CN115532315A - 一种二氧化碳加氢合成低碳醇催化剂的制备方法及应用 - Google Patents
一种二氧化碳加氢合成低碳醇催化剂的制备方法及应用 Download PDFInfo
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- CN115532315A CN115532315A CN202211219251.XA CN202211219251A CN115532315A CN 115532315 A CN115532315 A CN 115532315A CN 202211219251 A CN202211219251 A CN 202211219251A CN 115532315 A CN115532315 A CN 115532315A
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- catalyst
- ball
- carbon dioxide
- carbon
- cobalt
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 43
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 8
- 230000002194 synthesizing effect Effects 0.000 title description 2
- 238000000498 ball milling Methods 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 5
- LRBQNJMCXXYXIU-YIILYMKVSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)C(OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-YIILYMKVSA-N 0.000 claims abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 69
- 238000000227 grinding Methods 0.000 claims description 55
- 238000010438 heat treatment Methods 0.000 claims description 47
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 10
- 239000001263 FEMA 3042 Substances 0.000 claims description 10
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 10
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 10
- 229940033123 tannic acid Drugs 0.000 claims description 10
- 235000015523 tannic acid Nutrition 0.000 claims description 10
- 229920002258 tannic acid Polymers 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001994 activation Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 32
- 238000002156 mixing Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 229920001864 tannin Polymers 0.000 abstract description 3
- 239000001648 tannin Substances 0.000 abstract description 3
- 235000018553 tannin Nutrition 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000011056 performance test Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 229910021389 graphene Inorganic materials 0.000 description 7
- 239000002002 slurry Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- LRWQWQFSOAMWKT-UHFFFAOYSA-N [Cd].[Mo] Chemical compound [Cd].[Mo] LRWQWQFSOAMWKT-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001661 cadmium Chemical class 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 241000531116 Blitum bonus-henricus Species 0.000 description 1
- 235000008645 Chenopodium bonus henricus Nutrition 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- UOEHQMCXBPRFEY-UHFFFAOYSA-N O=[Rh](=O)=O Chemical compound O=[Rh](=O)=O UOEHQMCXBPRFEY-UHFFFAOYSA-N 0.000 description 1
- GZLCNRXKVBAALW-UHFFFAOYSA-N O=[Ru](=O)=O Chemical compound O=[Ru](=O)=O GZLCNRXKVBAALW-UHFFFAOYSA-N 0.000 description 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- 239000011609 ammonium molybdate Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229940063663 carbon dioxide 100 % Drugs 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B01J35/23—
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- B01J35/394—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
- B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
本发明公开了一种二氧化碳转化制备低碳醇催化剂及其制备方法和应用,属于二氧化碳资源化利用技术领域。所述制备方法为:将单宁酸、钴前驱物、助剂前驱物、载体通过机械球磨混合,经氨气活化、氢气/一氧化碳活化后即得催化剂产品。本发明提供的一种二氧化碳转化制备低碳醇催化剂的制备方法,单宁酸、钴前驱物、助剂前驱物和载体原料,在机械球磨的作用下创造Co单原子位点(Co2+)和Co纳米团簇位点(Co0),形成Cox+‑Co0双位点对,这些双位点可催化醇的生成和碳链的生长,极大地促进了低碳醇的选择性,低碳醇选择性高于80%,二氧化碳的转化率提高至30%以上;所述制备方法具有废液少、成本低廉和过程简单等特点,具有良好应用前景。
Description
技术领域
二氧化碳资源化利用技术领域,具体地说,涉及一种二氧化碳加氢制备低碳醇催化剂的制备方法及应用。
背景技术
二氧化碳是重要的温室气体之一,近年来其排放量迅速升高,引起全球暖化,威胁人类社会的可持续发展。因此,减少二氧化碳排放并降低其在大气中的浓度是目前人类面临的巨大挑战。通过碳捕集与利用技术将二氧化碳转化为具有高附加值的燃料和化学品不仅有助于碳减排,同时存在创造巨大经济效益的潜力。在二氧化碳转化的各类产品中,低碳混合醇(C1-4OH)可广泛用作燃料、溶剂以及化工原料,因此具有广泛的市场需求。然而,目前直接将二氧化碳转化为低碳醇仍未实现规模化工业应用。主要原因是缺乏高效催化剂实现高二氧化碳转化率和高C1-4OH选择性。
CN106994367A使用氧化石墨、硫化氢、镉盐、钼酸盐、硫酸铈作为原料制备硫掺杂石墨烯负载的镉钼基催化剂;将氧化石墨超声剥离成氧化石墨烯,低温冻干制备成氧化石墨烯气凝胶,硫化氢与其表面含氧官能团发生还原和掺杂,一步合成硫掺杂石墨烯气凝胶;镉盐沉积于硫掺杂石墨烯表面;钼和铈通过离子交换及高温条件与镉复合,最终制得高负载、比表面积大的硫掺杂石墨烯负载的镉钼基催化剂;该催化剂催化活性高,乙醇选择性好,但制备过程步骤繁长、复杂。
CN106311281A以镍盐和碱共沉淀制得的碱式碳酸镍为模板,通过离子交换法引入过渡金属钼,再浸渍碱金属钾,最后硫化得到具有层状结构的三元金属硫化物催化剂。该催化剂上二氧化碳加氢可直接得到乙醇、丙醇等高附加值的醇类燃料,乙醇在总醇中的摩尔分数达到43%,仍存在提升空间。
CN106925315A使用氧化石墨、硼氢化钠、氯化钾、碳酸钾、硫酸铈、可溶性铜盐作为原料制备催化剂,制备得到的催化剂以石墨烯为载体,铜为活化组分,钾和铈为助剂;催化活性高,选择性好,但制备流程复杂,产生大量废水。
综上所述,目前二氧化碳加氢制高级醇催化剂存在低碳醇选择性较低、成本高以及制备过程复杂等缺点。
发明内容
针对现有技术存在的不足,本发明的目的在于提供一种二氧化碳转化制备低碳醇的催化剂及其制备方法和应用,所述制备方法简单、成本低,所述催化剂在二氧化碳催化加氢制备低碳醇反应中对于低碳醇的选择性高。
为了实现上述目的,本发明采用如下技术方案:
一种用于二氧化碳转化制低碳醇的催化剂制备方法,包括如下步骤:将单宁酸、将钴前驱物、助剂前驱物、载体通过机械球磨混合,经氨气活化、氢气/一氧化碳活化后即得催化剂产品。
作为本发明技术方案的进一步优选,钴前驱物选自硝酸钴、醋酸钴、氯化钴、草酸钴、酞菁钴、硫酸钴中的一种或多种混合物。
作为本发明技术方案的进一步优选,载体选自铁、锆、铝、铈、锌、锰、钛、铜、镁、硅、镍、钼、钨、钒、镧的氧化物或碳材料中的一种或多种的混合物。
作为本发明技术方案的进一步优选,助剂选自铁、铂、钯、钌、铑、锆、铝、铈、锌、锰、钛、铜、镁、硅、镍、钼、钨、钒、镧的可溶化合物中的一种或多种的混合物。
作为本发明技术方案的进一步优选,钴前驱物∶助剂前驱物∶单宁酸∶载体的质量比为1~25∶0.1~15∶0.1~15∶50~98.8。
作为本发明技术方案的进一步优选,上述催化剂的制备方法中机械球磨采用的球磨机为行星式球磨机、罐装式球磨机、振动式磨矿机、搅拌式球磨机、针磨机、滚筒式球磨机和砂磨机中的一种;球磨罐为不锈钢球磨罐、聚四氟乙烯球磨罐、玛瑙球磨罐、尼龙球磨罐、刚玉球磨罐、二氧化锆球磨罐中的一种;研磨球为不锈钢研磨球、氧化铝研磨球、玛瑙研磨球或氧化锆研磨球中的一种或几种;机械球磨转速为10~1500r/min,机械球磨时间为0.5~72h。
作为本发明技术方案的进一步优选,氨气活化过程在含300~1000℃含氨气气氛中进行。
作为本发明技术方案的进一步优选,热处理过程在200~1000℃的含氢气或/和一氧化碳气氛中进行。
同时,本发明还请求保护上述方法制备得到的催化剂。
同时,本发明还请求保护上述催化剂在二氧化碳加氢催化制备低碳醇中的应用。与现有技术相比,本发明具有如下有益效果:
(1)本发明通过单宁酸锚定和氨气活化,引入钴单原子位点(Cox+)。钴单原子位点与钴纳米团簇位点(Co0)共存,形成Cox+-Co0双位点对。其中,Cox+和Co0位点上可分别形成HCOO和CHx中间体。Cox+-Co0双位点对协同强化HCOO-CHx偶联,促进碳链生长,将低碳醇的选择性提高至80以上%。
(2)本发明通过单宁酸与钴离子配位形成的催化剂分散性高,极大地提高了钴的利用率,将CO2的转化率提高至30%以上。
(3)本发明所提出的制备方法无需溶剂,因此不产生废液,避免了因为废液处理所产生的成本。
具体实施方式
下面将结合本发明实施方式,对本发明实施方式中的技术方案进行清楚、完整地描述,显然,所描述的实施方式仅仅是本发明一部分实施方式,而不是全部的实施方式。基于本发明中的实施方式,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式,都属于本发明保护的范围。
如无特殊说明外,本发明中所有商品或试剂均通过市场渠道购买。
实施例1
一种二氧化碳转化制低碳醇催化剂的制备方法,步骤如下:
(1)称取0.5g硫酸钴、1.0g单宁酸、0.1g硫酸镍,8.4g三氧化二铝混合均匀,得混合物;
(2)将步骤(1)中所得混合物和500g玛瑙研磨球置于1000mL的玛瑙研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速500r/min,球磨7h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于800℃ 1%氨气/99%氮气中热处理3h;待热处理结束,取出混合物。
(4)将步骤(3)中热处理后的混合物置于300℃的10%氢气/90%氮气中热处理3h;热处理结束后取出混合物;
在浆态床反应器中进行催化剂性能测试。
实施例2
一种二氧化碳转化制低碳醇催化剂的制备方法,步骤如下:
(1)称取2.0g醋酸钴、0.5g单宁酸、0.5g醋酸铁,7.0g二氧化锆混合均匀,得混合物;
(2)将步骤(1)中所得混合物和500g二氧化锆研磨球置于1000mL的二氧化锆研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速100r/min,球磨70h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于300℃ 10%氨气/90%氮气中热处理72h;待热处理结束,取出混合物。
(4)将步骤(3)中热处理后的混合物置于900℃的1%氢气/99%氩气中热处理6h;热处理结束后取出混合物;
在固定床反应器中进行催化剂性能测试。
实施例3
一种二氧化碳转化制低碳醇催化剂的制备方法,步骤如下:
(1)称取0.25g氯化钴、1.5g单宁酸、0.1g硝酸铝,8.15g四氧化三铁混合均匀,得混合物;
(2)将步骤(1)中所得混合物和500g不锈钢研磨球置于1000mL的不锈钢研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速1500r/min,球磨0.5h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于1000℃ 0.5%氨气/99.5%氮气中热处理0.5h;待热处理结束,取出混合物。
(4)将步骤(3)中热处理后的混合物置于200℃的100%氢气中热处理72h;热处理结束后取出混合物;
在浆态床反应器中进行催化剂性能测试。
实施例4
一种二氧化碳转化制低碳醇催化剂的制备方法,步骤如下:
(1)称取0.1g草酸钴、0.01g单宁酸、0.01g醋酸镁,9.88g二氧化铈混合均匀,得混合物;
(2)将步骤(1)中所得混合物和500g刚玉研磨球置于1000mL的刚玉研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入滚筒球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速200r/min,球磨70h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于400℃ 2%氨气/98%氦气中热处理4h;待热处理结束,取出混合物。
(4)将步骤(3)中热处理后的混合物置于1000℃的1%氢气/99%氦气中热处理0.5h;热处理结束后取出混合物;
在固定床反应器中进行催化剂性能测试。
实施例5
一种二氧化碳转化制低碳醇催化剂的制备方法,步骤如下:
(1)称取2.5g酞菁钴、1.0g单宁酸、1.5g硝酸镧,5.0g二氧化硅混合均匀,得混合物;
(2)将步骤(1)中所得混合物和500g氧化铝研磨球置于1000mL的尼龙研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入滚筒式球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速50r/min,球磨72h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于500℃ 1%氨气/99%氮气中热处理2h;待热处理结束,取出混合物。
(4)将步骤(3)中热处理后的混合物置于500℃的10%一氧化碳/90%氩气中热处理1h;热处理结束后取出混合物;
在固定床反应器中进行催化剂性能测试。
实施例6
一种二氧化碳转化制低碳醇催化剂的制备方法,步骤如下:
(1)称取1.0g硝酸钴、1.0g单宁酸、0.2g硝酸铜、0.2g硝酸锌、0.2g硝酸锰、0.2g硝酸钛、0.2g硝酸铈、0.5g硝酸锆,1.0g氧化锌、1.0g氧化锰、1.5g二氧化钛、1.5g氧化铜、1.5g氧化镁混合均匀,得混合物;
(2)将步骤(1)中所得混合物和500g二氧化锆研磨球置于1000mL的二氧化锆研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入滚筒式球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速200r/min,球磨60h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于700℃ 1%氨气/99%氮气中热处理5h;待热处理结束,取出混合物。
(4)将步骤(3)中热处理后的混合物置于300℃的20%氢气/80%氮气中热处理3h;热处理结束后取出混合物;
在浆态床反应器中进行催化剂性能测试。
实施例7
一种二氧化碳转化制低碳醇催化剂的制备方法,步骤如下:
(1)称取1.0g醋酸钴、1.96g单宁酸、0.01g氯铂酸、0.01g二氯化钯、0.01g三氧化钌、0.01g三氧化铑、2.0g三氧化钼、2.0g三氧化钨、2.0g二氧化钒、2.0g三氧化二镧混合均匀,得混合物;
(2)将步骤(1)中所得混合物和500g二氧化锆研磨球置于1000mL的二氧化锆研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速800r/min,球磨5h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于400℃ 5%氨气/95%氮气中热处理6h;待热处理结束,取出混合物。
(4)将步骤(3)中热处理后的混合物置于300℃的10%一氧化碳/90%氦气中热处理6h;热处理结束后去除混合物;
在固定床反应器中进行催化剂性能测试。
实施例8
一种二氧化碳转化制低碳醇催化剂的制备方法,步骤如下:
(1)称取2.0g醋酸钴、1.0g单宁酸、0.1g钼酸铵、0.1g钨酸铵、0.1g偏钒酸铵,6.7g二氧化锆混合均匀,得混合物;
(2)将步骤(1)中所得混合物和500g二氧化锆研磨球置于1000mL的二氧化锆研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行滚筒式球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速300r/min,球磨20h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于300℃ 1%氨气/99%氮气中热处理72h;待热处理结束,取出混合物。
(4)将步骤(3)中热处理后的混合物置于600℃的1%氢气/99%氮气气氛中热处理6h;热处理结束后去除混合物;
在固定床反应器中进行催化剂性能测试。
对比例1
一种二氧化碳转化制低碳醇催化剂的制备方法,步骤如下:
(1)称取0.5g硫酸钴、0.1g硫酸镍,9.4g三氧化二铝混合均匀,得混合物;
(2)将步骤(1)中所得混合物和500g玛瑙研磨球置于1000mL的玛瑙研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速500r/min,球磨7h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于800℃ 1%氨气/99%氮气中热处理3h;待热处理结束,取出混合物。
(4)将步骤(3)中热处理后的混合物置于300℃的10%氢气/90%氮气中热处理3h;热处理结束后取出混合物;
在浆态床反应器中进行催化剂性能测试。
测试例
固定床反应器:将0.3g制备得到的催化剂与2g SiC混合后置于反应器中,原料气(20v%二氧化碳、70v%氢气、10v%氮气混合物)以一定流量流过催化剂床层,采用的空速为2升/克催化剂/小时,将反应压力逐步升高至5MPa,将反应温度逐步升高至250℃开始反应,进行为期100h的性能测试,反应器出口产物保温在150℃,通入色谱进行在线分析。
浆态床反应器:将3g制备得到的催化剂与100mL高沸点蜡油在室温下混合,随后将该混合物转移至1L的连续搅拌反应器中。原料气(20v%二氧化碳、70v%氢气、10v%氮气混合物)以一定流量通入反应器,采用的空速为2升/克催化剂/小时,将反应压力逐步升高至5.0MPa,将反应温度逐步升高至230℃开始反应,反应器出口产物保温在150℃,通入色谱进行在线分析。
按照以下公式计算二氧化碳转化率和产物选择性:
二氧化碳转化率=(进口二氧化碳摩尔数-出口二氧化碳摩尔数)/进口二氧化碳摩尔数*100%;
产物选择性=出口产物摩尔数*产物中碳原子数/(进口二氧化碳摩尔数-出口二氧化碳摩尔数)*100%。
测试结果见表1所示。
表1催化剂催化性能测试结果
从表1中可以看到,本发明制备得到的催化剂能够较好地实现二氧化碳加氢制备低碳醇的技术效果,以实施例6为例,二氧化碳的转化率为31%,总醇选择性高达94%;其中乙醇和C2+醇的选择性高达88%。
本发明通过上述实施例来说明本发明的技术构思,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品个别原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种二氧化碳转化制低碳醇的催化剂制备方法,其特征在于,将单宁酸、钴前驱物、助剂前驱物和载体通过机械球磨混合,经氨气活化、氢气/一氧化碳活化后即得催化剂产品。
2.根据权利要求1所述的一种二氧化碳转化制备低碳醇催化剂的制备方法,其特征在于,钴前驱物选自硝酸钴、醋酸钴、氯化钴、草酸钴、酞菁钴、硫酸钴中的一种或多种的混合物。
3.根据权利要求1所述的一种二氧化碳转化制备低碳醇催化剂的制备方法,其特征在于,载体选自铁、锆、铝、铈、锌、锰、钛、铜、镁、硅、镍、钼、钨、钒、镧的氧化物或碳材料中的一种或多种的混合物。
4.根据权利要求1所述的一种二氧化碳转化制备低碳醇催化剂的制备方法,其特征在于,助剂选自铁、铂、钯、钌、铑、锆、铝、铈、锌、锰、钛、铜、镁、硅、镍、钼、钨、钒、镧的可溶化合物中的一种或多种的混合物。
5.根据权利要求1所述的一种二氧化碳转化制备低碳醇催化剂的制备方法,其特征在于,钴前驱物∶助剂前驱物∶单宁酸∶载体的质量比为1~25∶0.1~15∶0.1~15∶50~98.8。
6.根据权利要求1所述的一种二氧化碳转化制备低碳醇催化剂的制备方法,其特征在于,上述催化剂的制备方法中机械球磨采用的球磨机为行星式球磨机、罐装式球磨机、振动式磨矿机、搅拌式球磨机、针磨机、滚筒式球磨机和砂磨机中的一种;球磨罐为不锈钢球磨罐、聚四氟乙烯球磨罐、玛瑙球磨罐、尼龙球磨罐、刚玉球磨罐、二氧化锆球磨罐中的一种;研磨球为不锈钢研磨球、氧化铝研磨球、玛瑙研磨球或氧化锆研磨球中的一种或几种;机械球磨转速为10~1500r/min,机械球磨时间为0.5~72h。
7.根据权利要求1所述的一种二氧化碳转化制备低碳醇催化剂的制备方法,其特征在于,氨气活化过程在300~1000℃含氨气气氛中进行。
8.根据权利要求1所述的一种二氧化碳转化制备低碳醇催化剂的制备方法,其特征在于,热处理过程在200~1000℃的含氢气或/和一氧化碳气氛中进行。
9.权利要求1~8任一项所述方法制备得到的催化剂。
10.权利要求9所述催化剂在二氧化碳加氢催化制备低碳醇中的应用。
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