CN107952461A - A kind of loaded nano Co catalysts and its application - Google Patents
A kind of loaded nano Co catalysts and its application Download PDFInfo
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- CN107952461A CN107952461A CN201610903696.8A CN201610903696A CN107952461A CN 107952461 A CN107952461 A CN 107952461A CN 201610903696 A CN201610903696 A CN 201610903696A CN 107952461 A CN107952461 A CN 107952461A
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- nitrogen
- cobalt
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- 239000003426 co-catalyst Substances 0.000 title claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 106
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 106
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 106
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000003054 catalyst Substances 0.000 claims abstract description 93
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 50
- 230000009467 reduction Effects 0.000 claims abstract description 38
- 239000006185 dispersion Substances 0.000 claims abstract description 36
- 239000008187 granular material Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 35
- -1 nitrogenous compound Chemical class 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 235000013495 cobalt Nutrition 0.000 claims description 103
- 239000007789 gas Substances 0.000 claims description 61
- 239000001301 oxygen Substances 0.000 claims description 35
- 229910052760 oxygen Inorganic materials 0.000 claims description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008246 gaseous mixture Substances 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 3
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 1
- 229960004424 carbon dioxide Drugs 0.000 claims 1
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006722 reduction reaction Methods 0.000 description 34
- 238000000034 method Methods 0.000 description 29
- 230000004913 activation Effects 0.000 description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
- 239000003223 protective agent Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 235000013339 cereals Nutrition 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 7
- 150000001868 cobalt Chemical class 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229940126678 chinese medicines Drugs 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000013528 metallic particle Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 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
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000008118 PEG 6000 Substances 0.000 description 1
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 229910000428 cobalt oxide Inorganic materials 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
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 230000009514 concussion Effects 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
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of loaded nano Co catalysts and its application, the cobalt content in the catalyst based on the element is 3~65 weight %, and its preparation method includes：(1) nano cobalt granule is prepared, obtained nano cobalt granule is scattered in solvent, obtains nanometer cobalt dispersion liquid；(2) the nanometer cobalt dispersion liquid impregnated carrier obtained with step (1), and impregnated carrier is dried；(3) step (2) dried product is reduced；It is characterized in that, the step of including the catalyst and nitrogen or nitrogenous compound haptoreaction prior to, concurrently with, or after the reduction so that the nitrogen content in final catalyst based on the element is to less than or equal to 0.2 weight % more than 0.Compared with the catalyst that the prior art obtains, catalytic activity when catalyst provided by the invention is applied to F- T synthesis is high, methane selectively is low, C5+ high selectivity, and the stability with higher.
Description
Technical field
A kind of application the present invention relates to supported cobalt catalysts and its in Fischer-Tropsch synthesis.
Background technology
As Global Oil resource is more and more rare, people utilize coal and natural gas etc. to the pay attention to day by day of environmental protection
Clean fuel is prepared for raw material and chemicals is increasingly valued by people.F- T synthesis technology is that these coals and natural gas are clear
One of clean key technology utilized.
The primary product that synthesis gas changes into the Fischer-Tropsch synthesis of hydro carbons on a catalyst includes alkane and alkene, product
High-quality liquid fuel and chemicals are can obtain by deep processing.
At present, load type cobalt-base catalyst is a kind of fischer-tropsch synthetic catalyst with industrial application value.General load
Type cobalt-base catalyst is prepared using infusion process, and active component cobalt particle size is larger, and distribution is wide, and the utilization rate of cobalt is low and inactivation is existing
As obvious.In addition, in order to make cobalt oxide fully reduce Viability metallic cobalt, noble metal auxiliary agent generally is used, this just makes
Into significantly improving for catalyst cost.Therefore, the utilization rate that how to improve cobalt, the utilization for reducing noble metal, improve catalyst
Stability and catalytic performance are all difficult point and the direction of cobalt-base catalyst exploitation all the time.
CN102274726 discloses a kind of activation method for preparing supported cobalt catalysts.First prepare particle size 3~
The cobaltosic oxide nano particle comprising auxiliary agent of 20nm, then loads on carrier, finally by hydrogen reducing.The catalyst
Catalyst activity prepared by relatively traditional infusion process is doubled, but selectivity does not have significant change.
Kou Yuan et al. (catalysis journal, the 2013, the 10th phase, 1914~1925) disclose in the presence of protective agent, pass through control
The method that the method for system reduction prepares water phase Co nano particles, although low temperature active is higher, granule stability is poor.
The content of the invention
The technical problem to be solved in the present invention is to provide the catalyst of a kind of high activity, high selectivity and high stability, and
Application of the catalyst in F- T synthesis is provided.
In order to realize above-mentioned technical purpose, the present invention provides following technical solution, and particular content includes：
A kind of loaded nano Co catalysts, it is characterised in that cobalt content on the basis of catalyst and based on the element is 3
~65 weight %, the preparation method of the catalyst include：(1) nano cobalt granule is prepared, obtained nano cobalt granule is disperseed
In solvent, nanometer cobalt dispersion liquid is obtained；(2) the nanometer cobalt dispersion liquid impregnated carrier obtained with step (1), and to impregnated
Carrier is dried；(3) step (2) dried product is reduced；It is characterized in that, before the reduction, it is same
When or include afterwards by step (2) the dried product and the step of nitrogen or nitrogenous compound haptoreaction, the contact
The condition of reaction make it that the nitrogen content in final catalyst based on the element is to less than or equal to 0.2 weight % more than 0.
Present invention also offers application of the catalyst in F- T synthesis, is specially：By carbon monoxide and hydrogen
Mixture and catalyst haptoreaction of the present invention, reaction condition are：160~300 DEG C, 1~8MPa of pressure of temperature, hydrogen and
The molar ratio 0.4~2.5 of carbon monoxide：1,200~40000h of gas volume air speed-1。
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
, according to the invention it is preferred to, on the basis of the catalyst and in terms of cobalt element, in catalyst cobalt content for 5~
50 weight %.
According to the present invention, the nanometer cobalt described in step (1) is metallic cobalt, can prepare nanometer cobalt using any prior art
Particle, can also use control reduction method (controlled reduction) to prepare, such as ZL200710099011.X is mentioned
Method prepare.It is included in the presence of protective agent, carrying out reduction reaction to cobalt salt using reducing agent obtains.Selectively, it is described
The process that control reduction prepares nano cobalt granule carries out in the presence of reaction medium, in the presence of having reaction medium, reaction medium
It is preferably water, ethanol, four for the one or more in water, methanol, ethanol, propyl alcohol, acetic acid, lactic acid, tetrahydrofuran, citric acid
Hydrogen furans or its mixture.The wherein described water can be distilled water, deionized water etc..Specially：Cobalt salt and protective agent are added
Enter to obtain cobalt salt and protectant mixed solution into reaction medium, then reducing agent is added in mixed solution and is carried out instead
Should, obtain the nano cobalt granule.The condition of the control reduction reaction includes：Reaction temperature is -10~70 DEG C, the reaction time
For 0.01~4h；Reaction condition is preferably that reaction temperature is 0~40 DEG C, and the reaction time is 0.1~2h.The cobalt salt is cobalt
Inorganic salts or carboxylate, one or more of the reducing agent in sodium borohydride, potassium borohydride, hydrazine hydrate are described to go back
Former agent is 3~20 with element cobalt molar ratio：1, it is preferably 3~15：1；The protective agent is selected from PEG, PVP, oleic acid, linoleic acid
In one or more, the molar ratio of the protective agent and element cobalt is 10~500：1, it is preferably 20~200：1, as the guarantor
When shield agent is polymer, protectant molal quantity is in terms of monomer.
In a specific embodiment, the nano cobalt granule in the step (1) is prepared using control reduction method, bag
Include：In the presence of protective agent, reduction treatment is carried out to cobalt salt using reducing agent and is obtained.The cobalt salt is the inorganic salts or carboxylic of cobalt
Hydrochlorate, can be selected from one kind in cobalt chloride, cobalt nitrate, cobaltous sulfate, cobaltous formate, cobalt acetate, cobalt oxalate, cobalt benzoate or several
Kind, the reducing agent is reduces the material that cobalt salt generates metallic cobalt at normal temperatures, such as sodium borohydride, potassium borohydride, hydrazine hydrate
Deng one or more of the protective agent in PVP, PEG, oleic acid, linoleic acid.Control the reaction medium of reduction reaction can
Think the one or more in water, methanol, ethanol, propyl alcohol, acetic acid, lactic acid, citric acid, be preferably water and ethanol or its mixing
Thing, more preferably water.The wherein described water can be distilled water, deionized water etc..Reaction preferably at 0~40 DEG C into
OK, the molar ratio that the reaction time is preferably 0.1~2h, wherein reducing agent and cobalt is 3~20：1, it is preferably 3~15：1；Protective agent
Molar ratio with cobalt is 10~500：1, it is preferably 20~200：1, when the protective agent is polymer, protectant molal quantity
In terms of monomer.In order to make reaction preferably carry out, in reduction process is controlled, system can blanketing with inert gas, such as it is described also
Original carries out in glove box, and High Purity Nitrogen or high-purity argon gas are filled with glove box.In the present invention, preferably include to being prepared
The step of nano cobalt granule is washed, using nano cobalt granule weight as base in the nano cobalt granule that the washing makes
Standard, other metal impurities gross weight contents in addition to cobalt are not more than 100ppm.On the premise of it can reach washing and require, this hair
It is bright that washing methods is not limited, such as centrifuge washing can be used, i.e., reaction system is centrifuged, consolidated to what is obtained
Solvent washing is added in body material, then centrifuges again, operation as described above can be repeated, cleaning solvent can be
Water, ethanol or its mixture etc..After washing finishes, nano cobalt granule is disperseed to obtain nanometer cobalt dispersion liquid in a solvent, institute
It can be one in water, methanol, ethanol, propyl alcohol, acetic acid, lactic acid, citric acid, polyethylene glycol, polyvinylpyrrolidone to state solvent
Kind is several, is preferably water, methanol, ethanol, propyl alcohol, acetic acid, more preferably ethanol.The wherein described water can be distillation
Water, deionized water etc..In the present invention, the nanometer cobalt dispersion liquid is a kind of nanometer cobalt colloidal sol of stabilization.In order to make nanometer cobalt point
Dispersion liquid is more stable and is uniformly dispersed in decentralized medium, can be disperseed using ultrasonic means.Obtained nanometer cobalt point
In dispersion liquid, characterized with TEM, the particle diameter of the nano cobalt granule is 1~20nm, is preferably 3~15nm.
Method on being enough to make reduction reaction carry out under oxygen-free environment is known to those skilled in the art, such as：
Reaction carries out under nitrogen storage condition or in the glove box of inert gas shielding, does not repeat here.By nano cobalt granule point
Conventional method can be used by dissipating method in solvent, such as stirring, concussion and or ultrasound, preferred ultrasonic disperse.
The dipping of step (2) of the present invention refers to contact the nanometer cobalt dispersion liquid with carrier, and is received described
Rice cobalt granule is carried on the process on carrier, and under the premise of being enough to realize this purpose, the present invention does not have the method for the dipping
There is special limitation, for example, the dipping method that the dispersion liquid is mixed with carrier.In order to make nanometer cobalt dispersion liquid more it is stable and
Uniform to disperse and preferably have an effect with carrier, preferably described be immersed under ultrasound condition carries out.
According to catalyst provided by the invention, wherein the carrier is the heat-resisting nothing of porosity for being commonly used for catalyst carrier
Machine oxide, for example, selected from aluminium oxide, titanium oxide, magnesia, alumina-silica magnesium, silica-alumina, silica-oxygen
Change magnesium, silica-zirconia, silica thoria, silica-berylias, silica-titania, silica-zirconia, oxygen
Change titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, oxygen
One or more in SiClx-aluminium oxide-zirconium oxide, natural zeolite, clay.The specific surface area of carrier is 5~600 meters2/ gram,
Specific surface area is preferably 5~500 meters2/ gram, specific surface area is more preferably 10~500 meters2/ gram.
It is to remove the nanometer cobalt dispersion liquid that impregnated carrier, which is dried, in the present invention, described in step (2)
In solvent for the purpose of, on the basis of being enough to realize this purpose, the method for the drying is not particularly limited in the present invention, such as
It is dried using the method vacuumized, or is dried using the method vacuumized with reference to heating, or heating
Method is dried.
The various shapes met the requirements, such as microballoon, ball can be made depending on different requirements in carrier in the step (2)
Shape, tablet or bar shaped etc..Shaping can carry out according to a conventional method, for example, when the shape of required shaping carrier is that can meet slurry bed system
During the microballoon needed, the porosity heat-resistant inorganic oxide molding can be by preparing its precursor (for example, aluminium oxide
Precursor boehmite), afterwards, prepared by which is spray-dried and roasts method.Can also pass through purchase
Predecessor's powder of the commercially available porosity heat-resistant inorganic oxide met the requirements (obtains for example, spray-dried
The precursor boehmite powder of aluminium oxide) and roast method prepare.The method and condition of the roasting are catalyzed to prepare
The method and condition of the usual roasting of agent carrier.For example, method of the method for the roasting for roasting in air atmosphere, its
In, the condition of the roasting includes：Calcination temperature be 300~900 DEG C, preferably 350~850 DEG C, more preferably 550~
800 DEG C, roasting time for 0.5~12 it is small when, preferably 1~8 it is small when, more preferably 2~6 it is small when.In general, meeting
On the premise of slurry reactor requirement, the particle diameter of the microballoon molding is not particularly limited in the present invention, in the preferred case,
The average grain diameter of the molding is preferably 20~150 microns, wherein, the grain volume fraction less than 20 microns is not more than 5%,
It is preferred that the average grain diameter of the molding is 30~120 microns, more preferably 40~100 microns.Wherein, the carrier
Particle diameter is evaluated using ISO13320-1 grain size analyses-laser diffraction method measure.
Inventor further study show that, obtained nano cobalt granule is scattered in after solvent in the step (1) and
Before step (2), the step of being passed through oxygen-containing gas into nanometer cobalt dispersion liquid is further included, the catalyst performance thus finally obtained
More preferably.Specially：Oxygen-containing gas is passed through in nanometer cobalt dispersion liquid, oxygen and nano cobalt granule is acted on, obtains one kind
The nanometer cobalt dispersion liquid reacted with oxygen-containing gas, the step can also be described as being passivated nanometer cobalt using oxygen-containing gas
The step of processing.In the mixed gas containing oxygen in addition to oxygen, other components can be selected from nitrogen, inert gas
In one or more, oxygen content is not more than 21 volume % in the oxygen-containing gas, is preferably 0.01~5 volume %；It is described
The operating condition of oxygen-containing gas is passed through into nanometer cobalt dispersion liquid to be included：Temperature -10~60 DEG C, are preferably 0~50 DEG C, the time is
0.01~24h, is preferably 0.1~4h, on the basis of nanometer cobalt quality, the volume space velocity of oxygen-containing gas is 0.2~20Lg-1·
h- 1,Preferably 1~10Lg-1·h-1.The oxygen-containing gas is oxygen and the one or more in nitrogen, inert gas
Gaseous mixture, oxygen content is no more than 21 volume % in the oxygen-containing gas, is preferably 0.01~5 volume %.
, according to the invention it is preferred to, the catalytic condition causes the nitrogen content in final catalyst based on the element
For 0.01~0.1 weight %.
Step (2) dried product can be with the reduction at the same time with nitrogen or nitrogenous compound haptoreaction in the present invention
Carrying out, can also be carried out before or after the reduction, preferably described haptoreaction is after the reduction or is carried out at the same time,
More preferably described haptoreaction is carried out at the same time in the reduction.
When the reduction and described and nitrogen or nitrogenous compound haptoreaction are carried out at the same time, including by step (2) Suo Shu
Dried product and reducing gas and the gaseous mixture or reducing gas of nitrogen and the gaseous mixture haptoreaction of nitrogenous compound, institute
It is H to state reducing gas2, CO, the one or more in small molecule hydro carbons, be preferably H2, nitrogen or nitrogenous compound in the gaseous mixture
Content be more than 0 to less than or equal to 30 volume %, being preferably 0.001~20 volume %, reducing gas content be more than or equal to
10 volume % are preferably 20~80 volume %, surplus is inert gas to 100 volume % are less than；The reduction and with nitrogen or containing
The catalytic operating condition of nitrogen compound includes：Temperature is 100~800 DEG C, and the time be 0.5~144h, pressure is 0.1~
4MPa；Preferably, temperature is 200~700 DEG C, and more preferably 250~450 DEG C, pressure is 0.1~3MPa, further excellent
Elect 0.2~3MPa as, the time is 1~96h, more preferably 1h~48h.
It is described with nitrogen or to contain when described with nitrogen or when nitrogenous compound haptoreaction carries out before or after the reduction
Nitrogen compound haptoreaction is included step (2) the dried product and nitrogenous gas haptoreaction, wherein, nitrogenous gas
In contain nitrogen or nitrogenous compound, in nitrogenous gas the content of nitrogen or nitrogenous compound be more than 0 to less than or equal to 30 volume %,
Preferably 0.001~20 volume %, surplus are inert gas；The reduction carries out in reducing gas atmosphere, the also Primordial Qi
Body is H2, CO, the one or more in small molecule hydro carbons, be preferably H2, H in reducing gas2, CO, one kind in small molecule hydro carbons
Or several total contents is not less than 10 volume %, 20 volume % are preferably not less than；The haptoreaction and the behaviour of the reduction
It is independently selected from as condition：Temperature is 0~800 DEG C, and the time is 0.5~144h, and pressure is 0.1~4MPa, it is preferred that institute
State haptoreaction and the operating condition of the reduction is independently selected from：Temperature is 100~700 DEG C, more preferably 200
~450 DEG C, pressure is 0.1~3MPa, more preferably 0.2~3MPa, and the time is 1~96h, more preferably 1h~
48h。
According to the present invention, carry out reduction and or during with nitrogen or nitrogenous compound haptoreaction, meeting that other require premise
Under, inert gas can be contained in the atmosphere of reaction, inert gas is the one or more in the 0th race's gas.
According to the present invention, the nitrogenous compound is the one or more in ammonia, hydrazine, organic amine, is preferably methylamine.
Present invention also offers application of the catalyst in F- T synthesis, Fischer-Tropsch synthesis condition is specifically included in
Under, by the mixture of carbon monoxide and hydrogen and the catalyst haptoreaction, the reaction condition is：Temperature is 160~350
DEG C, pressure is preferably 1~8MPa, and the molar ratio of hydrogen and carbon monoxide is 0.4~2.5：1, the volume space velocity of gas for 200~
40000h-1；Reaction condition is preferably 190~280 DEG C, 1~5MPa of pressure of temperature, and the molar ratio 1.0 of hydrogen and carbon monoxide~
2.5：1, the volume space velocity of gas is 500~30000h-1。
Compared with prior art, catalyst provided by the invention is applied to that in Fischer-Tropsch synthesis catalysis can be greatly enhanced
The stability and catalytic activity of agent.
The present invention is described further for the following examples.
The particle diameter of nanometer cobalt can be obtained by transmission electron microscope (TEM) in nanometer cobalt dispersion liquid and catalyst, for example, using
FEI Co.'s FEI TECNAI G2F20S-TWIN type transmission electron microscopes, voltage 200kV, each sample is 500,000~100
Clapped under the conditions of ten thousand enlargement ratios and take 10-15 photos, Nano Measure are used from more than 200 particles of taken a picture middle selection
Software carries out grain diameter measurement, and measurement result is counted, and obtains nano cobalt granule grain in nanometer cobalt dispersion liquid and catalyst
Footpath data.Nitrogen in catalyst is measured by microcoulomb nitrogen determination method.
Catalyst preparation process carries out in nitrogen atmosphere glove box.
Prepare embodiment：
Embodiment 1
(1) prepared by nanometer cobalt dispersion liquid：In glove box under High Purity Nitrogen protection, added into the there-necked flask with stirring
210ml distilled water, 15.4g protective agents PVP-30k (Chinese medicines group, analysis are pure) and tetra- acetate hydrate cobalts of 3.5g (lark prestige, analysis
It is pure), kept for 15 minutes under normal temperature condition, to solid slow mechanism dissolved, will contain 2.8g sodium borohydrides using syringe and (try in Beijing
Agent, analysis it is pure) aqueous solution 30.8g fast injections into there-necked flask, continue after react 15 minutes under the conditions of stirring at normal temperature, general
Reaction solution is transferred to centrifuge tube and is centrifuged at a high speed, and then carries out centrifuge washing to nano cobalt granule with distilled water 6 times, often
Secondary dosage 50mL, obtains nano cobalt granule.Using ICP/AES methods (RIPP 127-90) measure wherein other gold in addition to cobalt
The weight content for belonging to total is less than 100ppm.Finally obtained nano cobalt granule is dispersed in 30mL absolute ethyl alcohols and obtains nanometer cobalt
Dispersion liquid.TEM measures nano cobalt granule particle size integrated distribution in 4-6nm.
(2) Passivation Treatment：Under agitation, the mixed gas of oxygen and nitrogen is passed through above-mentioned cobalt metallic particles dispersion liquid
In, the flow of 3L/h keeps 1h, and oxygen content is 0.1 volume % in mixed gas.
(3) load：Nano cobalt granule dispersion liquid after above-mentioned passivation is added into 5.9g aluminium oxide under the conditions of ultrasonic disperse
Microballoon (Sasol Products, 65 microns of average grain diameter, 180 meters of specific surface area2/ gram), after mixing, utilize rotary evaporation
Instrument removes excess of solvent under 50 DEG C of condition of water bath heating, obtains loaded nano cobalt catalyst precursor.
(4) reduction and with nitrogen substance haptoreaction：Carried out in fixed bed or fluidized-bed reactor, weigh 8.6g catalysis
Agent precursor is put into activated reactor, preferable gas composition, air speed and at a temperature of kept for certain time, be subsequently cooled to room
Temperature, catalyst is transferred in glove box, and the reaction kettle containing 150g rebasing oily (polyalphaolefin, Mobil, 4#) is added under oxygen-free environment
Interior, the catalyst after activating is used for follow-up performance evaluation.Activation condition is：0.2MPa, containing 0.005 volume % ammonias, 70
The lower 400 DEG C of reduction 4h of argon atmosphere of volume % hydrogen is activated, and is denoted as C-1, catalyst characterization data are shown in Table 1.
Embodiment 2
Compared with Example 1, it the difference is that only and processing be not passivated to nanometer cobalt dispersion liquid, directly load,
Activation method and condition are also identical, and obtained catalyst is denoted as C-2, and catalyst characterization data are shown in Table 1.
Comparative example 1
Compared with Example 2, it the difference is that only that activation condition is different, activation condition is as follows：Catalyst is existed
The lower 400 DEG C of reduction 4h of 0.2MPa, the argon atmosphere containing 70 volume % hydrogen is activated, and obtained catalyst is denoted as DC-1, urges
Agent characterize data is shown in Table 1.
Comparative example 2
Compared with Example 1, activation condition difference is differed only in, activation condition is：In 0.2MPa, containing 30 volume % hydrogen
The lower 400 DEG C of reduction 4h of argon atmosphere of gas is activated, and obtained catalyst is denoted as DC-2, and catalyst characterization data are shown in Table 1.
Embodiment 3
Compared with Example 1, activation condition difference is differed only in, activation condition is as follows：By catalyst in 2.0MPa, contain
The lower 350 DEG C of reduction 3h of the argon atmosphere of 50 volume % hydrogen and 0.001 volume % hydrazines is activated to obtain supported cobalt catalysts,
C-3 is denoted as, catalyst characterization data are shown in Table 1.
Embodiment 4
Compared with Example 1, activation condition difference is differed only in, activation condition is：By catalyst in 2.0MPa, containing 50
The lower 380 DEG C of reduction 8h of the argon atmosphere of volume % hydrogen and 0.01 volume % ethylenediamines is activated to obtain supported cobalt catalysis
Agent, is denoted as C-4, and catalyst characterization data are shown in Table 1.
Embodiment 5
Compared with Example 1, activation condition difference is differed only in, activation condition is：By catalyst in 2.0MPa, containing 70
Volume % hydrogen, 20 volume % nitrogen and the lower 400 DEG C of reduction 3h of 10 volume % argon atmospheres are activated to obtain high-performance supported
Type Co catalysts, are denoted as C-5, and catalyst characterization data are shown in Table 1.
Embodiment 6
(1) prepared by cobalt nano-particle：Under High Purity Nitrogen protection, added into the there-necked flask with stirring 210ml distilled water,
24.6g protective agents PEG-20000 (Chinese medicines group, analysis are pure) and 5.2g Cobaltous oxalate,tetrahydrates (lark prestige, analysis are pure), treat solid
Slow mechanism dissolved, stablizes 15 minutes under the conditions of ice-water bath, will contain 4.8g potassium borohydrides using syringe (Beijing reagent, analysis are pure)
Aqueous solution 32.8g fast injections into there-necked flask, after the reaction was continued 30 minutes, by reaction solution be transferred to centrifuge tube carry out at a high speed
Centrifuge, then carry out centrifuge washing to nano cobalt granule with distilled water 6 times, each dosage 50mL, obtains nano cobalt granule.
Using ICP/AES methods (RIPP 127-90) measure, wherein the total weight content of other metals is less than 100ppm in addition to cobalt.Most
Obtained nano cobalt granule is dispersed in 30mL absolute ethyl alcohols afterwards and obtains nanometer cobalt dispersion liquid.TEM measures nano cobalt granule grain
Footpath size integrated distribution is in 6-8nm.
(2) Passivation Treatment：Under static conditions, the mixed gas of oxygen and nitrogen is passed through above-mentioned cobalt metallic particles dispersion liquid
In, the flow of 1L/h keeps 4h, and oxygen content is 0.4 volume % in mixed gas.
(3) load：4.3g silicon oxide microspheres will be added after metallic cobalt nanoparticulate dispersion ultrasonic disperse after above-mentioned passivation
(70~150 microns of particle diameter, 250 meters of specific surface area2/ gram), the dry 24h of 100 DEG C of vacuum drying chamber is loaded after removing solvent
Type nanometer cobalt catalyst, is denoted as C-3, and catalyst characterization data are shown in Table 1.
(4) reduction and with nitrogen substance haptoreaction：Activation of catalyst carries out in fixed bed or fluidized-bed reactor, claims
Take 8.6g catalyst precarsors to be put into activated reactor, preferable gas composition, air speed and at a temperature of kept for certain time, so
Catalyst is transferred in glove box to room temperature by postcooling, added under oxygen-free environment containing the rebasing oil of 150g (polyalphaolefin, Mobil,
In reaction kettle 4#), the catalyst after activating is used for follow-up performance evaluation.Activation condition is：0.2MPa, containing 0.005 body
The lower 400 DEG C of reduction 4h of product % ammonias, the argon atmosphere of 70 volume % hydrogen is activated, and is denoted as C-6, catalyst characterization data are shown in
Table 1.
Embodiment 7
(1) prepared by cobalt nano-particle：Under High Purity Nitrogen protection, added into the there-necked flask with stirring 610ml distilled water,
104.0g protective agents PEG-6000 (Chinese medicines group, analysis are pure) and 5.65g cobalt chloride hexahydrates (lark prestige, analysis are pure), are treated solid
Body slow mechanism dissolved, stablizes 15 minutes under the conditions of ice-water bath, will contain 20g hydrazine hydrates (Beijing reagent, content using syringe
50%, analysis it is pure) aqueous solution 32g fast injections into there-necked flask, after the reaction was continued 30 minutes, reaction solution is transferred to centrifugation
Pipe is centrifuged at a high speed, and then carries out centrifuge washing to nano cobalt granule with distilled water 6 times, and each dosage 50mL, obtains
Nano cobalt granule.Using ICP/AES methods (RIPP 127-90) measure, wherein the total weight content of other metals is low in addition to cobalt
In 100ppm.Finally obtained nano cobalt granule is dispersed in 30mL absolute ethyl alcohols and obtains nanometer cobalt dispersion liquid.TEM, which is measured, to be received
Rice cobalt granule particle size integrated distribution is in 10-15nm.
(2) Passivation Treatment：Under static conditions, the mixed gas of oxygen and nitrogen is passed through above-mentioned cobalt metallic particles dispersion liquid
In, the flow of 5L/h keeps 1h, and oxygen content is 0.5 volume % in mixed gas.
(3) load：2.0g silica-oxidation will be added after metallic cobalt nanoparticulate dispersion ultrasonic disperse after above-mentioned passivation
Aluminium microballoon (70~150 microns of particle diameter, 250 meters of specific surface area2/ gram), the dry 24h of 100 DEG C of vacuum drying chamber is obtained after removing solvent
To loaded nano Co catalysts, C-7 is denoted as, catalyst characterization data are shown in Table 1.
(4) reduction and with nitrogen substance haptoreaction：Activation of catalyst carries out in fixed bed or fluidized-bed reactor, claims
Take 8.6g catalyst precarsors to be put into activated reactor, preferable gas composition, air speed and at a temperature of kept for certain time, so
Catalyst is transferred in glove box to room temperature by postcooling, added under oxygen-free environment containing the rebasing oil of 150g (polyalphaolefin, Mobil,
In reaction kettle 4#), the catalyst after activating is used for follow-up performance evaluation.Activation condition is：0.2MPa, containing 0.005 body
The lower 400 DEG C of reduction 4h of product % methylamines, the argon atmosphere of 70 volume % hydrogen is activated, and is denoted as C-1, catalyst characterization data are shown in
Table 1.
Catalyst performance evaluation
Embodiment 8：Evaluate embodiment
Performance evaluation carries out in continuous mixing kettle, and concrete operations include：By containing catalyst, rebasing oily autoclave from
Glove box takes out, and loads onto reaction kettle and is ready for performance evaluation, is first passed through nitrogen into line replacement and checks air-tightness.In flowing nitrogen
110 DEG C are warming up under gas, then is passed through synthesis gas and continues to heat up, synthesis gas composition is：H2:CO:N2=56:28:16, control pressure
Power is 2.5MPa, 220~240 DEG C of reaction temperature, 1000 revs/min of mixing speed, when reaction 24 is small after utilize online gas-chromatography
Tail gas composition analysis is carried out, calculates reactivity worth.The reaction was continued, when 240 is small and when 480 is small after utilize online gas phase color
Spectrum carries out tail gas composition analysis, calculates reactivity worth, and evaluation result is shown in Table 2 and table 3.
Catalyst performance index includes catalytic activity, methane selectively, C5+ selectivity and stability, wherein catalytic activity
It is defined as：Unit interval, the CO of every gram of catalyst conversion accounted for CO mole percents total in addition system；Methane selectively defines
For：The CO for being converted into methane accounts for the mole percent for having converted CO；C5+ selectivity is defined as：Generate C5The CO of+hydro carbons, which is accounted for, have been turned
Change the mole percent of CO；Stability represents that catalyst passes through catalytic activity reduction degree after long-time successive reaction, reduces
Fewer, stability is higher, conversely, stability is poorer.Specific evaluation result is shown in Table 2 and table 3, relative activity computational methods in table：
On the basis of the catalytic activity of R-1, the numerical value that the catalytic activity of remaining catalyst obtains by comparison is corresponding catalyst
Relative activity.
Table 1
Table 2
Table 3
It can be seen from the results in table 2 compared with the catalyst that the prior art obtains, catalyst provided by the invention is urged
Change activity is high, methane selectively is low, C5+ high selectivity；It is in table 3 the result shows that：Catalyst provided by the invention has higher
Stability.
Claims (12)
- A kind of 1. loaded nano Co catalysts, it is characterised in that cobalt content on the basis of catalyst and based on the element for 3~ 65 weight %, the preparation method of the catalyst include：(1) nano cobalt granule is prepared, obtained nano cobalt granule is scattered in In solvent, nanometer cobalt dispersion liquid is obtained；(2) the nanometer cobalt dispersion liquid impregnated carrier obtained with step (1), and to impregnated load Body is dried；(3) step (2) dried product is reduced；It is characterized in that, before the reduction, at the same time Or the step of including step (2) the dried product and nitrogen or nitrogenous compound haptoreaction afterwards, the contact are anti- The condition answered make it that the nitrogen content in final catalyst based on the element is to less than or equal to 0.2 weight % more than 0.
- 2. catalyst according to claim 1, it is characterised in that on the basis of catalyst and in terms of cobalt element, catalyst Middle cobalt content is 5~50 weight %；The catalytic condition make it that the nitrogen content in final catalyst based on the element is 0.01~0.1 weight %.
- 3. catalyst according to claim 1, it is characterised in that the reduction and described contacted with nitrogen or nitrogenous compound Reaction is carried out at the same time, including by the gaseous mixture or reducing gas of step (2) the dried product and reducing gas and nitrogen and The gaseous mixture haptoreaction of nitrogenous compound, the reducing gas are H2, CO, the one or more in small molecule hydro carbons, it is described In gaseous mixture the content of nitrogen or nitrogenous compound be more than 0 to less than or equal to 30 volume %, the reducing gas content be more than Equal to 10 volume % to 100 volume % are less than, surplus is inert gas；It is described reduction and with nitrogen or nitrogenous compound haptoreaction Operating condition include：Temperature is 100~800 DEG C, and the time is 0.5~144h, and pressure is 0.1~4MPa；Or it is described carried out with nitrogen or nitrogenous compound haptoreaction before or after the reduction, it is described with nitrogen or nitrogen Compound haptoreaction is included step (2) the dried product and nitrogenous gas haptoreaction, the catalytic behaviour Include as condition：Temperature is 0 DEG C~800 DEG C, and pressure is 0.1~4MPa, and the time is 0.5~144h；Wherein, contain in nitrogenous gas There are nitrogen or a nitrogenous compound, the content of nitrogen or nitrogenous compound is to less than or equal to 30 volume %, surplus more than 0 in nitrogenous gas For inert gas；The nitrogenous compound is the one or more in ammonia, hydrazine, organic amine.
- 4. catalyst according to claim 3, it is characterised in that the reduction and described contacted with nitrogen or nitrogenous compound Reaction is carried out at the same time, and the operating condition includes：Temperature is 200~700 DEG C, and pressure is 0.2~3MPa, and the time is 1~96h； Or it is described carried out with nitrogen or nitrogenous compound haptoreaction before or after the reduction, it is described with nitrogen or nitrogenous compound The operating condition of haptoreaction and the reduction including independently：Temperature is 100~700 DEG C, and pressure is 0.2~3MPa, Time is 1~96h.
- 5. catalyst according to claim 3, it is characterised in that in the gaseous mixture, the content of nitrogen or nitrogenous compound For 0.001~20 volume %, the reducing gas content is 20~80 volume %, and surplus is inert gas；The nitrogenous gas The content of middle nitrogen or nitrogenous compound is 0.001~20 volume %, and surplus is inert gas.
- 6. according to the catalyst described in claim 3~5 any one, it is characterised in that the nitrogenous compound methylamine.
- 7. catalyst according to claim 1, it is characterised in that the grain of the nano cobalt granule obtained in the step (1) Footpath is 1~20nm；Nanometer cobalt content is 1~10g nanometer cobalts/100mL solvents in the dispersion liquid that the step (1) obtains, described Solvent is in water, methanol, ethanol, propyl alcohol, acetic acid, lactic acid, citric acid, polyethylene glycol, polyvinylpyrrolidone in dispersion liquid One or more.
- 8. catalyst according to claim 1, it is characterised in that the step (1) disperses obtained nano cobalt granule After solvent and before step (2), the step of being passed through oxygen-containing gas into nanometer cobalt dispersion liquid is further included, it is described to nanometer cobalt The operating condition of oxygen-containing gas is passed through in dispersion liquid to be included：Temperature -10~60 DEG C, the time is 0.01~24h, with nanometer cobalt quality On the basis of, the volume space velocity of oxygen-containing gas is 0.2~20Lg-1h-1.
- 9. catalyst according to claim 8, it is characterised in that be passed through oxygen-containing gas in the dispersion liquid to nanometer cobalt Operating condition includes：0~50 DEG C of temperature, the time is 0.1~4h, on the basis of nanometer cobalt quality, the volume space velocity of oxygen-containing gas For 1~10Lg-1h-1。
- 10. catalyst according to claim 8 or claim 9, it is characterised in that the oxygen-containing gas for oxygen with selected from nitrogen, One or more of mixed gas in inert gas, oxygen content is no more than 21 volume % in the oxygen-containing gas.
- 11. catalyst according to claim 10, it is characterised in that 0.01~5 body of oxygen content in the oxygen-containing gas Product %.
- 12. application of any one of claim 1~11 catalyst in Fischer-Tropsch synthesis, including by carbon monoxide and hydrogen The mixture of gas and the catalyst haptoreaction, reaction condition are：160~350 DEG C, 1~8MPa of pressure of temperature, hydrogen and one The molar ratio 0.4~2.5 of carbonoxide：1,200~40000h of gas volume air speed-1。
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| CN1620411A (en) * | 2002-01-29 | 2005-05-25 | 埃克森美孚研究工程公司 | Fischer-tropsch catalyst enhancement |
| CN101274277A (en) * | 2008-05-19 | 2008-10-01 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing intermediate distillate oil used for slurry bed and preparation and application |
| CN101920201A (en) * | 2009-06-09 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing cobalt-based Fischer-Tropsch synthesis catalyst |
| CN102309991A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for cobalt-based Fischer-Tropsch synthesis catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1620411A (en) * | 2002-01-29 | 2005-05-25 | 埃克森美孚研究工程公司 | Fischer-tropsch catalyst enhancement |
| CN101274277A (en) * | 2008-05-19 | 2008-10-01 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing intermediate distillate oil used for slurry bed and preparation and application |
| CN101920201A (en) * | 2009-06-09 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing cobalt-based Fischer-Tropsch synthesis catalyst |
| CN102309991A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for cobalt-based Fischer-Tropsch synthesis catalyst |
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