WO2011108348A1 - 再生フィッシャー・トロプシュ合成触媒の製造方法及び炭化水素の製造方法 - Google Patents
再生フィッシャー・トロプシュ合成触媒の製造方法及び炭化水素の製造方法 Download PDFInfo
- Publication number
- WO2011108348A1 WO2011108348A1 PCT/JP2011/053039 JP2011053039W WO2011108348A1 WO 2011108348 A1 WO2011108348 A1 WO 2011108348A1 JP 2011053039 W JP2011053039 W JP 2011053039W WO 2011108348 A1 WO2011108348 A1 WO 2011108348A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- synthesis
- regenerated
- synthesis catalyst
- reaction
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 352
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 342
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 217
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 30
- 229930195733 hydrocarbon Natural products 0.000 title claims description 26
- 239000004215 Carbon black (E152) Substances 0.000 title description 13
- 230000000694 effects Effects 0.000 claims abstract description 116
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000007789 gas Substances 0.000 claims abstract description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000010025 steaming Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011148 porous material Substances 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- 230000001172 regenerating effect Effects 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 46
- 230000009467 reduction Effects 0.000 claims description 43
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 40
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 230000000875 corresponding effect Effects 0.000 description 51
- 230000014759 maintenance of location Effects 0.000 description 47
- 229910052751 metal Inorganic materials 0.000 description 36
- 239000002184 metal Substances 0.000 description 35
- 238000011084 recovery Methods 0.000 description 28
- 229910004298 SiO 2 Inorganic materials 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 22
- 229910052739 hydrogen Inorganic materials 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 22
- 238000011068 loading method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 150000003755 zirconium compounds Chemical class 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- BDSSZTXPZHIYHM-UHFFFAOYSA-N 2-phenoxypropanoyl chloride Chemical compound ClC(=O)C(C)OC1=CC=CC=C1 BDSSZTXPZHIYHM-UHFFFAOYSA-N 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 150000001869 cobalt compounds Chemical class 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
- TZWGXFOSKIHUPW-UHFFFAOYSA-L cobalt(2+);propanoate Chemical compound [Co+2].CCC([O-])=O.CCC([O-])=O TZWGXFOSKIHUPW-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
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- PFXYQVJESZAMSV-UHFFFAOYSA-K zirconium(iii) chloride Chemical compound Cl[Zr](Cl)Cl PFXYQVJESZAMSV-UHFFFAOYSA-K 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- 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
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G2/333—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
Definitions
- the present invention relates to a method for producing a regenerated Fischer-Tropsch synthesis catalyst and a method for producing hydrocarbons using the catalyst produced by the production method.
- FT synthesis method Fischer-Tropsch synthesis method
- carbon monoxide is reduced with molecular hydrogen (hydrogen gas). It is done.
- FT synthesis method it is possible to produce a liquid fuel base material rich in paraffin hydrocarbons and not containing sulfur, and wax can also be produced. This wax can be converted into middle distillates (fuel base materials such as kerosene and light oil) by hydrocracking.
- a Fischer-Tropsch synthesis catalyst (hereinafter also referred to as “FT synthesis catalyst”), which is a catalyst used in a Fischer-Tropsch synthesis reaction (hereinafter also referred to as “FT synthesis reaction”), is generally a silica or A catalyst in which an active metal such as iron, cobalt, or ruthenium is supported on a support such as alumina (see, for example, Patent Document 1).
- an active metal such as iron, cobalt, or ruthenium
- a support such as alumina
- the catalyst performance is improved by using a second metal in addition to the active metal (see, for example, Patent Document 2).
- the second metal include sodium, magnesium, lithium, zirconium, hafnium, and the like.
- the second metal is appropriately used according to the purpose, such as an improvement in the conversion rate of carbon monoxide or an increase in chain growth probability as an index of the amount of wax produced. ing.
- the combined use of the second metal has been studied from the viewpoint of minimizing the decrease in the activity of the catalyst.
- the performance required for a practical FT synthesis catalyst mainly includes catalyst activity, product selectivity, and catalyst life.
- catalyst deterioration factors that shorten the catalyst life include deposition of carbonaceous substances during the reaction (for example, see Non-Patent Document 1), oxidation of active metal (for example, see Non-Patent Document 2), active metal and support,
- There are many research examples such as formation of complex oxides by the reaction of (see, for example, Non-Patent Document 3).
- the present inventors have conducted extensive research and found that the activity can be recovered by treating the deteriorated FT synthesis catalyst with water vapor under specific conditions. Has been completed.
- the present invention relates to a method for producing a regenerated Fischer-Tropsch synthesis catalyst obtained by regenerating a spent catalyst used in a Fischer-Tropsch synthesis reaction, wherein the silica has an average pore diameter of 4 to 25 nm by a nitrogen adsorption method.
- the spent catalyst having cobalt and / or ruthenium supported on a carrier containing, and having an activity represented by initial carbon monoxide conversion of 40 to 95% based on the activity of the corresponding unused catalyst,
- a regenerated Fischer-Tropsch synthesis catalyst comprising a steaming step for contacting a mixed gas containing 1 to 30% by volume of water vapor and an inert gas at a pressure of atmospheric pressure to 5 MPa and a temperature of 150 to 350 ° C.
- a manufacturing method is provided.
- the method for producing a regenerated Fischer-Tropsch synthesis catalyst of the present invention preferably further comprises a reduction step of reducing the catalyst obtained through the steaming step in a gas containing molecular hydrogen or carbon monoxide.
- the silica-containing support preferably further contains 1 to 10% by mass of zirconium oxide based on the mass of the catalyst.
- the present invention provides a hydrocarbon comprising a raw material containing carbon monoxide and molecular hydrogen in a Fischer-Tropsch synthesis reaction in the presence of a regenerated Fischer-Tropsch synthesis catalyst produced by the above method.
- a manufacturing method is provided.
- a method for producing a regenerated FT synthesis catalyst that is used in an FT synthesis reaction and regenerates an FT synthesis catalyst having reduced activity to a reusable level by a simple method, and a regenerated FT synthesis produced by the method.
- a method for producing hydrocarbons using a catalyst is provided.
- the spent FT synthesis catalyst used in the production method of the regenerated FT synthesis catalyst of the present invention will be described by describing the production method of the catalyst at an unused stage.
- the carrier constituting the catalyst includes silica.
- the carrier containing silica include a small amount of porous inorganic oxides such as alumina, titania and magnesia, and silica containing metal components such as sodium, magnesium, lithium, zirconium and hafnium.
- the property of the carrier containing silica is not particularly limited, but the specific surface area measured by a nitrogen adsorption method is preferably 50 to 800 m 2 / g, and more preferably 150 to 500 m 2 / g. A specific surface area of less than 50 m 2 / g is not preferable because the active metal may aggregate and the catalyst may have low activity. On the other hand, when the specific surface area is greater than 800 m 2 / g, the rate of decrease in catalytic activity due to the deposition of the carbonaceous material may increase, which is not preferable.
- the average pore diameter of the carrier containing silica in the present invention by nitrogen adsorption method is 4 to 25 nm, preferably 8 to 22 nm.
- the active metal may agglomerate excessively outside the pores of the carrier, which is not preferable because the activity tends to decrease from the initial stage of the reaction.
- the average pore diameter is larger than 25 nm, it may be difficult to carry a predetermined amount of active metal in a sufficiently dispersed state because the specific surface area is low.
- the shape of the carrier is not particularly limited, but in consideration of practicality, it is generally a spherical, cylindrical shape, or a modified cylindrical shape having a cross section such as a three-leaf type or a four-leaf type, which is generally used in actual equipment for petroleum refining or petrochemistry. A shape such as is preferable.
- the particle diameter is not particularly limited, but is preferably 1 ⁇ m to 10 mm in view of practicality.
- the shape of the support is preferably spherical, and the average particle diameter is About 10 to 300 ⁇ m is preferable, and about 30 to 150 ⁇ m is more preferable.
- the carrier containing silica preferably further contains zirconium from the viewpoint of improving the activity and suppressing the decrease in the activity over time during use.
- the carrier is preferably one in which zirconium oxide is supported on particles containing silica.
- the content of zirconium is preferably 1 to 10% by mass, more preferably 2 to 8% by mass as zirconium oxide based on the mass of the catalyst. When the content is less than 1% by mass, the above effect due to the inclusion of zirconium tends to be difficult to exert. When the content exceeds 10% by mass, the pore volume of the support tends to decrease. This is not preferable.
- zirconium there is no restriction
- the impregnation method represented by the Incipient Wetness method, the equilibrium adsorption method, etc. can be used.
- Zirconyl sulfate, zirconyl acetate, zirconyl ammonium carbonate, zirconium trichloride and the like can be used as the zirconium compound used for loading, and zirconyl ammonium carbonate and zirconyl acetate are more preferable.
- These zirconium compounds are generally used for loading as a solution, preferably an aqueous solution.
- the excessive solution of the zirconium compound and the silica-containing particles supporting the zirconium compound are separated by solid-liquid separation means such as filtration, and the resulting solid content is separated. Wash with water. Then, the particle
- the drying method is not particularly limited, and examples thereof include heat drying in air and deaeration drying under reduced pressure. The drying is usually carried out at a temperature of 100 to 200 ° C., preferably 110 to 130 ° C., for 2 to 24 hours, preferably 5 to 12 hours.
- particles containing silica on which a zirconium compound is supported are fired to convert the zirconium compound into an oxide.
- the firing conditions are not particularly limited, but the firing can usually be performed at 340 to 600 ° C., preferably 400 to 450 ° C. in an air atmosphere for 1 to 5 hours.
- a carrier containing silica on which zirconium oxide is supported is obtained.
- a compound containing an active metal is supported on the carrier obtained as described above.
- the active metal cobalt and / or ruthenium are preferable from the viewpoint of carbon monoxide conversion activity and product selectivity.
- the compound containing these metal elements used for supporting cobalt and / or ruthenium is not particularly limited, and salts or complexes of mineral acids or organic acids of these metals can be used.
- the cobalt compound include cobalt nitrate, cobalt chloride, cobalt formate, cobalt acetate, cobalt propionate, and cobalt acetylacetonate.
- the ruthenium compound include ruthenium chloride, ruthenium nitrate, and tetraoxoruthenate.
- the amount of cobalt and / or ruthenium compound supported is not particularly limited, but is generally 3 to 50% by mass, preferably 10 to 30% by mass, based on the mass of the catalyst.
- the supported amount is less than 3% by mass, the activity tends to be insufficient, and when it exceeds 50% by mass, the active metal tends to aggregate and the activity tends to decrease.
- the support on which the active metal is supported is usually dried at a temperature of 100 to 200 ° C., preferably 110 to 130 ° C. for 2 to 24 hours, preferably 5 to 10 hours.
- An FT synthesis catalyst can be obtained by calcination in an air atmosphere at 340 to 600 ° C., preferably 400 to 450 ° C., for 1 to 5 hours to convert the active metal compound into an oxide.
- the FT synthesis catalyst is reduced by performing reduction in an atmosphere containing molecular hydrogen and converting the active metal from an oxide to a metal. It is common to use for a synthetic reaction.
- the activated catalyst is directly subjected to the FT synthesis reaction.
- a stabilization treatment is performed in order to prevent the catalyst from being deactivated due to contact with air during transportation or the like. Generally, it is shipped after being applied.
- the outer surface of the activated catalyst is coated with wax or the like to block contact with air, or the outer surface of the activated catalyst is lightly oxidized to form an oxide film. And a method for preventing further oxidation due to contact with air.
- This activated and stabilized catalyst can be directly subjected to the FT synthesis reaction.
- hydrocarbons are produced by the FT synthesis reaction.
- This hydrocarbon production method differs from the hydrocarbon production method using the regenerated FT synthesis catalyst described later in detail only in that the catalyst used is an unused catalyst or a regenerated catalyst. Because there is, it omits explanation from the viewpoint of avoiding duplication.
- the activity of the catalyst subjected to the FT synthesis reaction tends to decrease with the lapse of the reaction time.
- the catalyst whose activity is reduced to a specific range as compared with the unused catalyst becomes the used FT synthesis catalyst according to the method for producing the regenerated FT synthesis catalyst of the present embodiment.
- the FT synthesis reaction may be stopped and the regeneration may be performed while the used FT synthesis catalyst is housed in the reactor.
- the used FT synthesis catalyst in the FT synthesis reaction apparatus may be transferred to a regeneration apparatus connected to the FT synthesis reaction apparatus, and regeneration may be performed in the apparatus. At this time, all of the catalyst in the FT synthesis reaction apparatus may be transferred and regenerated, or a part thereof may be transferred and regenerated.
- the used FT synthesis catalyst extracted from the FT synthesis reaction apparatus may be transferred to a regeneration apparatus independent of the apparatus for regeneration. In this case, it is preferable that the used spent FT synthesis catalyst is not brought into contact with air. From the viewpoint of blocking the contact of the extracted used FT synthesis catalyst with the air, it is preferable to perform regeneration by transferring it to a regenerator connected to the FT synthesis reaction apparatus.
- a catalyst suitable for application of the present invention has an activity represented by an initial carbon monoxide conversion of 40 to 95% based on the activity of the corresponding unused catalyst, preferably It is a used FT synthesis catalyst that is 50 to 90%.
- the “initial carbon monoxide conversion rate” refers to the carbon monoxide conversion rate obtained when 2.5 hours have elapsed from the start of the reaction in the FT synthesis reaction carried out under predetermined reaction conditions.
- the corresponding activity of the corresponding unused catalyst as a reference refers to the above-mentioned used FT synthesis catalyst using the corresponding unused catalyst (the FT synthesis catalyst before being used in the FT synthesis reaction).
- the used FT synthesis catalyst whose activity retention rate exceeds 95%, it still has an activity that can be continuously used without being regenerated, and the range of activity improvement by regeneration is limited. It is reasonable not to be reclaimed.
- the decrease in activity may be due to multiple factors such as the deposition of carbonaceous materials and the formation of complex oxides between active metal atoms and supports. Therefore, it tends to be difficult to recover the activity to such an extent that the method of the present invention is effective and can be reused.
- a hydrocarbon compound that is a product of the FT synthesis reaction is attached to the used FT synthesis catalyst extracted from the FT synthesis reaction apparatus. Since this hydrocarbon compound contains a wax component, it is solid at room temperature. In order to use this used FT synthesis catalyst in the method for producing a regenerated FT synthesis catalyst of the present invention to sufficiently recover the activity, it is preferable to first remove hydrocarbon compounds adhering to the catalyst, that is, deoil.
- Examples of the deoiling step include a method in which a catalyst containing an attached hydrocarbon compound is washed with a hydrocarbon oil mainly composed of paraffin that does not contain a sulfur compound, a nitrogen compound, a chlorine compound, an alkali metal compound, or the like.
- a product oil of a FT synthesis method having a boiling point of about 400 ° C. or less or a normal paraffin having a similar structure is used as a cleaning oil in the same step.
- the temperature and pressure at the time of washing are arbitrarily determined, the washing effect is greater when the hydrocarbon oil is heated to a temperature near its boiling point and washed.
- an autoclave type container, a flow reactor type container, or the like can be used as an apparatus used for the deoiling step.
- 70% by mass or more of the oil (in terms of carbon content) contained in the catalyst before deoiling is removed.
- this removal rate is less than 70% by mass, the diffusion of water vapor in the catalyst support in the steaming process is not sufficient, and the recovery of activity tends not to be sufficient.
- the used FT synthesis catalyst that has been subjected to the deoiling process is brought into contact with a mixed gas containing water vapor and an inert gas.
- the water vapor concentration in the mixed gas is 1 to 30% by volume, preferably 5 to 20% by volume.
- a sufficient activity recovery effect tends not to be obtained.
- the water vapor concentration exceeds 30% by volume, it tends to cause excessive aggregation of the active metal and structural collapse of the support containing silica, which is not preferable.
- Nitrogen gas etc. are mentioned as said inert gas.
- the mixed gas may further contain molecular hydrogen or carbon monoxide. However, inclusion of both molecular hydrogen and carbon monoxide is not preferable because an FT synthesis reaction occurs and there is a concern of temperature increase due to reaction heat.
- the temperature in the steaming process is 150 to 350 ° C., preferably 170 to 250 ° C.
- the temperature is less than 150 degreeC, it exists in the tendency for the effect of activity recovery to be hard to be acquired.
- the temperature exceeds 350 ° C. the oxidation of the active metal atom proceeds due to the oxidizing action accompanying steaming, which tends to generate an inactive species for carbon monoxide conversion.
- the pressure in the steaming process is from atmospheric pressure to 5 MPa, preferably from atmospheric pressure to 3 MPa.
- the pressure exceeds 5 MPa, it is not preferable because the undesirable influence of the collapse of the support structure containing silica is superior to the effect of recovery of activity.
- the time for the above steaming process is largely unaffected by the temperature, the equipment used, etc., but is generally not specified, but is selected to be about 0.1 to 10 hours.
- the regenerated FT synthesis catalyst according to this embodiment can be obtained.
- the regenerated FT synthesis catalyst can be used for the FT synthesis reaction as it is.
- the catalyst obtained through the steaming process is further subjected to a reduction process for reducing the catalyst in a gas containing molecular hydrogen or carbon monoxide to produce a regenerated FT synthesis catalyst.
- a part of the active metal atoms tend to be oxidized from the metal to the oxide by the weak oxidizing action by the steaming.
- an FT synthesis reaction at least a part of the active metal atoms that have become oxides are reduced during the reaction by the action of molecular hydrogen and carbon monoxide, which are raw materials for the reaction, to form a metal. It becomes.
- the gas containing molecular hydrogen or carbon monoxide that is the atmosphere in the reduction step is not particularly limited, but hydrogen gas, a mixed gas of hydrogen gas and inert gas such as nitrogen gas, carbon monoxide, carbon monoxide and nitrogen Examples thereof include a mixed gas with an inert gas such as a gas.
- hydrogen gas a mixed gas of hydrogen gas and inert gas such as nitrogen gas, carbon monoxide, carbon monoxide and nitrogen
- examples thereof include a mixed gas with an inert gas such as a gas.
- the gas does not contain molecular hydrogen and contains carbon monoxide, it is produced as a by-product in the case of reduction with molecular hydrogen, and there is no generation of water that is supposed to inhibit the reduction of active metal atoms. , Higher reduction of active metal atoms tends to be obtained.
- the gas contains both molecular hydrogen and carbon monoxide because an FT synthesis reaction occurs in the reduction step and there is a concern of temperature increase due to reaction heat. However, it is permissible if each component is a mixture of a small amount.
- the reduction temperature is preferably 250 to 500 ° C., more preferably 350 to 450 ° C.
- the reduction temperature is lower than 250 ° C., the effect of increasing the reduction degree of the active metal atom tends to be insufficient.
- the reduction temperature exceeds 500 ° C., the activity tends to decrease because the aggregation of the active metal proceeds excessively.
- the reduction temperature is preferably 200 to 400 ° C., more preferably 250 to 350 ° C.
- the said temperature is lower than 200 degreeC, it exists in the tendency for sufficient reduction
- the temperature exceeds 400 ° C., carbon typified by carbon nanotubes tends to be easily generated from carbon monoxide.
- the atmospheric pressure is not particularly limited, but is generally about atmospheric pressure to 5 MPa.
- the reduction time largely depends on the reduction temperature, the apparatus to be used, and the like, and thus it is difficult to define it unconditionally, but it is generally about 0.5 to 30 hours.
- the regenerated FT synthesis catalyst according to this embodiment is obtained.
- the regenerated FT synthesis catalyst also needs to be transported with contact with air for the catalyst in the activated state. It is preferable to carry out the transfer or the like after performing the same stabilization treatment as that for the unused catalyst.
- [100 ⁇ initial carbon monoxide conversion rate of regenerated FT synthesis catalyst / corresponding initial carbon monoxide conversion rate of unused catalyst] (%) will be referred to as “activity recovery rate”.
- reaction apparatus a fixed bed reaction apparatus or a slurry bed reaction apparatus is preferable. Further, the reaction is preferably performed under the condition that the conversion rate of carbon monoxide constituting the raw material gas is 50% or more, and more preferably in the range of 70 to 90%. Note that there is basically no difference from the case of using an unused catalyst except that a regenerated catalyst is used as the catalyst.
- a bubble column type fluidized bed reaction apparatus can be used.
- the regenerated FT synthesis catalyst according to the present embodiment is suspended in hydrocarbon that is liquid at the reaction temperature (usually FT synthesized hydrocarbon produced in the reactor).
- a slurry is accommodated, and a mixed gas containing carbon monoxide gas and molecular hydrogen (generally a synthetic gas obtained by reforming hydrocarbons such as natural gas) is introduced into the slurry from the lower part of the reaction tower.
- the mixed gas dissolves in the hydrocarbons while rising in the form of bubbles in the reaction tower and comes into contact with the catalyst to generate hydrocarbons.
- the slurry is stirred by the rising of the bubbles of the mixed gas, and the fluid state is maintained.
- a cooling pipe through which a cooling medium for removing reaction heat flows is installed in the reaction tower, and the reaction heat is removed by heat exchange.
- the reaction temperature of the FT synthesis reaction can be determined by the target carbon monoxide conversion, but is preferably 150 to 300 ° C, more preferably 170 to 250 ° C.
- the reaction pressure is preferably 0.5 to 5.0 MPa, more preferably 2.0 to 4.0 MPa. If the reaction pressure is less than 0.5 MPa, the carbon monoxide conversion tends to be difficult to be 50% or more, and if it exceeds 5.0 MPa, local heat generation tends to occur, which is not preferable.
- the molecular hydrogen / carbon monoxide ratio (molar ratio) in the raw material gas is preferably 0.5 to 4.0, and more preferably 1.0 to 2.5.
- the molar ratio is less than 0.5, the reaction temperature tends to be high and the catalyst tends to be deactivated.
- it exceeds 4.0 the amount of methane that is an undesirable by-product tends to increase. It is in.
- the gas hourly space velocity of the raw material gas is 500 ⁇ 5000h -1, more preferably 1000 ⁇ 2500h -1. If the gas space velocity is less than 500h -1, the low productivity for the same amount of catalyst, if more than 5000h -1, the conversion of carbon monoxide is not preferred since it is difficult it becomes 50% or more.
- the regenerated FT synthesis catalyst according to this embodiment has a high activity recovery rate.
- the regenerated FT synthesis catalyst has a high chain growth probability ( ⁇ ).
- ⁇ chain growth probability
- the present invention is not limited to the above-described preferred embodiments, and can be appropriately modified without departing from the gist of the present invention.
- the reaction was conducted at a temperature of 230 ° C., a pressure of 2.3 MPa, and a stirring speed of 800 rpm.
- the gas composition at the outlet of the autoclave was analyzed over time by gas chromatography, and the above-mentioned initial carbon monoxide conversion was calculated from the analysis data. Further, from the analysis of the product, the chain growth probability ⁇ was determined by a conventional method. Separately, using the corresponding used FT synthesis catalyst and the corresponding unused catalyst, the FT synthesis reaction was carried out in the same manner as described above, and the initial carbon monoxide conversion was similarly determined. And according to the above-mentioned definition, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability ⁇ when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
- the FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
- a method for producing a regenerated FT synthesis catalyst that regenerates an FT synthesis catalyst that has been used in an FT synthesis reaction and has reduced activity to a reusable level by a simple method and the method.
- a method for producing hydrocarbons using the regenerated FT synthesis catalyst is provided.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
なお、以後、〔100×再生FT合成触媒の初期一酸化炭素転化率/相当する未使用の触媒の初期一酸化炭素転化率〕(%)を「活性回復率」と呼ぶこととする。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が92.3%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径11.2nm、ZrO2担持量8.5質量%(触媒の質量基準))25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素ガス=9.8/90.2の混合気体流通下、全圧1.5MPa、200℃で1時間スチーミングを行った(スチーミング工程)。続いて、同反応装置内にて、水素気流下、400℃で3時間、前記スチーミング後の触媒の還元を行った(還元工程)。これにより、再生FT合成触媒を得た。
上記により得られた再生FT合成触媒5gを、窒素ガス雰囲気下にてセタン30mlと共に内容積100mlのオートクレーブに移し、FT合成反応を行った。水素ガス/一酸化炭素が2/1(モル比)の混合ガスを原料とし、W(触媒質量)/F(合成ガス流量)=3g・h/molにて前記混合ガスを連続的に前記オートクレーブに流通させ、温度230℃、圧力2.3MPa、攪拌速度800rpmにおいて反応を行なった。オートクレーブ出口のガス組成をガスクロマトグラフィー法により経時的に分析し、この分析データから前述の初期一酸化炭素転化率を算出した。また、生成物の分析から、連鎖成長確率αを常法により求めた。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行ない、初期一酸化炭素転化率を同様に求めた。そして、前述の定義に従って、使用済みFT合成触媒の活性保持率、及び再生FT合成触媒の活性回復率を算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が50.1質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径12.4nm、ZrO2担持量7.9質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素ガス=11.2/88.8の混合気体流通下、全圧1.6MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が78.4質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径20.4nm、ZrO2担持量6.6質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=9.4/90.6の混合ガス流通下、全圧0.5MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が77.2質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径8.9nm、ZrO2担持量7.1質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=8.2/91.8の混合ガス流通下、全圧0.5MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が71.2質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径18.4nm、ZrO2担持量9.4質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=6.5/93.5の混合ガス流通下、全圧1.6MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が71.1質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径17.6nm、ZrO2担持量2.6質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=7.4/92.6の混合ガス流通下、全圧1.6MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が76.6質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径14.3nm、ZrO2担持量7.1質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=27.1/72.9の混合ガス流通下、全圧2.3MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が74.5質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径15.2nm、ZrO2担持量6.6質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=4.4/95.6の混合ガス流通下、全圧2.2MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が72.3質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径10.2nm、ZrO2担持量2.3質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=10.5/89.5の混合ガス流通下、全圧2.5MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が72.8質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径10.9nm、ZrO2担持量3.8質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=11.4/88.6の混合ガス流通下、全圧0.1MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が76.4質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径16.4nm、ZrO2担持量5.1質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=8.8/91.2の混合ガス流通下、全圧2.2MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が77.4質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径16.9nm、ZrO2担持量4.7質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=7.6/92.4の混合ガス流通下、全圧2.1MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が76.4質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径18.4nm、ZrO2担持量13.2質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=8.8/91.2の混合ガス流通下、全圧1.6MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が77.1質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径17.6nm、ZrO2担持量0.7質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=7.6/92.4の混合ガス流通下、全圧1.6MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率、及び再生FT合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が35.8質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径12.4nm、ZrO2担持量8.2質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=11.2/88.8の混合ガス流通下、全圧1.6MPa、210℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率を算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が75.3質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径14.3nm、ZrO2担持量7.1質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=41/59の混合ガス流通下、全圧2.3MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率を算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が74.1質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径15.2nm、ZrO2担持量6.6質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=0.4/99.6の混合ガス流通下、全圧2.2MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率を算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が70.2質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径10.9nm、ZrO2担持量3.8質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=11.4/88.6の混合ガス流通下、全圧5.5MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率を算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が75.2質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径12.3nm、ZrO2担持量6.3質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=4.4/95.6の混合ガス流通下、全圧2.2MPa、362℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率を算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が75.2質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径14.3nm、ZrO2担持量5.4質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=4.4/95.6の混合ガス流通下、全圧2.1MPa、121℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率を算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が75.3質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径27.2nm、ZrO2担持量6.6質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=9.4/90.6の混合ガス流通下、全圧0.5MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率を算出した。結果を表1に示す。
<再生FT合成触媒の調製>
後述の方法で測定した活性保持率が74.2質量%である、FT合成反応に使用済みであり、脱油された粉体状Co/SiO2-ZrO2触媒(平均細孔径3.3nm、ZrO2担持量7.1質量%)25gを、固定床流通式反応装置に充填し、体積比で水蒸気/窒素=8.2/91.8の混合ガス流通下、全圧0.5MPa、200℃で1時間スチーミングを行った。次に、同反応装置内にて、水素気流下、400℃で3時間還元を行った。これにより、再生FT合成触媒を得た。
触媒として上記により得られた再生FT合成触媒を用いた以外は実施例1と同様の操作にてFT合成反応を行なった。また、別途、相当する使用済みFT合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でFT合成反応を行なった。そして、実施例1と同様に、使用済みFT合成触媒の活性保持率、再生FT合成触媒の活性回復率を算出した。結果を表1に示す。
Claims (5)
- フィッシャー・トロプシュ合成反応に使用した使用済み触媒を再生して得られる再生フィッシャー・トロプシュ合成触媒の製造方法であって、
窒素吸着法による平均細孔径が4~25nmであるシリカを含む担体にコバルト及び/又はルテニウムが担持され、初期一酸化炭素転化率で表される活性が、相当する未使用の触媒の当該活性を基準として40~95%である前記使用済み触媒を、大気圧~5MPaの圧力、150~350℃の温度にて、1~30体積%の水蒸気及び不活性ガスを含む混合ガスに接触させるスチーミング工程を備えることを特徴とする再生フィッシャー・トロプシュ合成触媒の製造方法。 - 前記スチーミング工程を経て得られた触媒を、分子状水素又は一酸化炭素を含む気体中で還元する還元工程を更に備えることを特徴とする請求項1に記載の再生フィッシャー・トロプシュ合成触媒の製造方法。
- 前記シリカを含む担体が、更に触媒の質量を基準として1~10質量%の酸化ジルコニウムを含むこと特徴とする請求項1又は2に記載の再生フィッシャー・トロプシュ合成触媒の製造方法。
- 前記スチーミング工程を含む再生フィッシャー・トロプシュ合成触媒を製造するための全工程を、フィッシャー・トロプシュ合成反応装置と接続された再生装置内において実施することを特徴とする請求項1~3のいずれか一項に記載の再生フィッシャー・トロプシュ合成触媒の製造方法。
- 請求項1~4のいずれか一項に記載の方法により製造された再生フィッシャー・トロプシュ合成触媒の存在下に、一酸化炭素及び分子状水素を含む原料をフィッシャー・トロプシュ合成反応に供することを特徴とする炭化水素の製造方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2791270A CA2791270C (en) | 2010-03-05 | 2011-02-14 | Method for manufacturing a regenerated fischer-tropsch synthesis catalyst, and hydrocarbon manufacturing method |
AU2011222198A AU2011222198B2 (en) | 2010-03-05 | 2011-02-14 | Method for manufacturing a regenerated Fischer-Tropsch synthesis catalyst, and hydrocarbon manufacturing method |
CN201180012586.8A CN102791377B (zh) | 2010-03-05 | 2011-02-14 | 再生费托合成催化剂的制造方法和烃的制造方法 |
RU2012142320/04A RU2549569C2 (ru) | 2010-03-05 | 2011-02-14 | Способ получения регенерированного катализатора синтеза фишера-тропша и способ получения углеводородов |
US13/581,948 US8557725B2 (en) | 2010-03-05 | 2011-02-14 | Method for manufacturing a regenerated Fischer-Tropsch synthesis catalyst, and hydrocarbon manufacturing method |
ZA2012/07040A ZA201207040B (en) | 2010-03-05 | 2012-09-19 | Method for manufacturing a regenerated fischer-tropsch synthesis catalyst, and hydrocarborn manufacturing method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010049633A JP5771358B2 (ja) | 2010-03-05 | 2010-03-05 | 再生フィッシャー・トロプシュ合成触媒の製造方法及び炭化水素の製造方法 |
JP2010-049633 | 2010-03-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011108348A1 true WO2011108348A1 (ja) | 2011-09-09 |
Family
ID=44542011
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/053039 WO2011108348A1 (ja) | 2010-03-05 | 2011-02-14 | 再生フィッシャー・トロプシュ合成触媒の製造方法及び炭化水素の製造方法 |
Country Status (9)
Country | Link |
---|---|
US (1) | US8557725B2 (ja) |
JP (1) | JP5771358B2 (ja) |
CN (1) | CN102791377B (ja) |
AU (1) | AU2011222198B2 (ja) |
CA (1) | CA2791270C (ja) |
MY (1) | MY156577A (ja) |
RU (1) | RU2549569C2 (ja) |
WO (1) | WO2011108348A1 (ja) |
ZA (1) | ZA201207040B (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2791267C (en) * | 2010-03-05 | 2017-03-07 | Jx Nippon Oil & Energy Corporation | Fischer-tropsch synthesis catalyst, manufacturing method therefor, and hydrocarbon manufacturing method |
CN105903497B (zh) * | 2016-05-24 | 2019-06-07 | 江南大学 | 费托合成使用的钴基催化剂的再生处理方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59102440A (ja) * | 1982-11-22 | 1984-06-13 | シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ | フイツシヤ−トロプシユ触媒の製造法、そのようにして製造された触媒及び炭化水素の製造におけるかかる触媒の使用 |
JPH05208141A (ja) * | 1991-08-20 | 1993-08-20 | Shell Internatl Res Maatschappij Bv | 触媒の活性化方法 |
JP2005525922A (ja) * | 2002-01-29 | 2005-09-02 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | 担持触媒処理 |
WO2005099897A1 (ja) * | 2004-04-16 | 2005-10-27 | Nippon Oil Corporation | フィッシャー・トロプシュ合成用触媒および炭化水素の製造法 |
JP2007270049A (ja) * | 2006-03-31 | 2007-10-18 | Nippon Oil Corp | 一酸化炭素の還元による炭化水素の製造方法 |
JP2008073687A (ja) * | 2006-08-25 | 2008-04-03 | Nippon Steel Corp | 合成ガスから炭化水素を製造する触媒、触媒の製造方法、触媒の再生方法、及び合成ガスから炭化水素を製造する方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9010075D0 (en) | 1990-05-04 | 1990-06-27 | Shell Int Research | Process for the preparation of alumina based extrudates |
US6486220B1 (en) * | 1999-11-17 | 2002-11-26 | Conoco Inc. | Regeneration procedure for Fischer-Tropsch catalyst |
ES2227249T3 (es) * | 2000-07-03 | 2005-04-01 | Shell Internationale Research Maatschappij B.V. | Catalizador y procedimiento de preparacion de hidrocarburos. |
US6531517B1 (en) * | 2000-08-01 | 2003-03-11 | Exxonmobil Research And Engineering Company | Process for increasing carbon monoxide hydrogenation activity of catalysts via low temperature oxidation with water, steam or mixture thereof |
US6812179B2 (en) * | 2001-04-25 | 2004-11-02 | Syntroleum Corporation | Process for regenerating a slurry fischer-tropsch catalyst |
US6878655B2 (en) * | 2002-09-20 | 2005-04-12 | Conocophillips Company | Method and apparatus for the regeneration of hydrocarbon synthesis catalysts |
JP4907212B2 (ja) * | 2006-03-31 | 2012-03-28 | Jx日鉱日石エネルギー株式会社 | 一酸化炭素の還元触媒およびその調製方法 |
US9295976B2 (en) | 2006-08-25 | 2016-03-29 | Nippon Steel Engineering Co., Ltd | Catalyst for producing hydrocarbon from syngas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from sysngas |
EP1920836A1 (en) * | 2006-10-27 | 2008-05-14 | Shell Internationale Researchmaatschappij B.V. | Process for regenerating a cobalt catalyst |
-
2010
- 2010-03-05 JP JP2010049633A patent/JP5771358B2/ja not_active Expired - Fee Related
-
2011
- 2011-02-14 MY MYPI2012700602A patent/MY156577A/en unknown
- 2011-02-14 CN CN201180012586.8A patent/CN102791377B/zh not_active Expired - Fee Related
- 2011-02-14 RU RU2012142320/04A patent/RU2549569C2/ru not_active IP Right Cessation
- 2011-02-14 US US13/581,948 patent/US8557725B2/en not_active Expired - Fee Related
- 2011-02-14 AU AU2011222198A patent/AU2011222198B2/en not_active Ceased
- 2011-02-14 WO PCT/JP2011/053039 patent/WO2011108348A1/ja active Application Filing
- 2011-02-14 CA CA2791270A patent/CA2791270C/en not_active Expired - Fee Related
-
2012
- 2012-09-19 ZA ZA2012/07040A patent/ZA201207040B/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59102440A (ja) * | 1982-11-22 | 1984-06-13 | シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ | フイツシヤ−トロプシユ触媒の製造法、そのようにして製造された触媒及び炭化水素の製造におけるかかる触媒の使用 |
JPH05208141A (ja) * | 1991-08-20 | 1993-08-20 | Shell Internatl Res Maatschappij Bv | 触媒の活性化方法 |
JP2005525922A (ja) * | 2002-01-29 | 2005-09-02 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | 担持触媒処理 |
WO2005099897A1 (ja) * | 2004-04-16 | 2005-10-27 | Nippon Oil Corporation | フィッシャー・トロプシュ合成用触媒および炭化水素の製造法 |
JP2007270049A (ja) * | 2006-03-31 | 2007-10-18 | Nippon Oil Corp | 一酸化炭素の還元による炭化水素の製造方法 |
JP2008073687A (ja) * | 2006-08-25 | 2008-04-03 | Nippon Steel Corp | 合成ガスから炭化水素を製造する触媒、触媒の製造方法、触媒の再生方法、及び合成ガスから炭化水素を製造する方法 |
Non-Patent Citations (4)
Title |
---|
CHEN, J.-G. ET AL.: "Study on stability of Co/ Zr02/Si02 catalyst for F-T synthesis", STUDIES IN SURFACE SCIENCE AND CATALYSIS, vol. 136, 2001, pages 525 - 529 * |
KISS, G. ET AL.: "Hydrothermal deactivation of silica-supported cobalt catalysts in Fischer- Tropsch synthesis", JOURNAL OF CATALYSIS, vol. 217, no. 1, 25 March 2003 (2003-03-25), pages 127 - 140, XP002501074, DOI: doi:10.1016/S0021-9517(03)00054-X * |
SAIB, A.M. ET AL.: "Fundamental understanding of deactivation and regeneration of cobalt Fischer- Tropsch synthesis catalysts", CATALYSIS TODAY, vol. 154, no. 3-4, 15 March 2010 (2010-03-15), ELEVENTH INTERNATIONAL SYMPOSIUM ON CATALYST DEACTIVATION, DELFT(THE NETHERLANDS), pages 271 - 282, XP027197224 * |
VAN DE LOOSDRECHT, J. ET AL.: "Cobalt Fischer- Tropsch synthesis: Deactivation by oxidation?", CATAL. TODAY, vol. 123, no. 1-4, 12 April 2007 (2007-04-12), pages 293 - 302, XP022085601, DOI: doi:10.1016/j.cattod.2007.02.032 * |
Also Published As
Publication number | Publication date |
---|---|
US8557725B2 (en) | 2013-10-15 |
ZA201207040B (en) | 2013-05-29 |
JP5771358B2 (ja) | 2015-08-26 |
US20120322899A1 (en) | 2012-12-20 |
AU2011222198B2 (en) | 2016-01-21 |
RU2549569C2 (ru) | 2015-04-27 |
RU2012142320A (ru) | 2014-04-10 |
JP2011183282A (ja) | 2011-09-22 |
CN102791377A (zh) | 2012-11-21 |
CA2791270C (en) | 2018-04-03 |
MY156577A (en) | 2016-03-15 |
AU2011222198A1 (en) | 2012-09-06 |
CN102791377B (zh) | 2015-02-25 |
CA2791270A1 (en) | 2011-09-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
RU2389548C2 (ru) | Промотированный катализатор синтеза фишера-тропша, способ его получения и способ синтеза углеводородов фишера-тропша | |
CA2470945C (en) | Regeneration of catalysts for carbon monoxide hydrogenation | |
JP5676120B2 (ja) | 活性化フィッシャー・トロプシュ合成触媒の製造方法及び炭化水素の製造方法 | |
JP5759447B2 (ja) | フィッシャー・トロプシュ合成触媒の製造方法、並びに炭化水素の製造方法 | |
JP4808688B2 (ja) | 合成ガスから炭化水素を製造する触媒、触媒の製造方法、触媒の再生方法、及び合成ガスから炭化水素を製造する方法 | |
GB2482905A (en) | Fischer-Tropsch catalyst regeneration | |
EA010025B1 (ru) | Способ удаления cos из потока синтез-газа, включающего hs и cos | |
AU2007288693A1 (en) | Catalyst for producing hydrocarbon from synthetic gas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from synthetic gas | |
AU2002358297B2 (en) | Regeneration of supported catalysts for carbon monoxide hydrogenation | |
ZA200404975B (en) | Catalyst enhancement. | |
WO2012132905A1 (ja) | 活性化されたフィッシャー・トロプシュ合成反応用触媒および炭化水素の製造方法 | |
JP5100151B2 (ja) | 合成ガスから炭化水素を製造する触媒、触媒の製造方法、合成ガスから炭化水素を製造する方法、及び、触媒の再生方法 | |
JP5919145B2 (ja) | 合成ガスから炭化水素を製造する触媒の製造方法、合成ガスから炭化水素を製造する方法、及び触媒の再生方法 | |
JP5771358B2 (ja) | 再生フィッシャー・トロプシュ合成触媒の製造方法及び炭化水素の製造方法 | |
ZA200404977B (en) | Supported catalyst treatment. | |
JP2008291146A (ja) | 多孔質脱硫剤及びこれを用いた炭化水素油の脱硫方法 | |
CA2509230A1 (en) | Attrition resistant bulk metal catalysts and methods of making and using same | |
JP5932093B2 (ja) | 重質留分の分解反応を利用した炭素構造体の製造方法 | |
CN106391019B (zh) | 用于制备意图在费托反应中使用的催化剂的方法 | |
JP4732703B2 (ja) | オレフィンに富む炭化水素を製造するための触媒 | |
JP4126100B2 (ja) | 触媒寿命が延長されたスラリー炭化水素合成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180012586.8 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11750461 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011222198 Country of ref document: AU |
|
ENP | Entry into the national phase |
Ref document number: 2791270 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13581948 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1201004472 Country of ref document: TH |
|
ENP | Entry into the national phase |
Ref document number: 2011222198 Country of ref document: AU Date of ref document: 20110214 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012142320 Country of ref document: RU |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11750461 Country of ref document: EP Kind code of ref document: A1 |