CN105921147A - Composition of catalyst for hydrocarbon Fischer-Tropsch synthesis and applications thereof - Google Patents
Composition of catalyst for hydrocarbon Fischer-Tropsch synthesis and applications thereof Download PDFInfo
- Publication number
- CN105921147A CN105921147A CN201610238332.2A CN201610238332A CN105921147A CN 105921147 A CN105921147 A CN 105921147A CN 201610238332 A CN201610238332 A CN 201610238332A CN 105921147 A CN105921147 A CN 105921147A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- roasting
- carbon monoxide
- olefin polymeric
- complex carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 42
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 42
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 41
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 239000004215 Carbon black (E152) Substances 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 24
- 239000011029 spinel Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960000892 attapulgite Drugs 0.000 claims abstract description 5
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 230000000694 effects Effects 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
- 239000004575 stone Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- -1 Magnesium aluminate Chemical class 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 229910026161 MgAl2O4 Inorganic materials 0.000 claims description 3
- 239000002738 chelating agent Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 44
- 238000004519 manufacturing process Methods 0.000 abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 description 21
- 239000010941 cobalt Substances 0.000 description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 239000003502 gasoline Substances 0.000 description 16
- 230000009467 reduction Effects 0.000 description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 11
- 239000002028 Biomass Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002309 gasification Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000002798 spectrophotometry method Methods 0.000 description 6
- 208000019901 Anxiety disease Diseases 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000036506 anxiety Effects 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000002902 bimodal effect Effects 0.000 description 3
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003303 ruthenium Chemical class 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000237970 Conus <genus> Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 241000195474 Sargassum Species 0.000 description 1
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- SPDCFZAAMSXKTK-UHFFFAOYSA-N acetic acid;ruthenium Chemical compound [Ru].CC(O)=O SPDCFZAAMSXKTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 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
- 229940097267 cobaltous chloride Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- QORYBJZFIBBDSH-UHFFFAOYSA-N ruthenium zinc Chemical compound [Zn].[Zn].[Zn].[Ru] QORYBJZFIBBDSH-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001550 time effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B01J35/66—Pore distribution
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- 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
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- 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
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- 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
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- 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
- C10G2/333—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 platinum-group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
The invention relates to a composition of a catalyst for a method using Fischer-Tropsch (FT) reactions to prepare hydrocarbons from mixed gas mainly composed of hydrogen and carbon monoxide, and a method using FT reactions to prepare hydrocarbons from syngas mentioned above. The invention specifically relates to a catalyst composition, which is prepared by loading FT active metals and auxiliary metals onto a composite carrier composed of attapulgite and spinel oxide, and a hydrocarbon manufacturing method, which is characterized by using the FT synthesis catalyst mentioned above.
Description
Technical field
The present invention relates to the use of Fischer-Tropsch (FT) to react by the mixed gas as main constituent with hydrogen and carbon monoxide (hereinafter referred to as
For " synthesis gas ") carbon monoxide-olefin polymeric that uses when manufacturing hydro carbons and utilize FT reaction to be manufactured hydro carbons by above-mentioned synthesis gas
Method.More specifically, relate to comprising the active metal containing FT and be carried on the carbon monoxide-olefin polymeric of complex carrier and to use
The manufacture method of the hydro carbons that above-mentioned FT synthetic catalyst is characterized.
Background technology
As the method by synthesis gas Synthin, Fischer-Tropsch (Fischer-Tropsch) reaction, methanol-fueled CLC reaction etc.
It is well-known.Synthetic technology in ICL for Indirect Coal Liquefaction is by Germany scientist Frans Fischer and Hans
Tropsch in 1923 first find and with their name the first letter i.e. F-T name, be called for short F-T synthesis or Fischer-Tropsch
Synthesis.Rely on indirect liquefaction technology, not only can from coal the common petroleum goods such as extracting gasoline, diesel oil, kerosene, but also
Aviation Fuel, lubricating oil contour quality oil goods and the multiple high value-added product such as alkene, paraffin can be extracted.From
Since Fischer and Tropsch finds can to generate hydrocarbon compound on the iron catalyst of alkalization, Fiscber-Tropscb synthesis technology is just
Along with world's crude oil price fluctuation and political factor and prosperity and decline is indefinite.Fiscber-Tropscb synthesis takes the lead in starting industrialization in Germany
Application, within 1934, Rule chemical company has built up First indirect liquefaction process units, and yield is 70,000 tons/year, to nineteen forty-four,
Germany has 9 factories production capacity of totally 57 ten thousand tons/year.In the same period, Japan, France, China also have 6 suits to set up
Become.FT reaction be using the ferrum of iron family element, cobalt, nickel, platinum family element ruthenium etc. as the catalyst of active metal.On the other hand,
The reaction of known methanol-fueled CLC is carried out by Cu-series catalyst, and C2 oxygenatedchemicals (ethanol, acetaldehyde etc.) synthesis is catalyzed by rhodium system
Agent is carried out.
At present, Exxon-Mobil (Exxon-Mobil), BP (BP-Amoco), ConUS oil company
(ConocoPhillips) and artificial oil company (Syntroleum) etc. is the most developing the Fiscber-Tropscb synthesis technique of oneself, transfer the possession of
License technology, and plan having the outlying region of natural gas to build Fischer-Tropsch synthetic natural gas liquefaction plant.F-T closes
The main chemical reactions become: the primary response of F-T synthesis: generate alkane: nCO+ (2n+1) H2 = CnH2n+2+nH2O generates alkene:
nCO+(2n)H2 = CnH2n+nH2O additionally also has some side reactions, such as: generate methane: CO+3H2 = CH4+H2O generates first
Alcohol: CO+2H2 = CH3OH generates ethanol: 2CO+4H2 = C2H5OH+ H2O carbon deposit reacts: 2CO=C+CO2Except above 6
Beyond individual reaction, also has the side reaction generating the oxygenatedchemicalss such as the alcohol of higher carbon number and aldehyde, ketone, acid, ester.
Synthetic catalyst is mainly made up of periodic chart group VIII metals such as Co, Fe, Ni, Ru, in order to improve catalyst
Activity, stability and selectivity, also to add some auxiliary elements, such as metal-oxide or salt in addition to main constituent.Major part
Catalyst is required for carrier, such as aluminium oxide, silicon dioxide, Kaolin or kieselguhr etc..Only through CO+ after synthetic catalyst preparation
After H2 or H2 reduction activation, ability is the most active.At present, use in the world more ripe indirect liquefaction catalyst mainly have ferrum system and
The big class of cobalt system two, the mainly Fe-series catalyst that SASOL uses.SASOL fixed bed and paste state bed reactor use
Precipitated iron catalyst, uses fused iron catalyst in a fluidized bed reactor.
Only Sasol(ferrum, the cobalt of Fiscber-Tropscb synthesis cobalt and iron catalyst industrial applications in the world), Shell(cobalt)
Two, also have other some companies also to have this respect patent, but do not hear input large-scale industrial application, simply in pilot scale
On device use, these companies are broadly divided into following several: big oil company such as Exxon Mobil(cobalt), Statoil
(cobalt), BP(cobalt), Conoco(cobalt), Chevron(cobalt)；Specialty does company's such as Rentech(ferrum of artificial oil), Syntroleum
(cobalt)；Also have some specialties do company's such as Johnson Matthey(ferrum of catalyst, cobalt), Albemarle(ferrum, cobalt) etc..
But, current fischer-tropsch synthetic catalyst there is a problem in that: owing to FT reacts, CH4Etc. lower hydrocarbon, CO2So
The generation of gas componant be promoted, gasoline yield reduces；Or do not adapt to most suitable reaction problem, or catalyst
The relatively low easy inactivation of activity, poor stability, be under higher reaction temperatures, the relatively low grade of gasoline fraction productivity is stable.
Summary of the invention
It is an object of the invention to, it is provided that the catalyst for producing compositions of hydro carbons, it can be by synthesis gas by reaction
Obtain CO conversion ratio height, gas componant generates less and aromatic series, cycloalkane, alkene, the such higher octane of alkane of branched
It is worth the gasoline fraction that the selectivity of composition is high.Meanwhile, the good stability of catalyst, long-term non-inactivation, can efficiently by
Synthesis gas obtains the method for above-mentioned gasoline fraction.
Present inventor is studied for reaching above-mentioned purpose, found that react active metal species by FT
FT synthetic catalyst and there is the complex carrier of special construction, can manufacture with existing report manufactured gasoline by synthesis gas
The method phase specific activity of fraction is high, gas componant generates less and rich in aromatic series, cycloalkane, alkene, the alkane of branched
High-knock rating gasoline fraction, thus complete the present invention.
The present invention provides a kind of catalyst for fischer-tropsch synthesis compositions, the active component in described Fischer-Tropsch catalyst
For one or more of Co, Fe, Ru, active component content is about 0.1～30 matter relative to catalyst benchmark with amount of metal conversion
Amount %, metal promoter is about 0.1-5% relative to catalyst benchmark with amount of metal conversion.Active component and auxiliary agent are carried on compound
Carrier.
Described metal promoter is one or more of Ni, Zn, Mn, Zr.
Described complex carrier is concavo-convex stone and spinel oxide complex carrier, concavo-convex stone and spinel complex oxide
Mass ratio is 1:2-5, preferably 1:4-5, and complex carrier preparation process is:
I () adds deionized water in a kettle., stirring adds attapulgite, is uniformly mixed, and prepares slurry A；
(ii) with magnesium nitrate, aluminum nitrate as presoma, with citric acid or ethylene glycol as chelating agent, wiring solution-forming mix and blend are equal
Even, then carry out moisture evaporation, the colloidal sol of solution went from clear is transformed into the gel of thickness, and finally dry, roasting, prepares after roasting
Magnesium aluminate spinel metal-oxide MgAl2O4；
(iii) in slurry A, add described magnesium aluminate spinel oxide, control temperature and continue to be uniformly mixed, supersound process,
Prepare slurry B；
(iv) roasting after slurry B spray drying forming is obtained concavo-convex stone and the spinel oxide complex carrier P-M of catalyst.
Wherein, step (ii) drying condition be 100-150 DEG C dry 1-12 hour, roasting condition is: 200-400 DEG C of roasting
1-4 hour；The most described temperature of step is 100-200 DEG C；The most described roasting condition of step is that 350-800 DEG C of roasting 1-4 is little
Time, preferably 400-600 DEG C roasting 1-3 hour.
The preparation method of described carbon monoxide-olefin polymeric, it is characterised in that comprise the following steps:
(1) concavo-convex stone and spinel oxide complex carrier are prepared according to above-mentioned steps；
(2) auxiliary agent introduces: by the soluble salt solutions incipient impregnation of one or more of Ni, Zn, Mn, Zr to step (1)
On complex carrier, then dry, roasting；
(3) active component introduces: by the soluble salt solutions incipient impregnation of one or more that active component is Co, Fe, Ru
On the complex carrier containing auxiliary agent obtained by step (2), being then dried, roasting obtains carbon monoxide-olefin polymeric.Step (2) institute
Stating drying condition is: 100-120 DEG C, 10-20 hour time, and the condition of roasting is 250-500 DEG C of roasting 1-8 hour.Step (2)
Middle use nickel salt and the aqueous solution of zinc salt, use cobalt salt solution, preferably cobalt nitrate in step (3).Dried strip in described step (3)
Part is: 100-130 DEG C, 12-20 hour time, and the condition of roasting is 400-800 DEG C of roasting 1-8 hour.
The present invention provides the manufacture method of hydro carbons shown below.
The manufacture method of a kind of hydro carbons, it is characterised in that have: use containing the metal to Fischer-Tropsch reaction display activity
The Fischer-Tropsch catalyst being carried on complex carrier is anti-by the FT of the gas synthesis hydro carbons as main constituent with hydrogen and carbon monoxide
Should.
The manufacture method of hydro carbons, wherein, carries out described FT reaction at 260 ~ 350 DEG C.
The catalyst for producing compositions of the hydro carbons of the application of the invention, can be efficient by fischer-tropsch reaction by synthesis gas
Ground obtains the CO conversion ratio gas componant high, other of material synthesis gas and generates less and aromatic series, cycloalkane, alkene, branched
The gasoline fraction that the selectivity of the such antiknock component of alkane is high, the mass percent of product gasoline fraction can reach
More than 89%.And, selectivity of catalyst is good, and activity is higher, continuous operations 12 months, does not occur significantly inactivating sign,
Go for operating with full load of more than scale 10 ton day.
The addition of concavo-convex stone can reduce catalyst cost, forms effectively utilization for natural resources, and concavo-convex stone with
There is spinel-type ABxOy and form complex carrier, on the one hand can play the effect of bonding, on the other hand can be with spinelle oxygen
Compound forms complex carrier, can form mesopore-macropore distribution, bigger specific surface area and pore volume, and can utilize point
The load of the special crystal formation of spar, beneficially active component and dispersion, improve F-T synthesis selectivity, forms mesopore-macropore and carries
Body catalyst, catalyst carrier the first aperture is 10-32nm, accounts for the 20-35% of catalyst pore structure；Second aperture is 60-
70nm, accounts for the 40-60% of catalyst pore structure；
Further, carbon monoxide-olefin polymeric also includes one or more of transition metal promoter Ni, Zn, Mn, Zr, relative to catalysis
Agent benchmark is about 0.1-10%, preferably 0.1-5% with amount of metal conversion, and the effect of auxiliary agent contributes to carbon monoxide dissociation, increases long
The selectivity of chain hydrocarbon, reduces methane selectively.
In order to effectively utilize spinel carrier oxide, therefore, the sintering temperature of catalyst must be controlled, too high be more than
1000 DEG C can cause peroxide breaks down, and crystal formation destroys, it is impossible to play catalytic action.Compared with existing known method, by this
The carbon monoxide-olefin polymeric of embodiment or the manufacture method of the hydro carbons of present embodiment, can effectively manufacture high-octane rating
Gasoline fraction.In the reaction of the carbon monoxide-olefin polymeric used involved by present embodiment, by FT synthetic catalyst by closing
Become gas synthesis hydro carbons contact with carbon monoxide-olefin polymeric, even if also can suppress under high reaction temperature carbon number be 1 ~ 4 low
Level hydrocarbon, CO2Such gas componant generates, can efficiently generate hydrocarbon, and carbon monoxide-olefin polymeric can have under high-temperature
The effect of effect ground, is possibly realized so that manufacturing high-octane gasoline fraction.
Hereinafter, to from the hydro carbons being prepared into involved by present embodiment of the carbon monoxide-olefin polymeric involved by present embodiment
Manufacture method, employ the manufacture method of the hydro carbons of carbon monoxide-olefin polymeric involved by present embodiment, illustrate successively.
The FT synthetic catalyst active component used in present embodiment and auxiliary agent are carried on concavo-convex stone and magnesium aluminate spinel
On complex carrier.As ruthenium salt in active component, the water such as ruthenic chloride, nitric acid ruthenium, acetic acid ruthenium, chlorination six ammonium conjunction ruthenium can be listed
Dissolubility ruthenium salt.It addition, as cobalt salt, cobaltous chloride, cobalt nitrate, cobaltous acetate, cobaltous sulfate, cobaltous formate are preferably used.Additionally, about with
In impregnating ruthenium salt, the solution of cobalt salt supported, in addition to aqueous solution, it is also possible to be formed as the molten of the organic solvents such as alcohol, ether, ketone
Liquid.Now, select to dissolve in the salt of various organic solvent.
The content of the ruthenium in FT synthetic catalyst is scaled 0.1 ~ 5 mass % relative to catalyst benchmark with amount of metal, preferably
It is 0.3 ~ 2.5 mass %, more preferably 0.5 ~ 2 mass %.The content of ruthenium is relevant with active center.The content of ruthenium is less than 0.1 mass %
Time, active center becomes not enough, thus has the anxiety that can not be sufficiently catalyzed activity.On the other hand, the content of ruthenium is more than 5 matter
During amount %, ruthenium can not fully be supported on carrier, and dispersibility reduces, and easily causes the ruthenium species not interacted with carrier components
Produce.Therefore, the ruthenium supporting more than necessity only can increase catalyst cost, therefore the most preferred.
The content of the cobalt in FT synthetic catalyst is scaled 5 ~ 20 mass % relative to catalyst benchmark with amount of metal, preferably
It is 5 ~ 18 mass %, more preferably 5 ~ 20 mass %.When the content of cobalt is less than 3 mass %, the cobalt as active metal is very few, has not
Can confirm that the anxiety of significantly activity rising.On the other hand, when the content of cobalt is more than 20 mass %, being dried, at calcining later
Under reason, FT reaction condition, the cohesion of cobalt is easily carried out, and has the anxiety causing active center minimizing.And then, during the content excess of cobalt,
Be likely to result in the specific surface area of catalyst, pore volume lowers, and the yield of the gas componant in product easily increases, therefore
The most preferred.
Promoter metal content in FT synthetic catalyst relative to catalyst benchmark by amount of metal conversion in terms of be preferably 0.1 ~
10 mass %, more preferably 0.1 ~ 5 mass %, more preferably 0.1 ~ 0.5 mass %.
About the time being dried, calcine, must not make sweeping generalizations according to the difference for the treatment of capacity, but usually 1 ~ 20 hour.
If the time of process, then the evaporation of moisture likely became insufficient, and the activation of FT active metal species subtracts less than 1 hour
Weak, thus the most preferred.Even if it addition, the process time was more than 20 hours, catalysis activity is also basic compared with the situation of less than 20 hours
It is not changed in, therefore if it is considered that workability, productivity ratio, the most preferably less than 20 hours.Wherein, this is dried, calcination processing can
To carry out in atmosphere, or can also carry out under nitrogen, the such not reactive atmosphere of helium, it is also possible under the reducing atmospheres such as hydrogen
Carry out, there is no special provision.
The manufacture method of FT synthetic catalyst in addition to above-mentioned dipping supports method, the method being spray-dried.To now
Slurry concentration, there is no special provision, if but slurry concentration is too low, then the precipitation that can produce, catalyst component becomes uneven
Even, thus the most preferred.Whereas if slurry concentration is too high, then the conveying of slurry can become difficulty, and the slurry therefore selecting appropriateness is dense
Degree, and active component is caused waste.And then, now with concentration, the raising mouldability of catalyst, the spheroidizing of regulation slurry
For the purpose of, it is also possible to interpolation silicon dioxide gels etc. are as binding agent.As the addition of binding agent now, it is preferably and does not makes
It is catalyzed the degree of activity reduction, generally in the scope selection of 5 ~ 20 mass %.
Owing to carrier containing spinel oxide carrier in complex carrier, there is special crystal formation form, can be formed
Active metal embeds or the carrier surface of promoter metal, both can effectively utilize active metal, and can improve again active component
Dispersion, and the addition of the concavo-convex stone of natural material, it is to avoid form the composite oxides of catalytically inactive, bonding can be played steady
Fixed effect, therefore can keep while vector stabilisation, improves the dispersive property of active component, and can and active component
Form fine dispersion, reduce cost, save the common carrier such as molecular sieve；Further, the preparation of complex carrier is adjusted, by concavo-convex stone
Control, at 1:2-5, to advantageously form the various of the carrier of bimodal distribution, beneficially carrier property with the ratio of spinel compound
Property, and effectively controlling carrier specific surface area and pore structure, the complex carrier of formation had both possessed bigger specific surface area, again can be with shape
Becoming special crystal formation, interact with active component, beneficially the flow process distribution of target product, improves gasoline fraction productivity, and energy
Keeping comprcssive strength and the anti-wear performance of catalyst, this is significantly different with common zeolite or the most single carrier.
And complex carrier obtains also by fairly simple effective mixing method, or can carry out altogether by adding alkali liquor
Precipitation obtains, by controlling the operating parameter in preparation process, as temperature, pH value etc. can effectively regulate the pore volume of carrier, ratio
Surface area and pore structure, make Active components distribution more uniform, improve the selectivity of effective product, reduce liquid hydrocarbon and synthesize into
This, improve the bonded energy between carrier primary particle, improves the abrasion resistance properties of catalyst, extends the life-span of catalyst.
The manufacture method of hydro carbons: the manufacture method of the hydro carbons of present embodiment has: use above-mentioned FT synthetic catalyst group
Compound is reacted by the FT of synthesis gas Synthin, if making hydro carbons contact with carbon monoxide-olefin polymeric, then by cracking reaction, isomery
Changing the various reactions such as reaction, hydro carbons is changed.As a result of which it is, gasoline fraction increases, improve gasoline distribution.
Even if the FT synthetic catalyst especially used in present embodiment is CO under 230 ~ 350 DEG C of such hot conditionss
The excellent catalyst that conversion ratio and C5+ the selectivity selectivity of synthesis of hydro carbons of more than 5 (carbon number be) are the highest.
About the form of the reactor of each reaction, fixed bed, fluid bed, suspension bed, slurry bed (slurry can be listed
Bed) etc., there is no particular limitation.
In employing the manufacture method of hydro carbons of above-mentioned carbon monoxide-olefin polymeric, use catalyst group prepared as described above
Compound, for reaction.The manufacture method of hydro carbons based on fixed bed set forth below.The activity of catalyst is carried out by fixed bed
During evaluation, owing to powder body catalyst having the anxiety of the pressure reduction produced in reactor, therefore as the shape of catalyst, it is preferably and squeezes
The products formeds such as laminate, pearl product.As FT synthetic catalyst, zeolite and carbon monoxide-olefin polymeric big used in present embodiment
Little, depend on the scale of reactor, but be 0.5mm ~ 5mm, more preferably 1.0mm ~ 3mm as catalyst shape preferable particle size.
When particle diameter is more than 0.5mm, the differential pressure in reactor can be fully suppressed to rise.On the other hand, by set particle diameter 3mm with
Under, the coefficient of efficiency of catalyst can be made to improve such that it is able to react efficiently.
Carbon monoxide-olefin polymeric involved by present embodiment can carry out reduction treatment (activation before for reaction in advance
Process).
By this reduction treatment, catalyst can be activated to catalysis activity desired to reaction and display.Do not carry out
During this reduction treatment, FT active metal species is not reduced sufficiently, from without demonstrating desired catalysis activity.Also original place
Reason temperature is preferably 140 ~ 350 DEG C, more preferably 150 ~ 300 DEG C.If less than 140 DEG C, then FT active metal species is not filled
Divide reduction, thus sufficient reactivity can not be obtained.
In this reduction treatment, preferably use the reducibility gas with hydrogen as main constituent.At the reproducibility gas used
In body, the composition beyond hydrogen, such as steam, nitrogen, rare gas etc. can be comprised not hinder the amount of the degree of reduction scope.
This reduction treatment is not only affected by above-mentioned treatment temperature, also by hydrogen dividing potential drop and process time effects.Hydrogen dividing potential drop in reduction treatment
It is preferably 0.1 ~ 10MPa, more preferably 0.5 ~ 6MPa, most preferably 0.9 ~ 3MPa.The reduction treatment time leads to because of catalytic amount, hydrogen
Tolerance etc. and different, it is often preferred that 0.1 ~ 72 hour, more preferably 1 ~ 48 hour, most preferably 3 ~ 48 hours.If processed
Between less than 0.1 hour, then have the activation of catalyst to become insufficient anxiety.On the other hand, although even if it is little to be performed for more than 72
Time long reduction treatment, also will not bring harmful effect to catalyst, but not find that catalytic performance improves, thus produce
The undesirable problems such as processing cost increase.
In the manufacture method of hydro carbons, can be to having carried out as described above involved by the present embodiment of reduction treatment
Carbon monoxide-olefin polymeric is passed through synthesis gas carry out.As long as the synthesis gas used is with hydrogen and carbon monoxide for main constituent,
The composition being mixed into other in the scope not hindering reaction is not related.Such as an example, can employ
The manufacture method of the hydro carbons of the carbon monoxide-olefin polymeric involved by present embodiment uses the synthesis obtained by gasification of biomass
Gas.As the kind of biomass now, the agricultural aquatic resources biomass such as grain, building materials, paper pulp, agricultural, woods can be listed
Artificial forest biomass (the plantation such as industry, animal husbandry garbage the like waste biomass, Caulis Sacchari sinensis, Petiolus Trachycarpi, Sargassum
Biomass) etc..Wherein, the garbage biomass that do not utilize that with grain there is not competition are preferably used.Gas about biomass
Change method is not particularly limited.Such as the gasification process of biomass, there are direct gasification, indirect gasification, atmospheric gasification, pressurization
The various method such as gas, it addition, as gasification furnace form, be divided into fixed bed, fluid bed, entrained bed etc. multiple.Employing this
In the manufacture method of the hydro carbons of the carbon monoxide-olefin polymeric involved by embodiment, it is possible to use by either of which method gas
The biomass changed.
As the scope of this real hydrogen with the intrinsic standoff ratio of carbon monoxide, 0.6 ~ 2.7 is suitable, preferably 0.8 ~ 2.5,
More preferably 1 ~ 2.3.If this intrinsic standoff ratio is less than 0.6, then can find the tendency that the yield of the hydro carbons generated reduces, it addition, such as
Really this intrinsic standoff ratio is more than 2.7, then can find the tendency that in the hydro carbons generated, gas componant increases.
And then, in the manufacture method of the hydro carbons of the carbon monoxide-olefin polymeric employed involved by present embodiment, even if closing
It is also no problem for becoming the carbon dioxide that coexists in gas.As the carbon dioxide coexisted in synthesis gas, even such as by oil
The carbon dioxide that the reforming reaction of goods, natural gas wait until can also use without any problems.It addition, it is all right in synthesis gas
Coexist and be mixed into the carbon dioxide of other compositions not hindering FT to react.For example, it may be by the steam weight of petroleum product etc.
The material that whole reaction is released is such containing steam, the carbon dioxide of partially oxidized nitrogen etc..
On FT synthetic catalyst, if the H of usual synthesis gas2/ CO mol ratio is identical, then reaction temperature is the lowest, and chain is raw
Long probability, the C5+ selectivity selectivity of synthesis of hydro carbons of more than 5 (carbon number be) can become the highest, and CO conversion ratio can become
Must be the lowest.Whereas if reaction temperature is the highest, then chain growth probability and C5+ selectivity can become the lowest, but CO conversion ratio can become
Must be the highest.If it addition, H2/ CO is than increasing, then CO conversion ratio can increase, and chain growth probability and C5+ selectivity reduce, if H2/
CO ratio is low, the most in contrast.Being that FT reacts the effect brought about these parameters, its size can be according to the kind of the catalyst used
Class etc. and different.This enforcement is carried out at 1 terrace work reacted with conversion reaction by carrying out FT in same reactor simultaneously
During the manufacture method of the hydro carbons of mode, reaction temperature uses 230 ~ 350 DEG C, preferably 240 ~ 310 DEG C, and more preferably 250 ~ 300
℃.By reaction temperature is set in less than 350 DEG C, undesirable gas componant on FT synthetic catalyst can be suppressed raw
Become, it is possible to the gas componant that suppression is caused by the overcracking on zeolite generates.
CO conversion ratio=(the CO molal quantity in the unstrpped gas of time per unit)-(in the exit gas of time per unit
CO molal quantity)/(the CO molal quantity in the unstrpped gas of time per unit) × 100.
In below example, it is by employing activated carbon (Active Carbon) (60/ in detached dowel that CO analyzes
80 sieve meshes) thermal conductivity type gas chromatogram (TCD-GC) carry out.In unstrpped gas, use and be added with 25 as internal standard
Synthesis gas (the H of the Ar of volume %2Mixed gas with CO).Qualitative and quantitative analysis is by by the peak position of CO and face, peak
Long-pending it is compared to Ar to carry out.It addition, the composition analysis of product is to use capillary column (TC-1) by hydrogen flame ion
Detector gas chromatogram (FID-GC) is carried out.The qualification of the chemical composition of catalyst is to launch spectrophotometric analysis by ICP
Method is obtained.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further detailed explanation.
Embodiment 1
Preparing complex carrier 10g: add deionized water in a kettle., stirring adds attapulgite, is uniformly mixed, and prepares
Slurry A；With magnesium nitrate, aluminum nitrate as presoma, with citric acid or ethylene glycol as chelating agent, wiring solution-forming mix and blend are equal
Even, then carry out moisture evaporation, the colloidal sol of solution went from clear is transformed into the gel of thickness, and last 100-150 DEG C of dry 1-12 is little
Time, 200-400 DEG C of roasting roasting in 1-4 hour, prepare magnesium aluminate spinel metal-oxide MgAl2O4 after roasting；Slurry A adds
Enter described magnesium aluminate spinel oxide, control temperature and continue to be uniformly mixed, supersound process, prepare slurry B；Slurry B is sprayed
After mist drying and moulding, roasting obtains concavo-convex stone and the spinel oxide complex carrier of catalyst；
Employing incipient impregnation is sent out, and in 5g complex carrier, dipping is dissolved with 0.5g zinc nitrate, and 100-120 DEG C is dried, 500 DEG C of roastings
After burning 1-8 hour, the further aqueous solution of the ruthenic chloride of dipping 1.0 place 1 hour, it is dried 3 at 100 DEG C in atmosphere little
Time, and then calcine 3 hours at 500 DEG C, obtain the catalyst a1 as FT synthetic catalyst.Carried out by X-ray diffraction method
Structural analysis, found that the complex carrier in catalyst a1 has bimodal distribution, and maintains the structure of magnesium aluminate spinel.Separately
Outward, launch spectrophotometric method by ICP and carry out the chemical composition analysis of catalyst a1, found that ruthenium is in terms of metal converts
Being 5 mass %, zinc is calculated as 1 mass % with metal conversion.
In order to confirm the activity of catalyst a1, with the carborundum of 100 sieve meshes of 34.6g, the catalyst a1 of 6g is carried out dilute
Release, be filled in the reaction tube that internal diameter is 10mm, with hydrogen dividing potential drop be 0.9MPa G, temperature be 170 DEG C, flow is as 100(STP)
Ml/ minute (STP:standard temperatureand pressure) is passed through hydrogen and reduces for 3 hours.After reduction, switching
For H2/ the CO synthesis gas (comprising the Ar of about 25 volume %) than about 2, set to temperature as 260 DEG C, stagnation pressure enters as 0.9MPa G
Row reaction.
Comparative example 1
Use single molecular sieve carrier, obtain catalyst b similarly to Example 1, containing active component ruthenium-zinc Zeolite support
Catalyst b.Launch spectrophotometric method by ICP and carry out the chemical composition analysis of catalyst b, found that ruthenium changes with metal
Calculating is 5.0 mass %, and zinc is calculated as 1 mass % with metal conversion.FT reaction is carried out by method similarly to Example 1.
Reaction result and the composition analysis result of product now obtained are shown in table 1 and then by the hydro carbons of product
Other analysis result is shown in table 2.
Embodiment 2
Active component precursors becomes 0.3g ruthenic chloride and 0.4g cobalt nitrate solution, and other are identical with embodiment 1 condition, uses catalysis
Agent a2, implements at reaction temperature 270 DEG C, in addition, reacts by method similarly to Example 1.By reaction result
And the composition analysis result of the product now obtained is shown in table 1.
Embodiment 3
Active component precursors becomes ruthenic chloride, cobalt nitrate and ferric chloride solution, uses catalyst a3, active metal in catalyst a3
Ru:Co:Fe mass ratio be 1:1-4:1-3, implement at the reaction temperature 280 DEG C, in addition, with similarly to Example 1
Method is reacted.Reaction result and the composition analysis result of product that now obtains are shown in table 1.
Embodiment 4
Weighing the complex carrier of 4.5g so that it is the nickel nitrate being immersed in and the aqueous solution of zinc nitrate are also placed 1 hour, equal-volume soaks
Stain, then, in atmosphere, is dried 4 hours at 120 DEG C, roasting, then uses infusion process to be impregnated in by active component cobalt nitrate and contain
Having a complex carrier of auxiliary agent, 100 DEG C are dried 5 hours, and then calcine 4 hours at 600 DEG C, then thus obtain synthesizing as FT
The catalyst a4 of catalyst.Structural analysis is carried out, found that the complex carrier in catalyst a4 has by X-ray diffraction method
Bimodal distribution, and maintain the structure of magnesium aluminate spinel.It addition, launch spectrophotometric method by ICP to carry out catalyst a4
Chemical composition analysis, found that cobalt with metal conversion be calculated as 10.0 mass %, zinc 1%, nickel 1%.Use catalyst a4, also
Former temperature is to implement at 350 DEG C, in addition, reacts by method similarly to Example 1.
Comparative example 2
Using common alumina support to replace complex carrier, other conditions are the same as in Example 4, manufacture FT synthetic catalyst.Logical
Cross ICP transmitting spectrophotometric method and carry out the chemical composition analysis of catalyst c, found that cobalt is calculated as 10 matter with metal conversion
Amount %.
Comparative example 3
Being suitable for common Attapulgite carrier and replace complex carrier, other conditions are the same as in Example 4, manufacture FT synthesis catalytic
Agent.Launch spectrophotometric method by ICP and carry out the chemical composition analysis of catalyst d, found that cobalt is in terms of metal converts
Being 10 mass %, zinc 1%, nickel 1%, the catalytic effect of above-mentioned catalyst is listed in table 1.
Table 1 embodiment and comparative example fischer-tropsch synthetic catalyst evaluation result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Reaction temperature DEG C | 260 | 270 | 280 | 260 | 260 | 260 | 260 |
| CO conversion ratio % | 87.9 | 88.4 | 89.5 | 90.2 | 70.2 | 62.8 | 52.6 |
| CO2Conversion ratio % | 1.5 | 1.8 | 1.9 | 1.9 | 0.4 | 0.5 | 0.5 |
| CH4Conversion ratio % | 25.1 | 27.7 | 28.4 | 28.8 | 9.1 | 9.0 | 8.7 |
| C2-C4Selectivity % | 12.2 | 10.8 | 9.8 | 12.8 | 8.8 | 8.8 | 8.1 |
| C5+ selectivity % | 90.7 | 9.02 | 90.4 | 92.5 | 70. 1 | 72.1 | 73.2 |
| Petrol content C4-C10(wt%) | 90.9 | 92.3 | 93.9 | 94.2 | 40.1 | 40.1 | 42.1 |
| Kerosene distillate C11-C21(wt%) | 12.2 | 10.7 | 10.6 | 11.0 | 40.8 | 41.8 | 46.8 |
According to the result of table 1, employ comprise containing FT active metal promoter metal be carried on complex carrier FT
In the case of synthetic catalyst, and employ the situation phase comprising the carbon monoxide-olefin polymeric different containing FT active metal or carrier
Ratio, CO conversion ratio is the highest, and the ratio of the gasoline fraction in product becomes the highest, and carbon number is that the hydrocarbon of long-chain can select
Property ground cracking or isomerization, be converted into gasoline fraction, petrol content is high, can reach more than 90%.
The above, the only detailed description of the invention of the present invention, but protection scope of the present invention is not limited thereto, and any
Those of ordinary skill in the art in the technical scope that disclosed herein, the change that can expect without creative work or
Replace, all should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Fixed protection domain is as the criterion.
Claims (6)
1. a hydro carbons catalyst for fischer-tropsch synthesis compositions, it is characterised in that the activity in described Fischer-Tropsch catalyst
Component is one or more of Co, Fe, Ru, active component content relative to catalyst benchmark with amount of metal conversion be about 0.1～
30 mass %, metal promoter is about 0.1-5% relative to catalyst benchmark with amount of metal conversion, and active component is carried on auxiliary agent
Complex carrier；
Wherein, described complex carrier is concavo-convex stone and spinel oxide complex carrier, concavo-convex stone and spinel complex oxide
Mass ratio be 1:2-5, described complex carrier preparation process is:
I () adds deionized water in a kettle., stirring adds attapulgite, is uniformly mixed, and prepares slurry A；
(ii) with magnesium nitrate, aluminum nitrate as presoma, with citric acid or ethylene glycol as chelating agent, wiring solution-forming mix and blend are equal
Even, then carry out moisture evaporation, the colloidal sol of solution went from clear is transformed into the gel of thickness, and finally dry, roasting, prepares after roasting
Magnesium aluminate spinel metal-oxide MgAl2O4；
(iii) in slurry A, add described magnesium aluminate spinel oxide, control temperature and continue to be uniformly mixed, supersound process,
Prepare slurry B；
(iv) roasting after slurry B spray drying forming is obtained concavo-convex stone and the spinel oxide complex carrier of catalyst.
2. carbon monoxide-olefin polymeric as claimed in claim 1, it is characterised in that described metal promoter is the one of Ni, Zn, Mn, Zr
Plant or multiple.
3. carbon monoxide-olefin polymeric as claimed in claim 1, it is characterised in that step (ii) drying condition is 100-150 DEG C to be done
Dry 1-12 hour, roasting condition was: 200-400 DEG C of roasting 1-4 hour；The most described temperature of step is 100-200 DEG C；Step
The most described roasting condition is 350-800 DEG C of roasting 1-4 hour, preferably 400-600 DEG C roasting 1-3 hour.
4. carbon monoxide-olefin polymeric as claimed in claim 1, it is characterised in that carbon monoxide-olefin polymeric complex carrier have mesoporous-
Big pore size distribution, carrier the first aperture is 10-32nm, accounts for the 25-40% of catalyst pore structure；Second aperture is 60-80nm, accounts for and urges
The 40-55% of agent pore structure.
5. carbon monoxide-olefin polymeric application in Fischer-Tropsch synthesis as described in any one of claim 1-4, it is characterised in that will
Carbon monoxide-olefin polymeric is filled with fixed bed reactors, controls catalytic reaction temperature and is 260-350 DEG C, pressure 0.5-5MPa.
Applying the most as claimed in claim 5, it is characterised in that reduce before reaction, reducing condition is: pure hydrogen atmosphere
140～350 DEG C, hydrogen dividing potential drop is 0.1 ~ 10MPa, and volume space velocity is 500-2000h-1, the recovery time is 0.1 ~ 72 hour.
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| WO2018090388A1 (en) * | 2016-11-15 | 2018-05-24 | 万华化学集团股份有限公司 | Catalyst for resource utilization of aniline rectification residue and preparation method therefor |
| CN108855125A (en) * | 2017-05-08 | 2018-11-23 | 神华集团有限责任公司 | The method for handling catalyst of Fischer-Tropsch reaction synthetic water and preparation method thereof and processing Fischer-Tropsch reaction synthetic water |
| CN110732328A (en) * | 2018-07-23 | 2020-01-31 | 武汉科技大学 | multi-core shell structure nickel-based catalyst for carbon dioxide reforming reaction and preparation method and application thereof |
| CN112892538A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Application of catalyst in Fischer-Tropsch synthesis reaction |
| CN113332986A (en) * | 2021-06-01 | 2021-09-03 | 李�杰 | Catalyst containing spinel structure for preparing succinic anhydride by maleic anhydride hydrogenation and preparation method thereof |
| CN113634290A (en) * | 2021-08-11 | 2021-11-12 | 兖矿榆林精细化工有限公司 | Regeneration method of coal liquefaction catalyst |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018090388A1 (en) * | 2016-11-15 | 2018-05-24 | 万华化学集团股份有限公司 | Catalyst for resource utilization of aniline rectification residue and preparation method therefor |
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| CN108855125A (en) * | 2017-05-08 | 2018-11-23 | 神华集团有限责任公司 | The method for handling catalyst of Fischer-Tropsch reaction synthetic water and preparation method thereof and processing Fischer-Tropsch reaction synthetic water |
| CN110732328A (en) * | 2018-07-23 | 2020-01-31 | 武汉科技大学 | multi-core shell structure nickel-based catalyst for carbon dioxide reforming reaction and preparation method and application thereof |
| CN110732328B (en) * | 2018-07-23 | 2023-09-26 | 武汉科技大学 | Multi-core shell structure nickel-based catalyst for carbon dioxide reforming reaction and preparation method and application thereof |
| CN112892538A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Application of catalyst in Fischer-Tropsch synthesis reaction |
| CN113332986A (en) * | 2021-06-01 | 2021-09-03 | 李�杰 | Catalyst containing spinel structure for preparing succinic anhydride by maleic anhydride hydrogenation and preparation method thereof |
| CN113634290A (en) * | 2021-08-11 | 2021-11-12 | 兖矿榆林精细化工有限公司 | Regeneration method of coal liquefaction catalyst |
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| CN108404907A (en) | 2018-08-17 |
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