve by a hydrothermal method: 1.5g of fine silica gel, 1g of the template obtained in the step (1) in the preparation example 1, 0.1g of sodium hydroxide and 100mL of deionized water are stirred and mixed uniformly at room temperature, then the mixture is transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining to be crystallized at 180 ℃ for 24 hours, cooled at room temperature, washed to be neutral by using deionized water, then dried at 100 ℃ for 5 hours, and finally roasted at 550 ℃ in an air atmosphere for 5 hours to obtain the all-silicon molecular sieve product. The silicon source conversion was 55 wt%.
Comparative preparation example 2
Synthesizing an all-silicon molecular sieve by using tetrapropylammonium hydroxide as a template under a hydrothermal condition, adding 40g of tetrapropylammonium hydroxide aqueous solution (the mass fraction of the tetrapropylammonium hydroxide aqueous solution is 20 wt.%) into 30g of deionized water, dissolving, adding 5g of fine silica gel, stirring at room temperature for 2 hours, transferring the synthesized gel into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 180 ℃ for 48 hours, drying at 100 ℃ for 5 hours, and finally roasting at 550 ℃ for 5 hours in an air atmosphere to obtain a molecular sieve product, thereby preparing the microporous all-silicon molecular sieve. The XRD characterization results are similar to those of fig. 1 and are not shown here. The silicon source conversion was 64 wt%.
The structures of the all-silicon molecular sieves of the above preparation examples and comparative preparation examples were characterized, and the results are shown in table 1.
TABLE 1
Example 1
Dissolving 0.5g of palladium chloride in 100mL of HCl (0.1 mol/L) solution, adding 250mL of deionized water after complete dissolution to prepare an impregnation solution, then impregnating 100g of the all-silicon molecular sieve obtained in the preparation example 1 in the impregnation solution at room temperature for 5 hours, and then aging for 12 hours; stirring at 120 deg.c to evaporate water from the aged product to make the active component precursor supported on the carrier; then drying at 100 ℃ for 3h, and then roasting at 550 ℃ for 5h to obtain the catalyst with the deoxidation function.
The catalyst with the deoxidation function prepared in the example 1 is subjected to deoxidation reaction, and the deoxidation reaction conditions comprise that: ethylene feed gas with oxygen content of 3 vol% and pressure of 0.5MPa, temperature of 230 deg.C and volume space velocity of 5000h -1 And detecting that the oxygen content of the outlet gas is less than 0.1 volume percent. The life test results are shown in table 2.
Example 2
Dissolving 1.5g of chloroplatinic acid in 100mL of HCl (0.1 mol/L) solution, adding 250mL of deionized water after complete dissolution to prepare an impregnation solution, then impregnating 100g of the all-silicon molecular sieve obtained in preparation example 2 in the impregnation solution at room temperature for 8 hours, and then aging for 8 hours; then stirring at 100 ℃, evaporating the water in the aging product, and loading the active component precursor on the carrier; then drying at 120 ℃ for 5h, and then roasting at 500 ℃ for 5h to obtain the catalyst with the deoxidation function.
The catalyst with the deoxidation function prepared in the example 2 is subjected to deoxidation reaction, and the deoxidation reaction conditions comprise that: ethylene feed gas with oxygen content of 0.5 vol%, pressure of 0.5MPa, temperature of 210 deg.C, and volume space velocity of 10000h -1 And detecting that the oxygen content of the outlet gas is less than 0.01 percent by volume. The life test results are shown in table 2.
Example 3
Dissolving 1.6g of palladium chloride in 100mL of HCl (0.1 mol/L) solution, adding 250mL of deionized water after complete dissolution to prepare an impregnation solution, then impregnating 100g of the all-silicon molecular sieve obtained in the preparation example 1 in the impregnation solution at room temperature for 8 hours, and then aging for 12 hours; then stirring at 100 ℃, evaporating the water in the aging product, and loading the active component precursor on the carrier; then drying at 120 ℃ for 3h, and then roasting at 600 ℃ for 5h to obtain the catalyst with the deoxidation function. The deoxidation reaction conditions were the same as in example 1, and the results of the lifetime test are shown in Table 2.
Example 4
Dissolving 0.25g of palladium chloride in 100mL of HCl (0.1 mol/L) solution, adding 150mL of deionized water after completely dissolving to prepare an impregnation solution, then impregnating 100g of the all-silicon molecular sieve obtained in the preparation example 1 in the impregnation solution at room temperature for 5 hours, and then aging for 12 hours; then stirring at 100 ℃, evaporating the water in the aging product, and loading the active component precursor on the carrier; then drying the catalyst for 3h at 100 ℃, and then roasting the catalyst for 5h at 600 ℃ to obtain the catalyst with the deoxidation function.
The catalyst with the deoxidation function prepared in the example 4 is subjected to deoxidation reaction, and the deoxidation reaction conditions comprise: oxygen content of 3 bodyVolume percent of ethylene raw material gas, the pressure is 0.5MPa, the temperature is 250 ℃, and the volume space velocity is 5000h -1 And detecting that the oxygen content of the outlet gas is less than 0.2 volume percent. The life test results are shown in table 2.
Example 5
Dissolving 0.7g of chloroplatinic acid in 100mL of HCl (0.1 mol/L) solution, adding 350mL of deionized water after complete dissolution to prepare an impregnation solution, then impregnating 100g of the all-silicon molecular sieve obtained in preparation example 2 in the impregnation solution at room temperature for 6 hours, and then aging for 5 hours; stirring at 80 ℃, evaporating the water in the aging product, and loading the active component precursor on the carrier; then drying at 120 ℃ for 5h, and then roasting at 500 ℃ for 5h to obtain the catalyst with the deoxidation function.
The catalyst with the deoxidation function prepared in the example 5 is subjected to deoxidation reaction, and the deoxidation reaction conditions comprise: ethylene feed gas with oxygen content of 0.5 vol%, pressure of 0.5MPa, temperature of 250 deg.C, and volume space velocity of 10000h -1 And detecting that the oxygen content of the outlet gas is less than 0.1 volume percent. The life test results are shown in table 2.
Example 6
Dissolving 0.4g of palladium chloride in 100mL of HCl (0.1 mol/L) solution, adding 250mL of deionized water after complete dissolution to prepare an impregnation solution, then impregnating 100g of the all-silicon molecular sieve obtained in preparation example 3 in the impregnation solution at room temperature for 10 hours, and then aging for 10 hours; stirring at 150 deg.c to evaporate water in the aged product and to make the active component precursor supported on the carrier; then drying for 4h at 150 ℃, and then roasting for 3h at 600 ℃ to obtain the catalyst with the deoxidation function.
Example 7
Dissolving 0.05g of chloroauric acid in 100mL of HCl (0.1 mol/L) solution, adding 250mL of deionized water after complete dissolution to prepare an impregnation solution, then impregnating 100g of all-silicon molecular sieve obtained in preparation example 1 in the impregnation solution at room temperature for 8 hours, and then aging for 12 hours; then stirring at 100 ℃, evaporating the water in the aging product, and loading the active component precursor on the carrier; then drying at 120 ℃ for 3h, and then roasting at 600 ℃ for 5h to obtain the catalyst with the deoxidation function. The deoxidation reaction conditions were the same as in example 1, and the results of the lifetime test are shown in Table 2.
Example 8
Dissolving 0.1g of chloroauric acid in 100mL of HCl (0.1 mol/L) solution, adding 150mL of deionized water after completely dissolving to prepare an impregnation solution, then impregnating 100g of all-silicon molecular sieve obtained in preparation example 1 in the impregnation solution at room temperature for 8 hours, and then aging for 12 hours; then stirring at 100 ℃, evaporating the water in the aging product, and loading the active component precursor on the carrier; then drying at 120 ℃ for 3h, and then roasting at 600 ℃ for 5h to obtain the catalyst with the deoxidation function.
Example 9
The catalyst was prepared by following the procedure of example 1 except that 3g of palladium chloride was used.
Comparative example 1
The catalyst preparation was carried out according to the method of example 1, except that the all-silica molecular sieve of comparative preparation 1 was used instead of the all-silica molecular sieve of preparation 1. The deoxidation reaction conditions were the same as in example 1, and the results of the lifetime test are shown in Table 2.
Comparative example 2
The catalyst preparation was carried out according to the method of example 1, except that the all-silica molecular sieve of comparative preparation 2 was used instead of the all-silica molecular sieve of preparation 1. The deoxidation reaction conditions were the same as in example 1, and the results of the lifetime test are shown in Table 2.
TABLE 2
Note: the lifetime of a catalyst is characterized by the time of catalyst deactivation, which means: in a single catalytic reaction, the initial conversion of the catalyst is 100%, and when the conversion of the catalyst is less than 90% of the initial conversion, the catalyst is considered to be deactivated.
It can be seen from the results in table 2 that the all-silicon molecular sieve with hierarchical pores prepared by the present invention has a longer service life when used in the deoxygenation reaction.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. A method of preparing an all-silicon molecular sieve, the method comprising: mixing a silicon source, an alkali source and a template agent, and then carrying out solid phase crystallization and first roasting on the obtained mixture; wherein the template agent contains at least one of the compounds shown in the formula (1),
wherein R is 1 Is C 2 -C 6 Alkylene of (a), R 2 Is C 3 -C 5 Linear alkyl group of (1).
2. The method of claim 1, wherein the templating agent is prepared by: under the condition of nucleophilic substitution reaction, organic amine is contacted with halohydrocarbon in solvent, and the reaction product obtained by contact is subjected to OH - Ion exchange;
alternatively, the templating agent excludes tetrapropyl quaternary ammonium salt, tetrapropyl quaternary ammonium base, and cetyl trimethyl quaternary ammonium salt.
3. The method of claim 2, wherein the organic amine is a mono-aliphatic amine, the halogenated hydrocarbon is a dihalo-hydrocarbon; the molar ratio of the dihalogenated hydrocarbon to the monohydric aliphatic amine is 0.5-1:1;
preferably, the mono-aliphatic amine is C 6 -C 12 The dihalo-hydrocarbon is C 2 -C 6 A dihalohydrocarbon of (2);
more preferably, the mono-aliphatic amine is tri-n-propylamine and the dihalohydrocarbon is 1, 6-dibromohexane and/or 1, 6-diiodohexane.
4. The method of claim 2, wherein the organic amine is a di-aliphatic amine and the halohydrocarbon is a monohalohydrocarbon; the mole ratio of the monohalogenated hydrocarbon to the diamine is 4-8:1;
preferably, the aliphatic diamine is C 2 -C 6 The monohalogenated hydrocarbon is C 3 -C 5 The monohalogenated hydrocarbon of (a);
more preferably, the monohalogenated hydrocarbon is bromopropane and/or iodopropane and the diamine is ethylenediamine and/or hexamethylenediamine.
5. The method of claim 2, wherein the contacting temperature is 80-100 ℃; the time is 12-36h;
and/or the solvent is C 1 -C 5 Preferably methanol and/or ethanol.
6. The method of claim 1, wherein the silicon source is used in an amount of 0.1 to 2g and the alkali source is used in an amount of 0.05 to 0.2g, relative to 1g of the template;
and/or the silicon source is an organic silicon source and/or an inorganic silicon source, preferably at least one of silica gel, white carbon black, quartz and sodium silicate;
and/or the alkali source is inorganic alkali, preferably sodium hydroxide and/or potassium hydroxide;
preferably, the average pore diameter of the silica gel is 5-10nm, and the specific surface area is 100-300m 2 /g。
7. The method of claim 1, wherein the temperature of the solid phase crystallization is 160-200 ℃ and the time is 3-10h;
and/or the first roasting temperature is 500-550 ℃, and the time is 3-7h.
8. An all-silica molecular sieve produced by the process of any of claims 1 to 7.
9. A catalyst with a deoxygenation function, wherein the catalyst comprises a carrier and an active component loaded on the carrier, and the carrier comprises the all-silicon molecular sieve of any one of claims 1 to 8; the active component comprises a group VIII metal and/or a group IB metal.
10. The catalyst of claim 9, wherein the active component is contained in an amount of 0.01 to 2g in terms of metal element with respect to 100g of the all-silicon molecular sieve.
11. A method for preparing the catalyst of claim 9 or 10, comprising: loading an active component precursor on a carrier, and then carrying out second roasting, wherein the active component precursor comprises a VIII group metal precursor and/or IB group metal precursor, and the carrier comprises the all-silicon molecular sieve in any one of claims 1-8.
12. The preparation method according to claim 11, wherein the active component precursor is used in an amount such that the active component is contained in an amount of 0.01 to 2g in terms of metal element with respect to 100g of the all-silica molecular sieve in the obtained catalyst;
and/or the temperature of the second roasting is 450-600 ℃ and the time is 3-9h.
13. Use of the all-silica molecular sieve of any one of claims 1 to 12 and the catalyst of any one of claims 9 to 12 in deoxygenation reactions.
14. According to the rightThe use of claim 13, wherein the deoxygenation reaction conditions comprise: the temperature of the deoxidation reaction is 100-450 ℃, the pressure of the deoxidation reaction is 0.1-1.5MPa, and the volume space velocity of the raw material gas is 1000-20000h -1 The oxygen content in the feed gas is 0.1-10 vol%.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585638A (en) * | 1984-07-16 | 1986-04-29 | Mobil Oil Corporation | Synthesis of crystalline silicate ZSM-5 |
| CN101541426A (en) * | 2006-11-23 | 2009-09-23 | 法国石油公司 | Catalyst based on a silicon-containing material with hierarchical porosity and method for the hydrocracking/hydroconversion and hydroprocessing of hydrocarbon feedstocks |
| CN104310413A (en) * | 2014-10-21 | 2015-01-28 | 太原理工大学 | Preparation method and application of thin-layer nano flaky total-silicon molecular sieve for preparing caprolactam |
| CN104812704A (en) * | 2012-11-28 | 2015-07-29 | 埃克森美孚化学专利公司 | MFI with unusual morphology |
| CN106032278A (en) * | 2015-03-18 | 2016-10-19 | 中国石油大学(华东) | Preparation method of total-silicon molecular sieve Silicalite-1 having high hydrogen bond silicon hydroxyl content |
| CN106115729A (en) * | 2016-06-27 | 2016-11-16 | 河南师范大学 | A kind of synthesis under condition of no solvent has hierarchical porous structure MCM 41 and the method for metal-doped M MCM 41 molecular sieve |
| CN108640125A (en) * | 2018-05-16 | 2018-10-12 | 浙江科技学院 | A kind of preparation method of organic and inorganic molecular sieve |
| CN110028983A (en) * | 2019-04-26 | 2019-07-19 | 河南百优福生物能源有限公司 | A kind of method that biomass pyrolysis liquid hydrogenation deoxidation oil prepares aromatic hydrocarbons |
| WO2021115499A1 (en) * | 2019-12-10 | 2021-06-17 | Charles University, Faculty Of Science | Method of preparation of mfi zeolites with encapsulated metal nanoparticles |
| CN113244931A (en) * | 2020-02-11 | 2021-08-13 | 中国石油化工股份有限公司 | Catalyst and method for catalytic oxidation deoxidation of unsaturated hydrocarbon-containing gas |
-
2021
- 2021-08-19 CN CN202110955353.7A patent/CN115707654A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585638A (en) * | 1984-07-16 | 1986-04-29 | Mobil Oil Corporation | Synthesis of crystalline silicate ZSM-5 |
| CN101541426A (en) * | 2006-11-23 | 2009-09-23 | 法国石油公司 | Catalyst based on a silicon-containing material with hierarchical porosity and method for the hydrocracking/hydroconversion and hydroprocessing of hydrocarbon feedstocks |
| CN104812704A (en) * | 2012-11-28 | 2015-07-29 | 埃克森美孚化学专利公司 | MFI with unusual morphology |
| CN104310413A (en) * | 2014-10-21 | 2015-01-28 | 太原理工大学 | Preparation method and application of thin-layer nano flaky total-silicon molecular sieve for preparing caprolactam |
| CN106032278A (en) * | 2015-03-18 | 2016-10-19 | 中国石油大学(华东) | Preparation method of total-silicon molecular sieve Silicalite-1 having high hydrogen bond silicon hydroxyl content |
| CN106115729A (en) * | 2016-06-27 | 2016-11-16 | 河南师范大学 | A kind of synthesis under condition of no solvent has hierarchical porous structure MCM 41 and the method for metal-doped M MCM 41 molecular sieve |
| CN108640125A (en) * | 2018-05-16 | 2018-10-12 | 浙江科技学院 | A kind of preparation method of organic and inorganic molecular sieve |
| CN110028983A (en) * | 2019-04-26 | 2019-07-19 | 河南百优福生物能源有限公司 | A kind of method that biomass pyrolysis liquid hydrogenation deoxidation oil prepares aromatic hydrocarbons |
| WO2021115499A1 (en) * | 2019-12-10 | 2021-06-17 | Charles University, Faculty Of Science | Method of preparation of mfi zeolites with encapsulated metal nanoparticles |
| CN113244931A (en) * | 2020-02-11 | 2021-08-13 | 中国石油化工股份有限公司 | Catalyst and method for catalytic oxidation deoxidation of unsaturated hydrocarbon-containing gas |
Non-Patent Citations (2)
| Title |
|---|
| SYE HOE KEOH等: "Factors Governing the Formation of Hierarchically and Sequentially Intergrown MFI Zeolites by Using Simple Diquaternary Ammonium Structure-Directing Agents", CHEMISTRY OF MATERIALS, vol. 28, pages 8997 - 9007, XP055487336, DOI: 10.1021/acs.chemmater.6b03887 * |
| 边超群: "无溶剂法高温合成沸石分子筛", 中国博士学位论文全文数据库, no. 12, pages 016 - 65 * |
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