CN108479834A - A kind of fischer-tropsch synthetic catalyst and preparation method thereof - Google Patents
A kind of fischer-tropsch synthetic catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN108479834A CN108479834A CN201810225545.0A CN201810225545A CN108479834A CN 108479834 A CN108479834 A CN 108479834A CN 201810225545 A CN201810225545 A CN 201810225545A CN 108479834 A CN108479834 A CN 108479834A
- Authority
- CN
- China
- Prior art keywords
- fischer
- carrier
- tropsch synthetic
- auxiliary agent
- synthetic catalyst
- Prior art date
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- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 145
- 238000002360 preparation method Methods 0.000 title claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002091 nanocage Substances 0.000 claims abstract description 45
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 26
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 11
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 85
- 230000015572 biosynthetic process Effects 0.000 claims description 79
- 238000003786 synthesis reaction Methods 0.000 claims description 79
- 239000012752 auxiliary agent Substances 0.000 claims description 72
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 42
- 239000011261 inert gas Substances 0.000 claims description 33
- 238000002161 passivation Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 23
- 229910000765 intermetallic Inorganic materials 0.000 claims description 19
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 17
- 239000001103 potassium chloride Substances 0.000 claims description 17
- 235000011164 potassium chloride Nutrition 0.000 claims description 17
- 159000000000 sodium salts Chemical class 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 150000004696 coordination complex Chemical class 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 230000003993 interaction Effects 0.000 abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 6
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000004873 anchoring Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 89
- 238000006243 chemical reaction Methods 0.000 description 64
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 60
- 239000007789 gas Substances 0.000 description 54
- 235000019441 ethanol Nutrition 0.000 description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 42
- 239000001301 oxygen Substances 0.000 description 42
- 229910052760 oxygen Inorganic materials 0.000 description 42
- 239000000047 product Substances 0.000 description 42
- 229910052799 carbon Inorganic materials 0.000 description 40
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 26
- 229910002091 carbon monoxide Inorganic materials 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 230000005540 biological transmission Effects 0.000 description 23
- 238000001035 drying Methods 0.000 description 23
- 238000007598 dipping method Methods 0.000 description 22
- 238000010792 warming Methods 0.000 description 20
- 229960002413 ferric citrate Drugs 0.000 description 19
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 19
- 230000004224 protection Effects 0.000 description 18
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 14
- 238000004587 chromatography analysis Methods 0.000 description 12
- 239000008246 gaseous mixture Substances 0.000 description 12
- 238000011065 in-situ storage Methods 0.000 description 12
- 239000013589 supplement Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000004044 response Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 230000002459 sustained effect Effects 0.000 description 11
- 150000001860 citric acid derivatives Chemical class 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000004317 sodium nitrate Substances 0.000 description 7
- 235000010344 sodium nitrate Nutrition 0.000 description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229910021260 NaFe Inorganic materials 0.000 description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 229940011182 cobalt acetate Drugs 0.000 description 3
- -1 ethylene, propylene Chemical group 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000000052 vinegar Substances 0.000 description 3
- 235000021419 vinegar Nutrition 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 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 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 description 1
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- DKKCQDROTDCQOR-UHFFFAOYSA-L Ferrous lactate Chemical compound [Fe+2].CC(O)C([O-])=O.CC(O)C([O-])=O DKKCQDROTDCQOR-UHFFFAOYSA-L 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000004645 aluminates 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
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 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
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- QXOLLBTXUCQAEQ-UHFFFAOYSA-N cobalt;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Co].OC(=O)CC(O)(C(O)=O)CC(O)=O QXOLLBTXUCQAEQ-UHFFFAOYSA-N 0.000 description 1
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000004225 ferrous lactate Substances 0.000 description 1
- 235000013925 ferrous lactate Nutrition 0.000 description 1
- 229940037907 ferrous lactate Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire 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
-
- B01J35/393—
-
- B01J35/396—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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
The present invention provides a kind of fischer-tropsch synthetic catalysts, including carrier and active component, the carrier is N doping hollow nano cages, the Active components distribution is on the surface of carrier, the active component is the nano particle of metal oxide, the metal oxide is iron oxide or cobalt oxide, and the percentage that the load capacity of the metal oxide accounts for carrier with metallic element is calculated as 5~51wt.%, and the nitrogen content in the N doping hollow nano cages is 5~20at.%.The present invention is using the higher N doping hollow nano cages of nitrogen content as carrier, nitrogen-atoms in carrier has anchoring effect to metal oxide, the interaction of carrier and active component can be improved, and nitrogen-atoms has alkalinity, improve the surface alkalinty of carrier, it is combined simultaneously with the peculiar structure and active component of carrier, has obtained the fischer-tropsch synthetic catalyst that high selectivity, anti-sintering property are good and stability is high.
Description
Technical field
The present invention relates to F- T synthesis technical fields more particularly to a kind of fischer-tropsch synthetic catalyst and preparation method thereof.
Background technology
F- T synthesis (Fischer Tropsch Synthesis) refers under certain condition by synthesis gas (H2And CO) turn
The heterogeneous catalytic reaction process of hydrocarbon is turned to, can be used for producing low-carbon alkene (C= 2-C4 =), gasoline, diesel oil, paraffin
And the products such as other oxygen-bearing organic matters.Raw material of synthetic gas derives from a wealth of sources, can be by coal, natural gas, shale gas and biomass material
Equal conversions obtain.By F- T synthesis by the indirect reformers such as coal, natural gas, shale gas and biomass material be fuel and chemical industry
Product has stronger development prospect, the especially Optimum utilization to fossil energies such as coal, natural gas, shale gas and country
The adjustment of energy resource structure has important strategic importance.
C2 =-C4 =(ethylene, propylene and butylene) is important basic chemical industry raw material, with the rapid growth of global economy,
Yield is already more than 2.5 hundred million tons, and price also remains high always.Currently, C2 =-C4 =It is mainly derived from oil, but with the whole world
The increasingly depleted of petroleum resources, the importance for researching and developing new non-petroleum technology path are increasingly prominent.And utilize F- T synthesis system low
Carbon olefin is the alternative route for having larger application prospect, but develops C2 =-C4 =High selectivity and the good novel Fischer-Tropsch of stability
Synthetic catalyst is the key that FTO large-scale applications.
Currently, common fischer-tropsch synthetic catalyst is predominantly with oxide (such as Al2O3、SiO2Deng) be carrier iron system urge
Agent, but since the active force of carrier and active component is stronger, active component is difficult to restore and be not easy to be formed with catalytic activity
Cementite or reaction process in cementite be easily oxidized to inactive silicate and aluminate etc., lead to catalyst performance
Can be unstable, it is easy to inactivate.Recent studies indicate that adjustable with high-specific surface area, superior chemical stability and pore structure
The features such as new carbon (such as carbon nanotube (CNT), carbon nano-fiber (CNF), ordered mesopore carbon and graphene) load
The catalyst of Fe shows higher C2 =-C4 =Selectivity and catalytic activity, but the stability of this kind of catalyst is still poor, by
Weaker in carbon material carrier and the interaction of iron active component, this kind of catalyst is easy sintering, and then causes catalyst short
Inactivation is serious in time.
Invention content
The purpose of the present invention is to provide a kind of fischer-tropsch synthetic catalysts and preparation method thereof.Fischer-Tropsch provided by the present invention
The excellent in stability of synthetic catalyst.
To achieve the above object, described the present invention provides a kind of fischer-tropsch synthetic catalyst, including carrier and active component
Carrier is N doping hollow nano cages, and the Active components distribution is aoxidized in the surface of carrier, the active component for metal
The nano particle of object, the metal oxide are iron oxide or cobalt oxide, and the load capacity of the metal oxide is with metallic element
The percentage for accounting for carrier is calculated as 5~51wt.%, and the nitrogen content in the N doping hollow nano cages is 5~20at.%.
Preferably, the load capacity of the metal oxide is 10~35wt.%.
Preferably, the grain size of the metal oxide is 2~30nm.
Preferably, the nitrogen content in the N doping hollow nano cages is 7~16at.%.
Preferably, the fischer-tropsch synthetic catalyst further includes the first auxiliary agent, and first auxiliary agent is Na+Or K+, described first
The percentage that the load capacity of auxiliary agent accounts for carrier with the first auxiliary agent is calculated as 0.5~4wt.%.
Preferably, the fischer-tropsch synthetic catalyst further includes the second auxiliary agent, second auxiliary agent be element sulphur, described second
The percentage that the load capacity of auxiliary agent accounts for carrier with the second auxiliary agent is calculated as 0.1~0.5wt.%.
The present invention also provides the preparation methods of the fischer-tropsch synthetic catalyst described in above-mentioned technical proposal, including walk as follows
Suddenly：
(1) N doping hollow nano cages are provided；
(2) the N doping hollow nano cages are impregnated in the ethanol water of metallic compound, obtains Fischer-Tropsch conjunction
At catalyst precursor；The metallic compound is the metal salt or metal complex of iron or cobalt；
(3) the fischer-tropsch synthetic catalyst presoma is obtained into fischer-tropsch synthetic catalyst successively through the first roasting and passivation；
It (4), will when the fischer-tropsch synthetic catalyst includes the first auxiliary agent or includes simultaneously the first auxiliary agent and the second auxiliary agent
The fischer-tropsch synthetic catalyst heat treatment, then mixes with the ethanol water of sodium salt or sylvite, obtains the expense added with auxiliary agent
Tropsch synthesis catalyst presoma；The sodium salt or sylvite are at least one of sulfate, hydrochloride and nitrate；
By the fischer-tropsch synthetic catalyst presoma added with auxiliary agent through the second roasting, the Fischer-Tropsch added with auxiliary agent is obtained
Synthetic catalyst.
Preferably, first roasting and the second roasting are independently in N2Or it is carried out in inert gas, first roasting
Temperature with the second roasting is independently 300~600 DEG C, and time of first roasting and the second roasting is independently 0.5~
6h。
Preferably, the passivation carries out in oxygenous inert gas flow, and the time of the passivation is 0.5~2h, institute
The temperature for stating passivation is 15~40 DEG C.
Preferably, the heat treatment is carried out in vacuum condition, and the temperature of the heat treatment is 200~250 DEG C, at the heat
The time of reason is 2~2.5h.
The present invention provides a kind of fischer-tropsch synthetic catalyst, including carrier and active component, the carrier is that N doping is empty
Heart nano cages, for the Active components distribution on the surface of carrier, the active component is the nano particle of metal oxide, institute
It is iron oxide or cobalt oxide to state metal oxide, and the load capacity of the metal oxide is accounted for by metallic element in terms of the percentage of carrier
For 5~51wt.%, the nitrogen content in the N doping hollow nano cages is 5~20at.%.The present invention is higher with nitrogen content
N doping hollow nano cages be carrier, the nitrogen-atoms in carrier has anchoring effect to metal oxide, and carrier can be improved
With the interaction of active component, and nitrogen-atoms have alkalinity, improve the surface alkalinty of carrier, while peculiar with carrier
Structure and active component combine, and have obtained the F- T synthesis that target product selectivity is high, anti-sintering property is good and stability is high and have urged
Agent.The experimental results showed that using fischer-tropsch synthetic catalyst provided by the present invention in reaction temperature for 200~350 DEG C, react
Pressure is 1~20bar, and synthesis gas air speed carries out Fischer-Tropsch synthesis under conditions of being 1000~20000mL/ (hg), is catalyzed
After agent uses 50~200h, conversion ratio and selectivity are not decreased obviously, and the transmitted electron before and after comparative catalyst's use
Microscope (TEM) phenogram, does not observe apparent carbon deposition phenomenon.
Description of the drawings
TEM photos before and after 1 gained catalyst reaction of Fig. 1 embodiments；
1 gained catalyst of Fig. 2 embodiments uses the grain size distribution of front and rear surfaces active component.
Specific implementation mode
The present invention provides a kind of fischer-tropsch synthetic catalyst, including carrier and active component, the carrier is that N doping is empty
Heart nano cages, for the Active components distribution on the surface of carrier, the active component is the nano particle of metal oxide, institute
It is iron oxide or cobalt oxide to state metal oxide, and the load capacity of the metal oxide is accounted for by metallic element in terms of the percentage of carrier
For 5~51wt.%, the nitrogen content in the N doping hollow nano cages is 5~20at.%.
In the present invention, the specific surface area of the N doping hollow nano cages is preferably 500~2500m2/ g, more preferably
For 1600~2000m2/g；It is preferably 0.5~5cm that the hole of the N doping hollow nano cages, which holds,3/ g, more preferably 3~
5cm3/g；The grain size of the N doping hollow nano cages is preferably 5~100nm, more preferably 5~30nm.In the present invention,
Larger specific surface area is conducive to the load of active component, and larger hole has conducive to the progress of mass transfer in reaction process.
In the present invention, the nitrogen content in the N doping hollow nano cages be 5~20at.%, preferably 7~
16at.%.Nitrogen-atoms in carrier of the present invention has anchoring effect to metal oxide, and phase of the carrier with active component can be improved
Interaction, and nitrogen-atoms has alkalinity, improves the surface alkalinty of carrier, at the same with the peculiar structure and active component of carrier
In conjunction with helping to improve the anti-sintering property of catalyst.
The present invention is not particularly limited the source of N doping hollow nano cages, in embodiments of the present invention, the nitrogen
Doped hollow nano cages are prepared preferably by method disclosed in Chinese patent CN102530922A.
In the present invention, the load capacity of the metal oxide accounted for metallic element carrier percentage be calculated as 5~
51wt.%, preferably 10~35wt.%, more preferably 20~25wt.%.
In the present invention, the grain size of the metal oxide is preferably nanoscale, more preferably 2~30nm.In the present invention
In, the active component plays main catalytic action in the catalyst.
In the present invention, the fischer-tropsch synthetic catalyst preferably further includes the first auxiliary agent, and first auxiliary agent is preferably Na+
Or K+；The load capacity of first auxiliary agent is preferably 0.5~4wt.% in terms of the percentage that the first auxiliary agent accounts for carrier, more preferably
1~3wt.%；First auxiliary agent is preferably added in catalyst in a salt form；The salt includes nitrate, hydrochloride, vinegar
At least one of hydrochlorate, citrate, formates and carbonate.In the present invention, first auxiliary agent has alkalinity, can
Promote the Dissociative of CO, and then is conducive to improve the activity of catalyst and the selectivity of alkene.
In the present invention, the fischer-tropsch synthetic catalyst preferably further includes the second auxiliary agent, and second auxiliary agent is element sulphur；
The load capacity of second auxiliary agent in terms of the percentage that the second auxiliary agent accounts for carrier be preferably 0.1~0.5wt.%, more preferable 0.2~
0.4wt.%；The element sulphur is preferably carried in the form of sulfate on carrier.In the present invention, second auxiliary agent can
The chain growth probability for reducing reaction, improves the selectivity of alkene, and inhibit carbon distribution.
The present invention also provides the preparation methods of the fischer-tropsch synthetic catalyst described in above-mentioned technical proposal, including walk as follows
Suddenly：
(1) N doping hollow nano cages are provided；
(2) the N doping hollow nano cages are impregnated in the ethanol water of metallic compound, obtains Fischer-Tropsch conjunction
At catalyst precursor；The metallic compound is the metal salt or metal complex of iron or cobalt；
(3) the fischer-tropsch synthetic catalyst presoma is obtained into fischer-tropsch synthetic catalyst successively through the first roasting and passivation.
It (4), will when the fischer-tropsch synthetic catalyst includes the first auxiliary agent or includes simultaneously the first auxiliary agent and the second auxiliary agent
The fischer-tropsch synthetic catalyst heat treatment, then mixes with the ethanol water of sodium salt or sylvite, obtains the expense added with auxiliary agent
Tropsch synthesis catalyst presoma；The sodium salt or sylvite are at least one of sulfate, hydrochloride and nitrate；
By the fischer-tropsch synthetic catalyst presoma added with auxiliary agent through the second roasting, the Fischer-Tropsch added with auxiliary agent is obtained
Synthetic catalyst.
Present invention firstly provides N doping hollow nano cages.
The present invention is not particularly limited the source of N doping hollow nano cages, in embodiments of the present invention, the nitrogen
Doped hollow nano cages are prepared preferably by method disclosed in Chinese patent CN102530922A.
The present invention impregnates the N doping hollow nano cages in the ethanol water of metallic compound, obtains Fischer-Tropsch
Synthetic catalyst presoma.
In the present invention, the metallic compound is the metal salt or complex compound of iron or cobalt；The metallic compound is iron
Metal salt or complex compound when, preferably ferric nitrate, ferric citrate, ironic citrate, ferric acetate, ferric acetyl acetonade, ferric sulfate,
Ferric phosphate, ferrocene, ferric trichloride, ferrous acetate, ferrous nitrate, ferrous sulfate, ferrous lactate, frerrous chloride and citric acid are sub-
At least one of iron；When the metallic compound is the metal salt or complex compound of cobalt, preferably cobalt nitrate, citric acid cobalt, vinegar
In sour cobalt, acetylacetone cobalt, cobaltous sulfate, cobalt phosphate, cobaltic chloride, acetic acid Asia cobalt, colbaltous nitrate, Cobaltous sulfate and cobalt chloride
At least one.
In the present invention, in the ethanol water of the metallic compound concentration of metallic compound be preferably 0.02~
0.5mol/L, more preferably 0.1~0.3mol/L；The volumn concentration of ethyl alcohol in the ethanol water of the metallic compound
Preferably 10~50%, more preferably 30~40%.In the present invention, use ethanol water for the solvent of metallic compound,
Ethyl alcohol can reduce the surface tension of solution, and the solution of metallic compound can be promoted to evenly spread to carrier surface.
In the present invention, the volume of the ethanol water of the quality and metallic compound of the N doping hollow nano cages
The ratio between preferably 1g:10~50mL, more preferably 1g:25~35mL.
The ethanol water of the N doping hollow nano cages and metallic compound is preferably stirred by the present invention
It is even, then impregnated.In the present invention, the speed of the stirring is preferably 50~200r/min；The time of the stirring is preferred
For 0.5~1h.
In the present invention, the dipping process preferably stands dipping；The time of the dipping is preferably 5~for 24 hours, it is more excellent
It is selected as 10~18h；The present invention is not particularly limited the temperature of the dipping, and in embodiments of the present invention, the dipping is preferred
For room temperature immersion.
After the completion of dipping, the present invention preferably dries the product of the dipping, obtains fischer-tropsch synthetic catalyst presoma.
In the present invention, the product of dipping is directly dried, in drying process, solvent gradually volatilizees, metallic compound without filtering
In nitrogen-doped carbon nanocages surface homogeneous nucleation, be conducive to the uniformity for improving metallic compound dispersion.
In the present invention, the temperature of the product drying of the dipping is preferably 50~120 DEG C, more preferably 80~100 DEG C；
The time of impregnation product drying is preferably 1~for 24 hours, more preferably 5~20h, most preferably 10~15h；The dipping production
The mode of object drying is preferably forced air drying.
After obtaining fischer-tropsch synthetic catalyst presoma, the present invention is by the fischer-tropsch synthetic catalyst presoma successively through first
Roasting and passivation, obtain fischer-tropsch synthetic catalyst.
In the present invention, first roasting is preferably in N2Or it is carried out in inert gas；The temperature of first roasting is excellent
It is selected as 300~600 DEG C, more preferably 380~500 DEG C；The time of first roasting is preferably 0.5~6h, more preferably 2~
4h；The time of first roasting is preferably from meter when device temperature is warming up to roasting required temperature；The present invention is to being warming up to roasting
The heating rate for burning required temperature is not particularly limited, in embodiments of the present invention, described using conventional heating rate
Heating rate is preferably 1~20 DEG C/min.In the present invention, after the first roasting, the gold in fischer-tropsch synthetic catalyst presoma
Belong to compound (metal salt or metal complex of iron or cobalt) to be converted into metal carbides or simple substance (compound of iron is converted into carbon
Change iron, the compound of cobalt is converted into simple substance cobalt).
After the completion of first roasting, the product of the first roasting is passivated by the present invention, obtains fischer-tropsch synthetic catalyst.
In the present invention, the passivation preferably carries out in oxygenous inert gas flow；The time of the passivation is preferred
For 0.5~2h, more preferably 1~1.5h；The temperature of the passivation is preferably 15~40 DEG C, more preferably 20~30 DEG C.This hair
The rate of temperature fall that the bright temperature to first roasting is down to passivation required temperature is not particularly limited, using conventional cooling speed
Rate, in embodiments of the present invention, the cooling are preferably Temperature fall.In the present invention, in the product of the first roasting
Metal carbides are passivated to be converted into metal oxide.
In the present invention, the volume content of oxygen is preferably 0.5~2% in the oxygen containing inert gas flow, more preferably
It is 1~1.5%.It is passivated under the conditions of lower oxygen content, metal carbides can be reduced and be converted into metal oxide
Reaction rate reduces exothermic heat of reaction, prevents carrier from burning.
In the present invention, the flow of the oxygen containing inert gas flow is preferably 50~500mL/min.
After completing passivation, the present invention preferably grinds the product of the passivation, obtains fischer-tropsch synthetic catalyst.
The present invention is not particularly limited the mode of the grinding, will assemble that pockets of catalyst is levigate will preferably to urge
Agent is ground to less than 0.5mm.
When the fischer-tropsch synthetic catalyst includes the first auxiliary agent or includes simultaneously the first auxiliary agent and the second auxiliary agent, the present invention
The fischer-tropsch synthetic catalyst is heat-treated, is then mixed with the ethanol water of sodium salt or sylvite, obtaining load has auxiliary agent
Fischer-tropsch synthetic catalyst presoma；There is the fischer-tropsch synthetic catalyst presoma of auxiliary agent to be roasted through second described load, is born
It is loaded with the fischer-tropsch synthetic catalyst of auxiliary agent.
In the present invention, the sodium salt or sylvite are at least one of sulfate, hydrochloride, nitrate and acetate；
When sodium salt or sylvite are sulfate, gained catalyst is while the F- T synthesis including the first auxiliary agent and the second auxiliary agent is catalyzed
Agent.
In the present invention, the heat treatment of the fischer-tropsch synthetic catalyst is preferably carried out in vacuum condition, the heat treatment
Vacuum degree is preferably 0.1~1000Pa；The temperature of the heat treatment is preferably 200~250 DEG C；The time of the heat treatment is preferred
For 2~2.5h.In the present invention, it after being heat-treated to fischer-tropsch synthetic catalyst, then mixes with the ethanol water of auxiliary agent, Neng Gouxian
The other impurity for removing metal oxide surface absorption after the ethanol solution for adding auxiliary agent, are conducive to reinforcing aids and metal oxygen
The interaction of compound, and then catalytic performance can be improved.
After completing heat treatment, the present invention is water-soluble by the fischer-tropsch synthetic catalyst of the heat treatment and the ethyl alcohol of sodium salt or sylvite
Liquid mixes, and obtains the fischer-tropsch synthetic catalyst presoma added with auxiliary agent.
In the present invention, in the ethanol water of the sodium salt or sylvite the concentration of sodium salt or sylvite be preferably 0.005~
0.1mol/L, more preferably 0.005~0.06mol/L；The volume basis of ethyl alcohol in the ethanol water of the sodium salt or sylvite
Content is preferably 10~50%, and more preferably 30~40%.In the present invention, use ethanol water for the molten of sodium salt or sylvite
Agent, ethyl alcohol can reduce the surface tension of solution, and the solution of sodium salt or sylvite can be promoted to evenly spread to carrier surface.
In the present invention, the mixing of the ethanol water of the fischer-tropsch synthetic catalyst with sodium salt or sylvite of the heat treatment is excellent
It is selected as mechanical agitation mixing；The rotating speed of the mixing is preferably 50~200r/min；The time of the mixing is preferably 12~
24h。
After the completion of mixing, the present invention preferably dries mix products, before obtaining the fischer-tropsch synthetic catalyst added with auxiliary agent
Drive body.
In the present invention, the drying temperature of the mix products is preferably 80~120 DEG C, more preferably 100 DEG C；It is described dry
The dry time is preferably 1~3h, more preferably 2h；The mode of the drying is preferably forced air drying.
After the completion of the drying of mix products, the present invention is by the fischer-tropsch synthetic catalyst presoma added with auxiliary agent through the second roasting
It burns, obtains the fischer-tropsch synthetic catalyst added with auxiliary agent.
In the present invention, second roasting is preferably in N2Or it is carried out in inert gas；The temperature of second roasting is excellent
It is selected as 300~600 DEG C, more preferably 380~500 DEG C；The time of second roasting is preferably 0.5~6h, more preferably 2~
4h；The time of second roasting is preferably from meter when device temperature is warming up to roasting required temperature；The present invention is to being warming up to roasting
The heating rate for burning required temperature is not particularly limited, in embodiments of the present invention, described using conventional heating rate
Heating rate is preferably 1~20 DEG C/min.In the present invention, the second roasting can be by the presoma of auxiliary agent sylvite or sodium salt point
Solution improves the interaction of auxiliary agent and active component.
After the completion of second roasting, product of the present invention preferably by the second roasting is cooled to room temperature, and obtaining load has auxiliary agent
Fischer-tropsch synthetic catalyst.The present invention is not particularly limited the rate of the cooling, can be arbitrary cooling rate, in the present invention
In embodiment, the cooling is preferably natural cooling.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
(1) provide nitrogen content be 12at.%, specific surface area 1800m2/ g, Kong Rongwei 4.2cm3/ g, grain size be 10~
The N doping hollow nano cages (referred to as NCNC) of 30nm；
(2) 1.45g ferric citrates are mixed with the ethyl alcohol deionized water solution that 15mL ethyl alcohol volumetric concentrations are 20%, is obtained
To the ethanol water of ferric citrate；0.60gNCNC is mixed with the ethanol water of the ferric citrate, in 150r/
Min rotating speeds stir 0.5h, are then stored at room temperature dipping 6h；Drying box of the products obtained therefrom at 80 DEG C will be impregnated and dry 6h, obtain expense
Tropsch synthesis catalyst presoma (abbreviation Fe/NCNC presomas)；
(3) by the Fe/NCNC presomas under Ar air-flow protections, 380 DEG C of roasting 2h is warming up to, are then naturally cooled to
Room temperature；It then passes to the oxygen-containing inert gas that oxygen volume content is 1% and is passivated 0.5h in room temperature, the oxygen-containing inert gas
Flow is 200mL/min；Passivation products obtained therefrom is ground, fischer-tropsch synthetic catalyst (abbreviation Fe/NCNC), the Fe/ are obtained
The load capacity of iron oxide is accounted for the mass percent of carrier with Fe and is calculated as 27.7wt.% in NCNC.
Fe/NCNC obtained by 100mg the present embodiment is put into Fischer-Tropsch synthesis device, H is passed through with the flow of 20mL/min2,
In 400 DEG C of in-situ reducing 3h；After temperature of reactor is down to 350 DEG C, stopping is passed through H2, start to be passed through synthesis gas, the synthesis
Gas is H2It is 1 with CO volume ratios:1 gaseous mixture maintains 350 DEG C, is 1bar in pressure, synthesis gas air speed is 3000mL/ (h
G) condition carries out Fischer-Tropsch synthesis.
Gas after being reacted using chromatography, stable reaction (please supplement and start to be reacted to when stablizing required after 20h
Between), the conversion ratio of carbon monoxide is 3.5%, low-carbon alkene (C2 =-C4 =) selectivity be 54%, the selectivity of methane is
24%；Activity has no decline after sustained response 60h, and in 60h, the conversion ratio of carbon monoxide is 3.6%, low-carbon alkene (C2 =-C4 =) selectivity be 54%, the selectivity of methane is 24%；After reacting 200h, the conversion ratio of carbon monoxide is 3.8%, low-carbon alkene
Hydrocarbon (C2 =-C4 =) selectivity be 54%, the selectivity of methane is 25%.
Transmission electron microscope photo before catalyst reaction obtained by the present embodiment and after reaction 200h is as shown in Figure 1, urge
After agent uses 200h, there is not apparent carbon distribution in the surface of catalyst；To reacting front and back catalyst surface active component
Particle carries out random statistical, and 300 particles of active components is respectively selected to be counted, and catalyst uses the active component of front and rear surfaces
Particle diameter distribution as shown in Fig. 2, reaction before active component average grain diameter be 6.4nm, react 200h after, the average grain of active component
Diameter is 7.4nm, is not apparent from increase, also illustrates that particle surface does not occur apparent carbon distribution.
Embodiment 2
(1) provide nitrogen content be 12at.%, specific surface area 1800m2/ g, Kong Rongwei 4.2cm3/ g, grain size be 10~
The N doping hollow nano cages (referred to as NCNC) of 30nm；
(2) 0.784g ferric citrates are mixed with the ethyl alcohol deionized water solution that 20mL ethyl alcohol volumetric concentrations are 20%,
Obtain the ethanol water of ferric citrate；0.60gNCNC is mixed with the ethanol water of the ferric citrate,
150r/min rotating speeds stir 0.5h, are then stored at room temperature dipping 6h；Drying box of the products obtained therefrom at 80 DEG C will be impregnated and dry 8h, obtained
To fischer-tropsch synthetic catalyst presoma (abbreviation Fe/NCNC presomas)；
(3) by the Fe/NCNC presomas under Ar air-flow protections, 380 DEG C of roasting 2h is warming up to, are then naturally cooled to
Room temperature；It then passes to the oxygen-containing inert gas that oxygen volume content is 1% and is passivated 0.5h in room temperature, the oxygen-containing inert gas
Flow is 200mL/min；Passivation products obtained therefrom is ground, the fischer-tropsch synthetic catalyst (abbreviation that average grain diameter is 5.6nm is obtained
Fe/NCNC), the load capacity of iron oxide is accounted for the mass percent of carrier with Fe and is calculated as 15.0wt.% in the Fe/NCNC.
It is 5.6nm to count to obtain the iron oxide average grain diameter in catalyst through transmission electron microscope (TEM) photo.
Fe/NCNC obtained by 100mg the present embodiment is put into Fischer-Tropsch synthesis device, H is passed through with the flow of 20mL/min2,
In 400 DEG C of in-situ reducing 3h；After temperature of reactor is down to 350 DEG C, stopping is passed through H2, start to be passed through synthesis gas, the synthesis
Gas is H2It is 1 with CO volume ratios:1 gaseous mixture maintains 350 DEG C, is 1bar in pressure, synthesis gas air speed is 3000mL/ (h
G) condition carries out Fischer-Tropsch synthesis.
Gas after being reacted using chromatography, stable reaction (please supplement and start to be reacted to when stablizing required after 20h
Between), the conversion ratio of carbon monoxide is 2.1%, low-carbon alkene (C2 =-C4 =) selectivity be 53%, the selectivity of methane is
Activity has no decline after 26%, sustained response 200h, and the conversion ratio of carbon monoxide is 2.3%, low-carbon alkene (C2 =-C4 =) choosing
Selecting property is 53%, and the selectivity of methane is 26%.
The iron oxide average grain diameter for counting to obtain in reaction 200h rear catalysts through transmission electron microscope photo is
7.8nm。
Embodiment 3
(1) provide nitrogen content be 12at.%, specific surface area 1800m2/ g, Kong Rongwei 4.2cm3/ g, grain size be 10~
The N doping hollow nano cages (referred to as NCNC) of 30nm；
(2) 0.328g ferric citrates are mixed with the ethyl alcohol deionized water solution that 30mL ethyl alcohol volumetric concentrations are 20%,
Obtain the ethanol water of ferric citrate；0.60gNCNC is mixed with the ethanol water of the ferric citrate, 150
Turn/min rotating speeds stirring 0.5h, is then stored at room temperature dipping 6h；Drying box of the products obtained therefrom at 80 DEG C will be impregnated and dry 12h, obtained
To fischer-tropsch synthetic catalyst presoma (abbreviation Fe/NCNC presomas)；
(3) by the Fe/NCNC presomas under Ar air-flow protections, 380 DEG C of roasting 2h is warming up to, are then naturally cooled to
Room temperature；It then passes to the oxygen-containing inert gas that oxygen volume content is 1% and is passivated 0.5h in room temperature, the oxygen-containing inert gas
Flow is 100mL/min；Passivation products obtained therefrom is ground, fischer-tropsch synthetic catalyst (the abbreviation Fe/ that grain size is 4.1nm is obtained
NCNC), the load capacity of iron oxide is accounted for the mass percent of carrier with Fe and is calculated as 6.3wt.% in the Fe/NCNC.
It is 4.1nm to count to obtain the iron oxide average grain diameter in catalyst through transmission electron microscope photo.
Fe/NCNC obtained by 100mg the present embodiment is put into Fischer-Tropsch synthesis device, H is passed through with the flow of 20mL/min2,
In 400 DEG C of in-situ reducing 3h；After temperature of reactor is down to 350 DEG C, stopping is passed through H2, start to be passed through synthesis gas, the synthesis
Gas is H2It is 1 with CO volume ratios:1 gaseous mixture maintains 350 DEG C, is 1bar in pressure, synthesis gas air speed is 3000mL/ (h
G) condition carries out Fischer-Tropsch synthesis.
Gas after being reacted using chromatography, stable reaction (please supplement and start to be reacted to when stablizing required after 10h
Between), the conversion ratio of carbon monoxide is 1.6%, low-carbon alkene (C2 =-C4 =) selectivity be 52%, the selectivity of methane is
Activity only slightly declines after 26%, sustained response 60h, and the conversion ratio of carbon monoxide is 1.3%, low-carbon alkene (C2 =-C4 =) choosing
Selecting property is 52%, and the selectivity of methane is 28%.
The iron oxide average grain diameter for counting to obtain reaction 60h rear catalysts surface through transmission electron microscope photo is
6.9nm。
Embodiment 4
(1) provide nitrogen content be 12at.%, specific surface area 1800m2/ g, Kong Rongwei 4.2cm3/ g, grain size be 10~
The N doping hollow nano cages (referred to as NCNC) of 30nm；
(2) 2.53g ferric citrates are mixed with the ethyl alcohol deionized water solution that 50mL ethyl alcohol volumetric concentrations are 20%, is obtained
To the ethanol water of ferric citrate；0.60gNCNC is mixed with the ethanol water of the ferric citrate, in 150r/
Min rotating speeds stir 0.5h, are then stored at room temperature dipping 6h；Drying box of the products obtained therefrom at 80 DEG C will be impregnated to dry for 24 hours, obtain expense
Tropsch synthesis catalyst presoma (abbreviation Fe/NCNC presomas)；
(3) by the Fe/NCNC presomas under Ar air-flow protections, 380 DEG C of roasting 2h is warming up to, are then naturally cooled to
Room temperature；It then passes to the oxygen-containing inert gas that oxygen volume content is 1% and is passivated 0.5h in room temperature, the oxygen-containing inert gas
Flow is 500mL/min；Passivation products obtained therefrom is ground, the fischer-tropsch synthetic catalyst (abbreviation that average grain diameter is 8.6nm is obtained
Fe/NCNC), the load capacity of iron oxide is accounted for the mass percent of carrier with Fe and is calculated as 48.2wt.% in the Fe/NCNC.
The iron oxide average grain diameter for counting to obtain catalyst surface through transmission electron microscope photo is 8.6nm.
Fe/NCNC obtained by 100mg the present embodiment is put into Fischer-Tropsch synthesis device, H is passed through with the flow of 20mL/min2,
In 400 DEG C of in-situ reducing 3h；After temperature of reactor is down to 350 DEG C, stopping is passed through H2, start to be passed through synthesis gas, the synthesis
Gas is H2It is 1 with CO volume ratios:1 gaseous mixture maintains 350 DEG C, is 1bar in pressure, synthesis gas air speed is 3000mL/ (h
G) condition carries out Fischer-Tropsch synthesis.
Gas after being reacted using chromatography, stable reaction (please supplement and start to be reacted to when stablizing required after 20h
Between), the conversion ratio of carbon monoxide is 4.3%, low-carbon alkene (C2 =-C4 =) selectivity be 53%, the selectivity of methane is
Activity has no decline after 20%, sustained response 100h, and the conversion ratio of carbon monoxide is 4.5%, low-carbon alkene (C2 =-C4 =) choosing
Selecting property is 52%, and the selectivity of methane is 20%.
The iron oxide average grain diameter for counting to obtain reaction 100h rear catalysts surface through transmission electron microscope photo is
8.6nm。
Embodiment 5
(1) provide nitrogen content be 5at.%, specific surface area 2000m2/ g, Kong Rongwei 4.6cm3/ g, grain size are 5~25nm
N doping hollow nano cages (referred to as NCNC)；
(2) 0.784g ferric citrates are mixed with the ethyl alcohol deionized water solution that 20mL ethyl alcohol volumetric concentrations are 20%,
Obtain the ethanol water of ferric citrate；0.60gNCNC is mixed with the ethanol water of the ferric citrate,
150r/min rotating speeds stir 0.5h, are then stored at room temperature dipping 6h；Drying box of the products obtained therefrom at 80 DEG C will be impregnated and dry 8h, obtained
To fischer-tropsch synthetic catalyst presoma (abbreviation Fe/NCNC presomas)；
(3) by the Fe/NCNC presomas under Ar air-flow protections, 380 DEG C of roasting 2h is warming up to, are then naturally cooled to
Room temperature；It then passes to the oxygen-containing inert gas that oxygen volume content is 1% and is passivated 0.5h in room temperature, the oxygen-containing inert gas
Flow is 200mL/min；Passivation products obtained therefrom is ground, the fischer-tropsch synthetic catalyst (abbreviation that average grain diameter is 7.6nm is obtained
Fe/NCNC), the load capacity of iron oxide is accounted for the mass percent of carrier with Fe and is calculated as 15.0wt.% in the Fe/NCNC.
The iron oxide average grain diameter for counting to obtain catalyst surface through transmission electron microscope photo is 7.6nm.
Fe/NCNC obtained by 100mg the present embodiment is put into Fischer-Tropsch synthesis device, H is passed through with the flow of 20mL/min2,
In 400 DEG C of in-situ reducing 3h；After temperature of reactor is down to 350 DEG C, stopping is passed through H2, start to be passed through synthesis gas, the synthesis
Gas is H2It is 1 with CO volume ratios:1 gaseous mixture maintains 350 DEG C, is 1bar in pressure, synthesis gas air speed is 3000mL/ (h
G) condition carries out Fischer-Tropsch synthesis.
Gas after being reacted using chromatography, stable reaction (please supplement and start to be reacted to when stablizing required after 10h
Between), the conversion ratio of carbon monoxide is 2.4%, low-carbon alkene (C2 =-C4 =) selectivity be 48%, the selectivity of methane is
Activity does not have degradation after 28%, sustained response 50h, and the conversion ratio of carbon monoxide is 2.1%, low-carbon alkene (C2 =-C4 =)
Selectivity is 47%, and the selectivity of methane is 29%.
The iron oxide average grain diameter for counting to obtain reaction 50h rear catalysts surface through transmission electron microscope photo is
9.2nm。
Embodiment 6
(1) provide nitrogen content be 12at.%, specific surface area 1800m2/ g, Kong Rongwei 4.2cm3/ g, grain size be 10~
The N doping hollow nano cages (referred to as NCNC) of 30nm；
(2) 1.20g Fe(NO3)39H2Os are mixed with the ethyl alcohol deionized water solution that 15mL ethyl alcohol volumetric concentrations are 20%,
Obtain the ethanol water of ferric nitrate；0.60gNCNC is mixed with the ethanol water of the ferric nitrate, in 150r/min rotating speeds
0.5h is stirred, dipping 6h is then stored at room temperature；Drying box of the products obtained therefrom at 80 DEG C will be impregnated and dry 8h, F- T synthesis is obtained and urge
Agent presoma (abbreviation Fe/NCNC presomas)；
(3) by the Fe/NCNC presomas under Ar air-flow protections, 380 DEG C of roasting 2h is warming up to, are then naturally cooled to
Room temperature；It then passes to the oxygen-containing inert gas that oxygen volume content is 1% and is passivated 0.5h in room temperature, the oxygen-containing inert gas
Flow is 200mL/min；Passivation products obtained therefrom is ground, fischer-tropsch synthetic catalyst (abbreviation Fe/NCNC), the Fe/ are obtained
The load capacity of iron oxide is accounted for the mass percent of carrier with Fe and is calculated as 27.7wt.% in NCNC.
The iron oxide average grain diameter for counting to obtain catalyst surface through transmission electron microscope photo is 7.1nm.
Fe/NCNC obtained by 100mg the present embodiment is put into Fischer-Tropsch synthesis device, H is passed through with the flow of 20mL/min2,
In 400 DEG C of in-situ reducing 3h；After temperature of reactor is down to 350 DEG C, stopping is passed through H2, start to be passed through synthesis gas, the synthesis
Gas is H2It is 1 with CO volume ratios:1 gaseous mixture maintains 350 DEG C, is 1bar in pressure, synthesis gas air speed is 3000mL/ (h
G) condition carries out Fischer-Tropsch synthesis.
Gas after being reacted using chromatography, stable reaction (please supplement and start to be reacted to when stablizing required after 20h
Between), the conversion ratio of carbon monoxide is 3.1%, low-carbon alkene (C2 =-C4 =) selectivity be 51%, the selectivity of methane is
Activity has no decline after 25%, sustained response 100h, and the conversion ratio of carbon monoxide is 3.2%, low-carbon alkene (C2 =-C4 =) choosing
Selecting property is 52%, and the selectivity of methane is 25%.
The iron oxide average grain diameter for counting to obtain reaction 50h rear catalysts surface through transmission electron microscope photo is
7.4nm。
Embodiment 7
(1) provide nitrogen content be 16at.%, specific surface area 1780m2/ g, Kong Rongwei 3.8cm3/ g, grain size be 10~
The N doping hollow nano cages (referred to as NCNC) of 30nm；
(2) 1.45g ferric citrates are mixed with the ethyl alcohol deionized water solution that 30mL ethyl alcohol volumetric concentrations are 20%, is obtained
To the ethanol water of ferric citrate；0.60gNCNC is mixed with the ethanol water of the ferric citrate, in 160r/
Min rotating speeds stir 0.5h, are then stored at room temperature dipping 6h；Drying box of the products obtained therefrom at 80 DEG C will be impregnated and dry 12h, obtain expense
Tropsch synthesis catalyst presoma (abbreviation Fe/NCNC presomas)；
(3) by the Fe/NCNC presomas under Ar air-flow protections, 380 DEG C of roasting 2h is warming up to, are then naturally cooled to
Room temperature；It then passes to the oxygen-containing inert gas that oxygen volume content is 1% and is passivated 0.5h in room temperature, the oxygen-containing inert gas
Flow is 200mL/min；Passivation products obtained therefrom is ground, fischer-tropsch synthetic catalyst (abbreviation Fe/NCNC), the Fe/ are obtained
The load capacity of iron oxide is accounted for the mass percent of carrier with Fe and is calculated as 27.6wt.% in NCNC；
(4) it is 5.0Pa in vacuum degree, the condition that temperature is 200 DEG C is heat-treated by 1gFe/NCNC in vacuum drying chamber
2h is cooled to room temperature, the Fe/NCNC being heat-treated；It is 40% that 0.0517g potassium nitrate, which is dissolved in 10mL ethyl alcohol volumetric concentrations,
Ethyl alcohol deionized water solution obtains the ethyl alcohol deionized water solution of potassium nitrate；By the Fe/NCNC of the heat treatment and potassium nitrate
Ethyl alcohol deionized water solution is stirred 0.5h in 150r/min rotating speeds, will mix drying box of the products obtained therefrom at 100 DEG C and dries
2h obtains load auxiliary agent K+Fischer-tropsch synthetic catalyst presoma (abbreviation KFe/NCNC presomas)；
(5) by the KFe/NCNC presomas in N2Under air-flow protection, 350 DEG C of roasting 2h are warming up to, then natural cooling
To room temperature, load auxiliary agent K is obtained+Fischer-tropsch synthetic catalyst (abbreviation KFe/NCNC)；K in gained KFe/NCNC+Load capacity with
K+The mass percent for accounting for carrier is calculated as 3.3wt.%.
The iron oxide average grain diameter for counting to obtain catalyst surface through transmission electron microscope photo is 6.5nm.
KFe/NCNC obtained by 100mg the present embodiment is put into Fischer-Tropsch synthesis device, H is passed through with the flow of 20mL/min2,
In 400 DEG C of in-situ reducing 3h；After temperature of reactor is down to 340 DEG C, stopping is passed through H2, start to be passed through synthesis gas, the synthesis
Gas is H2It is 1 with CO volume ratios:1 gaseous mixture maintains 340 DEG C, is 10bar in pressure, synthesis gas air speed is 4000mL/ (h
G) condition carries out Fischer-Tropsch synthesis.
Gas after being reacted using chromatography, stable reaction (please supplement and start to be reacted to when stablizing required after 10h
Between), the conversion ratio of carbon monoxide is 48%, low-carbon alkene (C2 =-C4 =) selectivity be 58%, the selectivity of methane is 11%,
After sustained response 200h, the conversion ratio of carbon monoxide is 49%, low-carbon alkene (C2 =-C4 =) selectivity be 57%, the choosing of methane
Selecting property is 13%.
The iron oxide average grain diameter for counting to obtain reaction 200h rear catalysts surface through transmission electron microscope photo is
8.4nm。
Embodiment 8
(1) provide nitrogen content be 16at.%, specific surface area 1780m2/ g, Kong Rongwei 3.8cm3/ g, grain size be 10~
The N doping hollow nano cages (referred to as NCNC) of 30nm；
(2) 1.45g ferric citrates are mixed with the ethyl alcohol deionized water solution that 30mL ethyl alcohol volumetric concentrations are 20%, is obtained
To the ethanol water of ferric citrate；0.60gNCNC is mixed with the ethanol water of the ferric citrate, in 160r/
Min rotating speeds stir 0.5h, are then stored at room temperature dipping 6h；Drying box of the products obtained therefrom at 80 DEG C will be impregnated and dry 12h, obtain expense
Tropsch synthesis catalyst presoma (abbreviation Fe/NCNC presomas)；
(3) by the Fe/NCNC presomas under Ar air-flow protections, 380 DEG C of roasting 2h is warming up to, are then naturally cooled to
Room temperature；It then passes to the oxygen-containing inert gas that oxygen volume content is 1% and is passivated 0.5h in room temperature, the oxygen-containing inert gas
Flow is 200mL/min；Passivation products obtained therefrom is ground, fischer-tropsch synthetic catalyst (abbreviation Fe/NCNC), the Fe/ are obtained
The load capacity of iron oxide is accounted for the mass percent of carrier with Fe and is calculated as 27.6wt.% in NCNC；
(4) it is 5Pa in vacuum degree by 1gFe/NCNC in vacuum drying chamber, the condition that temperature is 200 DEG C is heat-treated 2h,
It is cooled to room temperature, the Fe/NCNC being heat-treated；0.0740g sodium nitrate is dissolved in the second that 10mL ethyl alcohol volumetric concentrations are 40%
Alcohol deionized water solution obtains the ethyl alcohol deionized water solution of sodium nitrate；By the second of the Fe/NCNC of the heat treatment and sodium nitrate
Alcohol deionized water solution is stirred 0.5h in 150 turns/min rotating speeds, will mix drying box of the products obtained therefrom at 100 DEG C and dries
2h obtains load auxiliary agent Na+Fischer-tropsch synthetic catalyst presoma (abbreviation NaFe/NCNC presomas)；
(5) by the NaFe/NCNC presomas in N2Under air-flow protection, 350 DEG C of roasting 2h are warming up to, then natural cooling
To room temperature, load auxiliary agent Na is obtained+Fischer-tropsch synthetic catalyst (abbreviation NaFe/NCNC)；Na in gained NaFe/NCNC+Load
Amount is with Na+The mass percent for accounting for carrier is calculated as 3.3wt.%.
The iron oxide average grain diameter for counting to obtain catalyst surface through transmission electron microscope photo is 6.5nm.
NaFe/NCNC obtained by 100mg the present embodiment is put into Fischer-Tropsch synthesis device, is passed through with the flow of 20mL/min
H2, in 400 DEG C of in-situ reducing 3h；After temperature of reactor is down to 340 DEG C, stopping is passed through H2, start to be passed through synthesis gas, the conjunction
It is H at gas2It is 1 with CO volume ratios:1 gaseous mixture maintains 340 DEG C, is 10bar in pressure, synthesis gas air speed is 5000mL/
(hg) condition carries out Fischer-Tropsch synthesis.
Gas after being reacted using chromatography, stable reaction (please supplement and start to be reacted to when stablizing required after 10h
Between), the conversion ratio of carbon monoxide is 54%, low-carbon alkene (C2 =-C4 =) selectivity be 59%, the selectivity of methane is 11%,
After sustained response 100h, the conversion ratio of carbon monoxide is 56%, low-carbon alkene (C2 =-C4 =) selectivity be 60%, the choosing of methane
Selecting property is 11%.
The iron oxide average grain diameter for counting to obtain reaction 100h rear catalysts surface through transmission electron microscope photo is
8.3nm。
Embodiment 9
(1) provide nitrogen content be 19at.%, specific surface area 1690m2/ g, Kong Rongwei 3.4cm3/ g, grain size be 10~
The N doping hollow nano cages (referred to as NCNC) of 30nm；
(2) 1.45g ferric citrates are mixed with the ethyl alcohol deionized water solution that 30mL ethyl alcohol volumetric concentrations are 20%, is obtained
To the ethanol water of ferric citrate；0.60gNCNC is mixed with the ethanol water of the ferric citrate, in 160r/
Min rotating speeds stir 0.5h, are then stored at room temperature dipping 6h；Drying box of the products obtained therefrom at 80 DEG C will be impregnated and dry 12h, obtain expense
Tropsch synthesis catalyst presoma (abbreviation Fe/NCNC presomas)；
(3) by the Fe/NCNC presomas under Ar air-flow protections, 380 DEG C of roasting 2h is warming up to, are then naturally cooled to
Room temperature；It then passes to the oxygen-containing inert gas that oxygen volume content is 1% and is passivated 0.5h in room temperature, the oxygen-containing inert gas
Flow is 200mL/min；Passivation products obtained therefrom is ground, fischer-tropsch synthetic catalyst (abbreviation Fe/NCNC), the Fe/ are obtained
The mass percent that the load capacity of iron oxide in NCNC accounts for carrier with Fe is calculated as 27.6wt.%；
(4) it is 5Pa in vacuum degree by 1gFe/NCNC in vacuum drying chamber, the condition that temperature is 200 DEG C is heat-treated 2h,
It is cooled to room temperature, the Fe/NCNC being heat-treated；0.0133g sodium sulphate and 0.0580g sodium nitrate are dissolved in 10mL ethyl alcohol volumes
A concentration of 40% ethyl alcohol deionized water solution obtains the ethyl alcohol deionized water solution of sodium containing auxiliary agent and sulphur；By the heat treatment
Fe/NCNC and sodium containing auxiliary agent and the ethyl alcohol deionized water solution of sulphur be stirred 0.5h in 150 turns/min rotating speeds, by mixing
The drying box that product is obtained at 100 DEG C dries 2h, obtains load auxiliary agent Na+With the fischer-tropsch synthetic catalyst presoma (letter of element sulphur
Claim NaSFe/NCNC presomas)；
(5) by the NaSFe/NCNC presomas in N2Under air-flow protection, it is warming up to 350 DEG C and roasts 2h, it is then naturally cold
But to room temperature, load auxiliary agent Na is obtained+With the fischer-tropsch synthetic catalyst (abbreviation NaSFe/NCNC) of element sulphur；Gained NaSFe/
Na in NCNC+Load capacity with Na+The mass percent for accounting for carrier is calculated as 3.3wt.%, and the load capacity of S elements accounts for carrier with S
Mass percent is calculated as 0.5wt.%.
The iron oxide average grain diameter for counting to obtain catalyst surface through transmission electron microscope photo is 6.3nm.
NaSFe/NCNC obtained by 100mg the present embodiment is put into Fischer-Tropsch synthesis device, is passed through with the flow of 20mL/min
H2, in 400 DEG C of in-situ reducing 3h；After temperature of reactor is down to 340 DEG C, stopping is passed through H2, start to be passed through synthesis gas, the conjunction
It is H at gas2It is 1 with CO volume ratios:1 gaseous mixture maintains 340 DEG C, is 10bar in pressure, synthesis gas air speed is 5000mL/
(hg) condition carries out Fischer-Tropsch synthesis.
Gas after being reacted using chromatography, stable reaction (please supplement and start to be reacted to when stablizing required after 10h
Between), the conversion ratio of carbon monoxide is 42%, low-carbon alkene (C2 =-C4 =) selectivity be 60%, the selectivity of methane is 10%,
After sustained response 60h, the conversion ratio of carbon monoxide is 41%, low-carbon alkene (C2 =-C4 =) selectivity be 61%, the choosing of methane
Selecting property is 9%；The reaction was continued has no decline to the activity of 100h rear catalysts, and the conversion ratio of carbon monoxide is 41%, low-carbon alkene
Hydrocarbon (C2 =-C4 =) selectivity be 61%, the selectivity of methane is 9%.
The iron oxide average grain diameter for counting to obtain reaction 100h rear catalysts surface through transmission electron microscope photo is
8.2nm。
Embodiment 10
(1) provide nitrogen content be 15at.%, specific surface area 1760m2/ g, Kong Rongwei 3.8cm3/ g, grain size be 10~
The N doping hollow nano cages (referred to as NCNC) of 30nm；
(2) 0.541g cobalt acetates are mixed with the ethyl alcohol deionized water solution that 25mL ethyl alcohol volumetric concentrations are 20%, is obtained
The ethanol water of cobalt acetate；0.60gNCNC is mixed with the ethanol water of the cobalt acetate, is stirred in 160r/min rotating speeds
Then 0.5h is stored at room temperature dipping 6h；Drying box of the products obtained therefrom at 80 DEG C will be impregnated and dry 12h, obtain F- T synthesis catalysis
Agent presoma (abbreviation Co/NCNC presomas)；
(3) by the Co/NCNC presomas under Ar air-flow protections, 400 DEG C of roasting 2h is warming up to, are then naturally cooled to
Room temperature；It then passes to the oxygen-containing inert gas that oxygen volume content is 1% and is passivated 0.5h in room temperature, the oxygen-containing inert gas
Flow is 200mL/min；Passivation products obtained therefrom is ground, fischer-tropsch synthetic catalyst (abbreviation Co/NCNC), the Co/ are obtained
The mass percent that the load capacity of cobalt oxide in NCNC accounts for carrier with Co is calculated as 30wt.%.
The cobalt oxide average grain diameter for counting to obtain catalyst surface through transmission electron microscope photo is 6.7nm.
Co/NCNC obtained by 100mg the present embodiment is put into Fischer-Tropsch synthesis device, H is passed through with the flow of 20mL/min2,
In 380 DEG C of in-situ reducing 5h；After temperature of reactor is down to 250 DEG C, stopping is passed through H2, start to be passed through synthesis gas, the synthesis
Gas is H2It is 2 with CO volume ratios:1 gaseous mixture maintains 250 DEG C, is 20bar in pressure, synthesis gas air speed is 4000mL/ (h
G) condition carries out Fischer-Tropsch synthesis.
Gas after being reacted using chromatography, stable reaction (please supplement and start to be reacted to when stablizing required after 10h
Between), the conversion ratio of carbon monoxide is 60%, the alkane (C that carbon atom number is 5 or more5+) selectivity be 82%, the selection of methane
Property be 6%, activity has no decline after sustained response 200h, and the conversion ratio of carbon monoxide is 60%, the alkane that carbon atom number is 5 or more
Hydrocarbon (C5+) selectivity be 83%, the selectivity of methane is 5%.
The cobalt oxide average grain diameter for counting to obtain reaction 200h rear catalysts surface through transmission electron microscope photo is
7.8nm。
Embodiment 11
(1) provide nitrogen content be 15at.%, specific surface area 1760m2/ g, Kong Rongwei 3.8cm3/ g, grain size be 10~
The N doping hollow nano cages (referred to as NCNC) of 30nm；
(2) 0.27g cobalt acetates are mixed with the ethyl alcohol deionized water solution that 30mL ethyl alcohol volumetric concentrations are 20%, obtains vinegar
The ethanol water of sour cobalt；0.60gNCNC is mixed with the ethanol water of the cobalt acetate, is stirred in 160r/min rotating speeds
Then 0.5h is stored at room temperature dipping 6h；Drying box of the products obtained therefrom at 80 DEG C will be impregnated and dry 12h, obtain F- T synthesis catalysis
Agent presoma (abbreviation Co/NCNC presomas)；
(3) by the Co/NCNC presomas under Ar air-flow protections, 400 DEG C of roasting 2h is warming up to, are then naturally cooled to
Room temperature；It then passes to the oxygen-containing inert gas that oxygen volume content is 1% and is passivated 0.5h in room temperature, the oxygen-containing inert gas
Flow is 200mL/min；Passivation products obtained therefrom is ground, fischer-tropsch synthetic catalyst (abbreviation Co/NCNC), the Co/ are obtained
The mass percent that the load capacity of cobalt oxide in NCNC accounts for carrier with Co is calculated as 15wt.%；
(4) it is 5Pa in vacuum degree by 1gCo/NCNC in vacuum drying chamber, the condition that temperature is 200 DEG C is heat-treated 2h,
It is cooled to room temperature, the Co/NCNC being heat-treated；0.0740g sodium nitrate is dissolved in the second that 10mL ethyl alcohol volumetric concentrations are 40%
Alcohol deionized water solution obtains the ethyl alcohol deionized water solution of sodium nitrate；By the second of the Co/NCNC of the heat treatment and sodium nitrate
Alcohol deionized water solution is stirred 0.5h in 150 turns/min rotating speeds, will mix drying box of the products obtained therefrom at 100 DEG C and dries
2h obtains load auxiliary agent Na+Fischer-tropsch synthetic catalyst presoma (abbreviation NaCo/NCNC presomas)；
(5) by the NaCo/NCNC presomas in N2Under air-flow protection, 350 DEG C of roasting 2h are warming up to, then natural cooling
To room temperature, load auxiliary agent Na is obtained+Fischer-tropsch synthetic catalyst (abbreviation NaCo/NCNC)；Na in gained NaCo/NCNC+Load
Amount is with Na+The mass percent for accounting for carrier is calculated as 3.3wt.%.
The cobalt oxide average grain diameter for counting to obtain catalyst surface through transmission electron microscope photo is 6.7nm.
NaCo/NCNC obtained by 100mg the present embodiment is put into Fischer-Tropsch synthesis device, is passed through with the flow of 20mL/min
H2, in 320 DEG C of in-situ reducing 10h；After temperature of reactor is down to 250 DEG C, stopping is passed through H2, start to be passed through synthesis gas, the conjunction
It is H at gas2It is 2 with CO volume ratios:1 gaseous mixture maintains 250 DEG C, is 10bar in pressure, synthesis gas air speed is 2000mL/
(hg) condition carries out Fischer-Tropsch synthesis.
Gas after being reacted using chromatography, stable reaction (please supplement and start to be reacted to when stablizing required after 10h
Between), the conversion ratio of carbon monoxide is 46%, low-carbon alkene (C2 =-C4 =) selectivity be 48%, carbon atom number be 5 or more alkane
Hydrocarbon (C5+) selectivity be 42%, the selectivity of methane is 5%, and after sustained response 100h, the conversion ratio of carbon monoxide is 47%,
Low-carbon alkene (C2 =-C4 =) selectivity be 47%, carbon atom number be 5 or more alkane (C5+) selectivity be 43%, methane
Selectivity be 5%.
The cobalt oxide average grain diameter for counting to obtain reaction 100h rear catalysts surface through transmission electron microscope photo is
7.6nm。
Comparative example 1
(1) provide nitrogen content be 0at.%, specific surface area 1950m2/ g, Kong Rongwei 4.9cm3/ g, grain size are 10~30nm
Hollow nano cages (referred to as NCNC)；That is the method with reference to disclosed in patent CN102530922A will be used containing the steam of C and N
Steam containing C is replaced；
(2) 0.784g ferric citrates are mixed with the ethyl alcohol deionized water solution that 20mL ethyl alcohol volumetric concentrations are 20%,
Obtain the ethanol water of ferric citrate；0.60gNCNC is mixed with the ethanol water of the ferric citrate,
160r/min rotating speeds stir 0.5h, are then stored at room temperature dipping for 24 hours；Drying box of the products obtained therefrom at 80 DEG C will be impregnated and dry 8h,
Obtain fischer-tropsch synthetic catalyst presoma (abbreviation Fe/NCNC presomas)；
(3) by the Fe/NCNC presomas under Ar air-flow protections, 380 DEG C of roasting 2h is warming up to, are then naturally cooled to
Room temperature；It then passes to the oxygen-containing inert gas that oxygen volume content is 1% and is passivated 0.5h in room temperature, the oxygen-containing inert gas
Flow is 200mL/min；Passivation products obtained therefrom is ground, fischer-tropsch synthetic catalyst (abbreviation Fe/NCNC), the Fe/ are obtained
The load capacity of iron oxide is accounted for the mass percent of carrier with Fe and is calculated as 15wt.% in NCNC.
The iron oxide average grain diameter for counting to obtain catalyst surface through transmission electron microscope photo is 8.1nm.
100mg this comparative example gained Fe/NCNC is put into Fischer-Tropsch synthesis device, H is passed through with the flow of 20mL/min2,
In 400 DEG C of in-situ reducing 3h；After temperature of reactor is down to 350 DEG C, stopping is passed through H2, start to be passed through synthesis gas, the synthesis
Gas is H2It is 1 with CO volume ratios:1 gaseous mixture maintains 350 DEG C, is 1bar in pressure, synthesis gas air speed is 3000mL/ (h
G) condition carries out Fischer-Tropsch synthesis.
Gas after being reacted using chromatography, stable reaction (please supplement and start to be reacted to when stablizing required after 10h
Between), the conversion ratio of carbon monoxide is 2.7%, low-carbon alkene (C2 =-C4 =) selectivity be 44%, the selectivity of methane is
27%, the reaction was continued 10h, the activity of catalyst start it is rapid decline, when reacting 50h, the conversion ratio of carbon monoxide is reduced to
2.1%, low-carbon alkene (C2 =-C4 =) selectivity be 45%, the selectivity of methane is 29%.
The iron oxide average grain diameter for counting to obtain reaction 50h rear catalysts surface through transmission electron microscope photo is
17.5nm。
Comparative example 1 is compared into (active component content of the two is identical, and carrier structure is identical) with embodiment 5 (carrier is nitrogenous)
It is found that catalyst provided herein, in reaction 50h, the activity of catalyst does not significantly decrease, and 1 institute of comparative example
The activity for obtaining catalyst is then decreased obviously, and illustrates that the stability of catalyst provided by the present invention is more excellent.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of fischer-tropsch synthetic catalyst, including carrier and active component, the carrier is N doping hollow nano cages, described
Active components distribution is the nano particle of metal oxide in the surface of carrier, the active component, and the metal oxide is
Iron oxide or cobalt oxide, the percentage that the load capacity of the metal oxide accounts for carrier with metallic element are calculated as 5~51wt.%,
Nitrogen content in the N doping hollow nano cages is 5~20at.%.
2. fischer-tropsch synthetic catalyst according to claim 1, which is characterized in that the load capacity of the metal oxide is with gold
The percentage that category element accounts for carrier is calculated as 10~35wt.%.
3. fischer-tropsch synthetic catalyst according to claim 1 or 2, which is characterized in that the grain size of the metal oxide is 2
~30nm.
4. fischer-tropsch synthetic catalyst according to claim 1, which is characterized in that in the N doping hollow nano cages
Nitrogen content is 7~16at.%.
5. fischer-tropsch synthetic catalyst according to claim 1, which is characterized in that the fischer-tropsch synthetic catalyst further includes
One auxiliary agent, first auxiliary agent are Na+Or K+, the percentage that the load capacity of first auxiliary agent accounts for carrier with the first auxiliary agent is calculated as
0.5~4wt.%.
6. fischer-tropsch synthetic catalyst according to claim 5, which is characterized in that the fischer-tropsch synthetic catalyst further includes
Two auxiliary agents, second auxiliary agent are element sulphur, and the percentage that the load capacity of second auxiliary agent accounts for carrier with the second auxiliary agent is calculated as
0.1~0.5wt.%.
7. a kind of preparation method of claim 1~6 any one of them fischer-tropsch synthetic catalyst, includes the following steps：
(1) N doping hollow nano cages are provided；
(2) the N doping hollow nano cages are impregnated in the ethanol water of metallic compound, obtains F- T synthesis and urges
Agent presoma；The metallic compound is the metal salt or metal complex of iron or cobalt；
(3) the fischer-tropsch synthetic catalyst presoma is obtained into fischer-tropsch synthetic catalyst successively through the first roasting and passivation；
It (4), will be described when the fischer-tropsch synthetic catalyst includes the first auxiliary agent or includes simultaneously the first auxiliary agent and the second auxiliary agent
Fischer-tropsch synthetic catalyst is heat-treated, and is then mixed with the ethanol water of sodium salt or sylvite, is obtained the Fischer-Tropsch added with auxiliary agent and is closed
At catalyst precursor；The sodium salt or sylvite are at least one of sulfate, hydrochloride and nitrate；
By the fischer-tropsch synthetic catalyst presoma added with auxiliary agent through the second roasting, the F- T synthesis added with auxiliary agent is obtained
Catalyst.
8. preparation method according to claim 7, which is characterized in that first roasting and the second roasting are independently in N2
Or carried out in inert gas, the temperature of first roasting and the second roasting is independently 300~600 DEG C, first roasting
Time with the second roasting is independently 0.5~6h.
9. preparation method according to claim 7, which is characterized in that it is described passivation in oxygenous inert gas flow into
The time of row, the passivation is 0.5~2h, and the temperature of the passivation is 15~40 DEG C.
10. preparation method according to claim 7, which is characterized in that the heat treatment is carried out in vacuum condition, the heat
The temperature of processing is 200~250 DEG C, and the time of the heat treatment is 2~2.5h.
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