JPH0370691B2 - - Google Patents
Info
- Publication number
- JPH0370691B2 JPH0370691B2 JP58248035A JP24803583A JPH0370691B2 JP H0370691 B2 JPH0370691 B2 JP H0370691B2 JP 58248035 A JP58248035 A JP 58248035A JP 24803583 A JP24803583 A JP 24803583A JP H0370691 B2 JPH0370691 B2 JP H0370691B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- ruthenium
- reaction
- manganese
- manganese dioxide
- 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.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 119
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 69
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 50
- 229910052707 ruthenium Inorganic materials 0.000 claims description 47
- 238000004519 manufacturing process Methods 0.000 claims description 36
- 229930195733 hydrocarbon Natural products 0.000 claims description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims description 22
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 description 46
- 238000000034 method Methods 0.000 description 33
- 150000001336 alkenes Chemical class 0.000 description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 20
- 239000010457 zeolite Substances 0.000 description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000012190 activator Substances 0.000 description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 239000011572 manganese Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000009835 boiling Methods 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- 239000012876 carrier material Substances 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000001354 calcination Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- -1 aliphatic primary alcohols Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- 238000001308 synthesis method Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003304 ruthenium compounds Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 description 1
- XZQYTGKSBZGQMO-UHFFFAOYSA-I Rhenium(V) chloride Inorganic materials Cl[Re](Cl)(Cl)(Cl)Cl XZQYTGKSBZGQMO-UHFFFAOYSA-I 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GBDZMMXUOBAJMN-UHFFFAOYSA-K azane;ruthenium(3+);trichloride Chemical compound N.N.N.N.N.N.[Cl-].[Cl-].[Cl-].[Ru+3] GBDZMMXUOBAJMN-UHFFFAOYSA-K 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229940075417 cadmium iodide Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- VLWBWEUXNYUQKJ-UHFFFAOYSA-N cobalt ruthenium Chemical compound [Co].[Ru] VLWBWEUXNYUQKJ-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 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
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 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
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UXMRNSHDSCDMLG-UHFFFAOYSA-J tetrachlororhenium Chemical compound Cl[Re](Cl)(Cl)Cl UXMRNSHDSCDMLG-UHFFFAOYSA-J 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- VGBPIHVLVSGJGR-UHFFFAOYSA-N thorium(4+);tetranitrate Chemical compound [Th+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VGBPIHVLVSGJGR-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
本発明は水素と一酸化炭素とからオレフイン類
を製造する方法に関するものである。
水素と一酸化炭素との混合ガスを高めた温度お
よび圧力下で触媒と接触させることにより炭化水
素類を製造することは、いわゆるフイツシヤー・
トロプシユ（FT）法による炭化水素合成法とし
て公知である。
一酸化炭素の接触水素は使用した触媒及び適用
した反応条件により炭素原子数１〜40個を含むパ
ラフインとオレフインとより成る混合物を生じ、
場合によつてはアルコール、アルデヒド、ケト
ン、エステルあるいは脂肪酸のような酸素を含む
化合物も生じる。また選定された合成条件下では
少量の芳香族炭化水素も生成される。
一酸化炭素の水素化に関する著しい活性は周期
律表第８族の元素、特に鉄、コバルト、ニツケ
ル、ルテニウムによつて示される。これら元素の
特徴は有する水素化活性及び一次生成物としての
α−オレフインの触媒表面への再吸着による二次
反応の程度の差によつて生成物の分布およびその
組成に著しく差を生じる。ニツケル、コバルト及
びルテニウム系触媒は主として枝分れのない飽和
炭化水素の混合物を与え、他方鉄を含む触媒を用
いて多量の不飽和脂肪族化合物、更に酸素を含む
化合物特に脂肪族第一級アルコールを含有する炭
化水素を製造することが出来ることはすでに公知
である。また約20より多い炭素数を有し、大気圧
ないし高められた圧力で約200〜300℃の反応温度
で炭化水素60wt％以上含有する混合物は困難な
く公知方法により製造することが出来る。鉄系触
媒を用いると不飽和炭化水素成分に富む混合生成
物を与えるが副生する炭酸ガス量及び含酸素化合
物量が多く炭化水素の生成選択性が悪い。一方ル
テニウム系触媒は鉄系触媒に比べて、金属当りの
FT反応活性は数倍高いが、水素化活性も高いた
め、生成物中の飽和炭化水素成分が多く、反応圧
力及び反応温度に対して依存性が高く、FT反応
を論ずる指標として良く用いられるシユルツ・フ
ローリー則の連鎖成長確立α値が反応温度上昇と
共に、その値は大きく減少する傾向にある。この
様な理由からルテニウム系触媒を用いてC2〜C4
の低級炭化水素あるいはC5以上のオレフイン系
炭化水素を多く含有する反応生成物を選択的に導
くことは、非常に困難と云われている。
また平衡論から一酸化炭素の水素化反応を見る
と、炭化水素生成の自由エネルギー変化ΔFと平
衡定数Ｋとの間には−ΔF＝RTlnKという関係か
らある温度で一酸化炭素の水素化反応が平衡論的
に見て有利かどうか判断できる。一般的には低温
領域ではオレフインの生成より、パラフインの生
成の方が有利となる。たとえばプロピレン／プロ
パン生成比よりもエチレン／エタン生成比の方が
小さく、FT反応生成物の選択性でプロピレン／
プロパン生成比を上げるよりもエチレン／エタン
生成比を上げる方が平衡論的に見る限り、より困
難と云える。C2〜C4の低級オレフイン類の選択
的生成は平衡論的に不利であるが、この不利さを
速度論的にいかに克服するかが良い低級オレフイ
ン選択性を得るための鍵となつている。従つて一
酸化炭素を水素と接触反応させることにより高転
化率かつ高選択率でオレフイン系炭化水素が製造
できれば得られるメリツトは大きい。
従来マンガンの酸化物を含む触媒を用いてフイ
ツシヤー・トロプシユ反応を行ない炭化水素類を
製造する方法は特公昭56−48491号、米国特許第
4177203号および米国特許第4206134号により公知
である。特公昭56−48491号には鉄と酸化マンガ
ンとよりなる混合物を1050℃で焼成して得られる
触媒を用いるとガス状オレフインが高収率で得ら
れると記載されている。しかしながら後述の比較
例５で示すようにマンガン酸化物と鉄とよりなる
触媒は一酸化炭素転化率が極端に低く触媒活性は
非常に低いし、これを1050℃で焼成してもやはり
触媒活性は非常に低いことがわかつた。米国特許
第4177203号にもマンガン50％以上と鉄50％以下
とからなる触媒を用いるとC2〜C4炭化水素が選
択率よく生成すると記載されているが、後述比較
例５に示すようにマンガンと鉄とよりなる触媒は
活性が非常に低い。そして米国特許第4206134号
にはルテニウムを一酸化マンガンに担持した触媒
を用いてFT反応を行なうとC2〜C4オレフインの
生成が多く、またメタンの生成は少ないと記載さ
れている。しかしながら後述比較例１に示したよ
うに一酸化マンガンにルテニウムを担持した触媒
はオレフイン類の生成量は非常に低い。
今回我々は、マンガン酸化物の荷電数及びその
結晶性に着目し、代表的な均一固相酸化還元系と
して認識すべき二酸化マンガン（MnO2）のユニ
ークな物性と興味深い挙動を一酸化炭素と水素と
の接触反応（FT反応）に見い出した。
本発明の主な目的はオレフイン系炭化水素、殊
にC2〜C4のような低級オレフイン類を選択率よ
く製造する方法を提供することにあり、他の目的
はメタンの生成を抑えてオレフイン類を選択率よ
く製造する方法を提供することにあり、また他の
目的はオレフイン類に富む炭化水素を転化率よく
製造する方法を提供することにある。
すなわち本発明の要旨は、マンガン酸化物担体
に担持されたルテニウム触媒に水素および一酸化
炭素を含む混合ガスを接触させて炭化水素類を製
造する方法において、担体としてγ型二酸化マン
ガンを用いることを特徴とするオレフイン類の製
造法に存する。
本発明の触媒はγ型二酸化マンガンよりなる担
体にルテニウムを担持して調製されるものである
が、必要によりキヤリヤー物質およびまたは活性
化剤を含有させてもよい。
触媒調製に用いる二酸化マンガンは結晶化度の
低い型に属するγ型の二酸化マンガンであり、こ
れはヨウ化カドミウム型の層状格子構造に類似で
ある。
ここで使用されるγ型二酸化マンガンは例えば
マンガン塩溶液の化学的酸化法に属する
中性MnSO4の沸とう溶液にKMnO4溶液の添
加による合成方法
硫酸マンガン（）と硫酸との混合沸とう水
溶液に過硫酸アンモニウムを加えて合成する方
法
硫酸マンガン（）と硝酸カリウムとの混合
温水溶液に過マンガン酸カリウムを加えて合成
する方法
マンガン塩溶液の電解酸化法に属する
熱酸性MnSO4溶液のグラフアイト電極によ
る陽極酸化による合成方法
熱酸性MnSO4溶液の白金電極による陽極酸
化による合成方法
および焼成と酸処理法に属する
β−MnO2を600℃に加熱、沸とう希H2SO4
で浸出による合成方法
MnCO3（0.1％NaOH添加）を酸素ガス中350
℃で焼成、希硫酸で処理する合成方法
により合成される。他の公知γ型二酸化マンガン
合成法及び変成法で合成されるγ型二酸化マンガ
ンでもよい。
これらの物質上に支持されたルテニウムのFT
炭化水素合成特性を実質上、阻害しないような他
の難溶物質をキヤリヤー物質として触媒中に含有
させることも可能である。たとえばTiO2、SiO2、
Al2O3、Cr2O3、V2O5、WO3、MoO3等の金属酸
化物やゼオライトをキヤリヤー物質として二酸化
マンガンと均質混合することも出来る。
本発明においてゼオライトは結晶性アルミノけ
い酸塩ゼオライトを意味し、その例としてはＹ型
ゼオライト、Ｘ型ゼオライト、Ａ型ゼオライト、
モルデナイト、ZSM系ゼオライト（ZSM系ゼオ
ライトとしては例えばZSM−４、ZSM−５、
ZSM−34などがあり、昭和57年１月11日日本技
術経済センター出版部発行「最近のゼオライト技
術と応用の進歩総合資料集」46〜57頁、高橋浩ほ
か編昭和50年２月１日講談社発行「ゼオライト」
46〜47頁、特開昭57−70828号明細書等に詳述さ
れている。）などがある。これらゼオライトは
Na、Ｋなど金属置換型のものでもよいが、水素
形のものが好ましく、また合成品でも天然産のも
のでもよい。またこれらゼオライトを脱アルミニ
ウム処理したものも使用できる。脱アルミニウム
方法の一例はゼオライトを酸（塩酸、硫酸などの
無機酸、酢酸、しゆう酸、アジピン酸などの有機
酸のいずれでもよい。）、あるいはEDTA（エチレ
ンジアミンテトラ酢酸ナトリウム）などのキレー
ト剤の水溶液中で加熱処理してゼオライト中のア
ルミニウムの一部を溶出させる。モルデナイト、
ZSM−５などのような耐酸性のあるゼオライト
は酸処理でよいが、Ｙ型ゼオライトなどのような
耐酸性の低いゼオライトはキレート剤水溶液で処
理する。処理時の温度、酸またはキレート剤の濃
度、処理時間等に特に制限はないが、通常濃度は
数％程度（例えば約１〜15wt％）、温度は溶液の
沸とう温度、時間は約30分〜数時間程度の条件で
行なう。後必要により乾燥、焼成する。これらキ
ヤリヤー物質はγ型二酸化マンガンと均質混合し
たり、あるいはγ型二酸化マンガンにルテニウム
を担持したものと物理的に混合して用いることが
できる。キヤリヤー物質の好ましい配合量は触媒
の全重量にもとづき約0.01〜90wt％、特に約５〜
60wt％である。キヤリヤー物質は触媒表面積を
大きくしたり、機械的強度を強くしたり、あるい
は触媒価格を安価にするのに有効である。特にゼ
オライト、クロミアのようなキヤリヤー物質は生
成オレフインのオリゴマー化に有効で、より高沸
点の生成物が得られる。触媒中キヤリヤー物質の
配合量が多すぎるとオレフイン生成の選択性が悪
くなつてしまう。
本発明の触媒はγ型二酸化マンガンよりなる担
体にルテニウムを担持する。ルテニウムの配合量
は触媒の全重量にもとづき約0.1〜50wt％、特に
約0.1〜30wt％（Ru換算値）が好ましい。ルテニ
ウムの配合量が少なすぎると触媒活性は低くな
り、また多すぎるとオレフイン生成の選択性が低
下してしまう。触媒中のルテニウムは通常金属単
体が大部分を占めるが酸化物など化合物の形でも
よい。
また触媒には活性を高めるため更に活性化剤を
含有させてもよい。活性化剤の例としてはマグネ
シウム、亜鉛、アルミニウム、カドミウム、銅、
チタン、鉄、コバルト、パラジウム、ロジウム、
白金、レニウム、イリジウム、ニツケル、ランタ
ン、銀、トリウム等があり、触媒中においては金
属単体の形でも塩化物、アンモニウム塩、硝酸
塩、酸化物等の化合物の形をしていてもよい。触
媒調製時に原料として使用する活性化剤成分の例
は塩化マグネシウム、塩化亜鉛、塩化アルミニウ
ム、塩化カドミウム、塩化銅、三塩化チタン、四
塩化チタン、塩化鉄、塩化コバルト、塩化パラジ
ウム、塩化ロジウム、塩化白金、塩化レニウム、
塩化イリジウム等の塩化物及びそのアンモニウム
塩あるいは硝酸銀、硝酸トリウム等の硝酸塩等が
ある。活性化剤の配合量は触媒の全重量にもとづ
き金属単体換算で約0.01〜35wt％、特に約0.1〜
20wt％が好ましい。（活性化剤とキヤリヤー物質
との好ましい合計配合量は約0.01〜90wt％であ
る。）これら活性化剤は担体として使用する二酸
化マンガン合成時に添加したり二酸化マンガンと
混合してもよいが好適には二酸化マンガン合成後
のルテニウム担持前、担持後あるいはルテニウム
との同時担持が好ましい。触媒中活性化剤の配合
量が多すぎると相対的にルテニウムや二酸化マン
ガンの配合量が少なくなり、触媒活性が低下した
りオレフイン生成の選択性が低下してしまう。
本発明の方法の実施に使用されるルテニウム触
媒はアルミナにルテニウムを担持した触媒
（Ru／Al2O3）などのような他の触媒系の製造に
対して当業界に既知の技法によつて製造される。
二酸化マンガンよりなる担体へのルテニウムの担
持は例えば担体をルテニウム化合物の溶液中に浸
漬して、担体上に吸着させたり、イオン交換して
付着させたり、アルカリなどの沈殿剤を加えて沈
着させたり、溶液を蒸発乾固したり、あるいは溶
液を担体上へ滴下したりして行なうなど、担体と
ルテニウム化合物を含む溶液とを接触させて担持
することができる。これらの場合に使用できるル
テニウム化合物の例としては塩化ルテニウム、硝
酸ルテニウム、酢酸ルテニウム、塩化六アンモニ
ア・ルテニウムなど水に可溶なもの、あるいはル
テニウムカルボニルクラスター等有機溶剤に可溶
なものなどがある。こうして得られた生成物は常
法により成型しまたは成型することなく、乾燥す
る。乾燥はたとえば常温〜300℃で約10〜48時間
保持することにより行なうことができる。最も好
ましい乾燥方法は、常温で乾燥させた後空気中で
約90〜110℃に数時間加熱するか、あるいはただ
ちに空気中で約90〜110℃に数時間加熱する方法
である。キヤリヤー物質および活性化剤は二酸化
マンガンと混合したり、担体上に担持したり、二
酸化マンガンにルテニウムを担持したものと混合
したりする。
本発明の方法において使用されるこの支持され
たルテニウム／二酸化マンガン系触媒は、水素ガ
スによる還元及び合成ガスの導入される以前に空
気中でその触媒をある高められた温度で焼成され
るか否かによつて生成物分布及び担持されるルテ
ニウムの平均粒子径は変動する。焼成の温度が高
い程ルテニウムの平均粒子径は大きくなり、生成
する炭化水素の分布も高級炭化水素成分をより多
く生成する。C2〜C4の低級オレフインを目的と
する場合には、この空気中焼成処理を省略し、直
接H2ガスによる還元工程に導くのが好ましい。
この場合、平均ルテニウム粒子径は2nｍ以下を
示す。低級オレフインよりもより高沸点成分に富
むオレフインが得たい場合は約600℃以下好まし
くは約300〜600℃の温度で焼成する。焼成時間は
約30分〜24時間が好ましい。焼成はルテニウム担
持前に担体のみを焼成しても、ルテニウム担持後
の触媒を焼成しても、あるいは担体のみを焼成す
るとともに触媒をも焼成してもよいが、最も好ま
しいのはルテニウム担持後に焼成することであ
る。600℃をこえる高温条件下で焼成を行なうと
触媒活性は低下してしまい、オレフイン生成の選
択性は低下してしまう。
本発明の実施に使用される担体は粉末、顆粒、
形状、圧出形など何れの形状でも良く、約１〜
200m2／ｇ好適には約10〜100m2／ｇ最も好適には
約25〜100m2／ｇのB.E.T表面積を持ちうる。ル
テニウムは選択された担体上に約0.1〜50wt％、
好適には約0.1〜30wt％、最も好適には0.5〜25wt
％の濃度で沈着されるが、その百分率は、Ｘ線回
折のような標準法で測定して、約0.1〜20nｍ、好
適には約0.1〜10nｍ、最も好適には0.1〜5nｍの
平均粒子径（球形として仮定しての直径）をもつ
ルテニウムを含んだ触媒の全重量に基づくもので
ある。
好適な態様において上述されたように、あるい
は同様な方法によつて製造されたルテニウム触媒
は合成ガスで負荷する前に水素あるいは一酸化炭
素のような還元性雰囲気で約300℃以上、好適に
は約400℃以上の温度で約0.5〜４時間加熱処理さ
れる。この場合約1atmの大気圧の圧力を維持す
るのが好ましい。水素等で還元処理する際、水素
と同時に水、メタノールあるいはエタノール等の
含酸素化合物あるいは硫化水素等を導入する前処
理工程により触媒表面処理を導き、この活性化及
び硫化処理を実施することで生成物分布を制御す
ることも可能である。この加熱処理を行なう還元
工程あるいは前処理工程は、FT合成反応が還元
性雰囲気で行なわれ、従つて上記工程と同じよう
な触媒還元効果を持つであろうから、必ずしも別
の工程として行なわれる必要はないことに留意す
べきである。
本発明の方法の反応操作条件はFT合成に典型
的なものである。圧力は０〜100Kg／cm2Ｇ、好適
には０〜30Kg／cm2Ｇ、最も好適には０〜20Kg／cm2
Ｇの範囲にある。減圧下に行なつてもよい。温度
は約100〜500℃、好適には約200〜450℃、最も好
適には約250〜400℃の範囲にある。水素対一酸化
炭素モル比（H2／CO比）は約0.1〜10、好適には
約0.5〜４最も最適には0.5〜１でやや一酸化炭素
が過剰量で存在する混合ガスである。供給ガスの
空間速度（GHSV）は約100hr-1〜50000hr-1の範
囲である。反応室を去る混合ガスは形成された炭
化水素生成物を除去した後に装置に全部、又は部
分的に再び供給する。
本発明の方法において使用される触媒は一般に
固定床の型で適用する。しかしながらこれを微細
に分配された型で使用する流動床及び懸濁床など
も適用できる。また触媒は連続的又は不連続的に
再生するため、反応容器から除去しても良い。こ
のために、これらを特別な容器中で空気と共に燃
焼することにより、触媒表面上に付着せる不純物
を除去し、引続き公知方法で還元し使用出来る。
触媒の前処理としての還元工程または反応中に
触媒中のルテニウム化合物は大部分金属単体とな
る。また触媒調製時担体として使用されたγ型二
酸化マンガンは反応中他の結晶型、Mn2O3や
Mn3O4など他のマンガン酸化物に変つてゆくと
思われるが、γ型二酸化マンガン以外のマンガン
酸化物から調製した触媒では触媒選択性が非常に
低く、本発明の目的は達成されない。
本発明方法の効果について述べる。本発明の方
法は使用される触媒が、難溶な二酸化マンガン及
び活性剤あるいはキヤリヤー物質としての各種金
属酸化物からなる群から選ばれる担体に支持され
たルテニウムからなる触媒を用いることにより一
酸化炭素と水素から不飽和炭化水素を選択的に生
成する。殊に反応圧力０〜５Kg／cm2Ｇではガス状
の低級オレフイン類が、また約５Kg／cm2Ｇ以上で
は高級不飽和炭化水素が一酸化炭素と水素を用い
て、高められた温度及び圧力下で接触水素化する
ことにより良好な収率で得られ、また生成する炭
化水素化合物の分布はC3留分以上でシユルツ・
フローリー則に従うものの、ルテニウム系触媒を
用いたFT合成反応では副生のさけられない、メ
タン生成量が極端に少なく、C2以上の不飽和炭
化水素が良好な収率で得られることが判明した。
また本発明方法では触媒調製時の焼成条件を変え
たり、触媒中にゼオライト、クロミア等のキヤリ
ヤー物質を配合することによりより高沸点のオレ
フイン類を製造することができる。また本発明触
媒は耐イオウ性が強く、イオウ分を不純物として
含有する原料ガスも使用できる。
以下実施例により本発明を説明する。以下の例
中反応条件のH2／COモル比は特記しない限り1.0
で行なつた。
参考例 １
本発明実施例に使用する各種マンガン酸化物は
以下の方法により合成した。
γ型二酸化マンガンは、炭素を陽極として硫酸
マンガン（）と硫酸の混合温水溶液（90℃）を
電解して極板上に生成する電解二酸化マンガン
（Ａ法）および炭酸マンガンに0.1％の水酸化ナト
リウムを添加し空気中350℃で酸化し、希硫酸で
熱処理し、過水洗し、0.8規定のアンモニア水
でPHを4.0以上にPH調整し、過し、そして乾燥
して調製した二酸化マンガン（Ｂ法）である。
上記２法による二酸化マンガンは、いずれも結
晶性が悪く、第１図に示すごとくＸ線回折パター
ンを示した。第１図のＸ線回折図はFaKαを光源
とし、Mnをフイルターとして測定したもので、
横軸は角度2θを、縦軸はＸ線強度をあらわす。
参考例 ２
比較例で使用するマンガン酸化物は以下の方法
により合成した。β−MnO2は、硫酸マンガン
（）六水和物を空気中150〜190℃で２−３日間
加熱し、その後沸騰希硝酸つづいて沸騰水で洗浄
し、さらに450〜500℃の温度で再加熱し合成し
た。以下MnO、Mn2O3、Mn3O4は、公知方法に
より合成あるいは市販試薬を用いた。
実施例１、比較例１
Ru／γ−MnO2（触媒１）を次の様に調製し評
価した。Ａ法によるMnO288.5ｇを塩化ルテニウ
ム2.28ｇを水とエタノールとの等容量混合溶液40
mlに溶解させた溶液中に含浸する。一昼夜放置後
水−アスピレーターで脱溶剤し、90〜100℃のオ
ーブン中で乾燥し触媒１とした。このように調製
した触媒１にはRu1.0重量％を含んでいた。この
触媒を反応容器に２ml（2.57ｇ）充填し、水素ガ
ス雰囲気下400℃×2hr還元処理した。続いて水素
ガス中で反応温度以下（約100℃）に冷却したの
ち一酸化炭素と水素よりなる反応ガスと交換し、
触媒層に流入した。同様にしてルテニウム含有量
4.0wt％の触媒２を調製し、この触媒についても
反応ガスを通じて反応を行なつた。反応条件、生
成物組成は表１、第２〜４図に明記される。第２
〜４図の反応条件は圧力常圧、
GHSV150hr-1H2／COモル比１である。
比較のため上記触媒１の製法と同様な方法で触
媒担体としてMnO、Mn2O3、Mn3O4を用いるマ
ンガン酸化物のマンガン荷電数を変化させた触媒
３，４，５を調製し評価した。表１は触媒担体と
して用いるマンガン酸化物のマンガン荷電数の差
異によりRu／Mn系触媒のいわゆる選択特性（オ
レフイン特性）を比較して例示している。Ru／
MnO2系触媒では、そこに示された他のマンガン
酸化物から調製した触媒に較べて、メタンの生成
が有意に低く、かつC2〜C4の低級オレフインの
選択性が特に高いことに留意すべきである。
The present invention relates to a method for producing olefins from hydrogen and carbon monoxide. The production of hydrocarbons by contacting a gas mixture of hydrogen and carbon monoxide with a catalyst at elevated temperature and pressure is known as the
This method is known as a hydrocarbon synthesis method using the Tropschule (FT) method. Catalytic hydrogenation of carbon monoxide yields, depending on the catalyst used and the reaction conditions applied, a mixture consisting of paraffins and olefins containing from 1 to 40 carbon atoms;
In some cases, oxygen-containing compounds such as alcohols, aldehydes, ketones, esters or fatty acids are also formed. Small amounts of aromatic hydrocarbons are also produced under the selected synthesis conditions. A remarkable activity with respect to the hydrogenation of carbon monoxide is shown by the elements of group 8 of the periodic table, especially iron, cobalt, nickel and ruthenium. The characteristics of these elements cause significant differences in the distribution of the products and their compositions due to the hydrogenation activity they have and the degree of secondary reaction due to readsorption of α-olefin as the primary product onto the catalyst surface. Nickel-, cobalt- and ruthenium-based catalysts give a mixture of predominantly unbranched saturated hydrocarbons, while iron-containing catalysts give large amounts of unsaturated aliphatic compounds, as well as oxygen-containing compounds, especially aliphatic primary alcohols. It is already known that it is possible to produce hydrocarbons containing . Also, mixtures having a carbon number greater than about 20 and containing 60 wt % or more of hydrocarbons at atmospheric pressure or elevated pressure and a reaction temperature of about 200 to 300° C. can be produced without difficulty by known methods. When an iron-based catalyst is used, a mixed product rich in unsaturated hydrocarbon components is obtained, but the amount of carbon dioxide gas and oxygen-containing compounds produced as by-products is large, and the selectivity for hydrocarbon production is poor. On the other hand, compared to iron-based catalysts, ruthenium-based catalysts have a higher
Although the FT reaction activity is several times higher, the hydrogenation activity is also high, so the product contains many saturated hydrocarbon components, and is highly dependent on the reaction pressure and reaction temperature, and is often used as an indicator to discuss the FT reaction.・The chain growth probability α value of Flory's law tends to decrease significantly as the reaction temperature increases. For these reasons, ruthenium-based catalysts are used to convert C 2 to C 4
It is said to be extremely difficult to selectively derive a reaction product containing a large amount of lower hydrocarbons or olefinic hydrocarbons of C5 or higher . Also, looking at the hydrogenation reaction of carbon monoxide from the perspective of equilibrium theory, the relationship between the free energy change ΔF of hydrocarbon production and the equilibrium constant K is -ΔF=RTlnK, so the hydrogenation reaction of carbon monoxide will occur at a certain temperature. You can judge whether it is advantageous from an equilibrium perspective. Generally, in the low temperature range, the production of paraffin is more advantageous than the production of olefin. For example, the ethylene/ethane production ratio is smaller than the propylene/propane production ratio, and the propylene/ethane production ratio is smaller than the propylene/propane production ratio.
From an equilibrium standpoint, it can be said that increasing the ethylene/ethane production ratio is more difficult than increasing the propane production ratio. The selective production of C 2 to C 4 lower olefins is disadvantageous in terms of equilibrium, but how to overcome this disadvantage kinetically is the key to obtaining good selectivity for lower olefins. . Therefore, there would be great benefits if olefinic hydrocarbons could be produced at high conversion rates and high selectivity by catalytically reacting carbon monoxide with hydrogen. Conventional methods for producing hydrocarbons by carrying out the Fischier-Tropsch reaction using a catalyst containing manganese oxide are disclosed in Japanese Patent Publication No. 56-48491 and U.S. Patent No.
No. 4,177,203 and US Pat. No. 4,206,134. Japanese Patent Publication No. 56-48491 describes that gaseous olefins can be obtained in high yield by using a catalyst obtained by calcining a mixture of iron and manganese oxide at 1050°C. However, as shown in Comparative Example 5 below, a catalyst made of manganese oxide and iron has an extremely low carbon monoxide conversion rate and a very low catalytic activity, and even if it is calcined at 1050°C, the catalytic activity is still low. It turned out to be very low. U.S. Pat. No. 4,177,203 also states that C 2 to C 4 hydrocarbons are produced with good selectivity when a catalyst consisting of 50% or more manganese and 50% or less iron is used, but as shown in Comparative Example 5 below, Catalysts made of manganese and iron have very low activity. US Pat. No. 4,206,134 states that when the FT reaction is carried out using a catalyst in which ruthenium is supported on manganese monoxide, a large amount of C 2 -C 4 olefin is produced, and a small amount of methane is produced. However, as shown in Comparative Example 1 below, the catalyst in which ruthenium is supported on manganese monoxide produces a very low amount of olefins. This time, we focused on the charge number of manganese oxide and its crystallinity, and investigated the unique physical properties and interesting behavior of manganese dioxide (MnO 2 ), which should be recognized as a typical homogeneous solid-phase redox system, in relation to carbon monoxide and hydrogen. It was discovered in the contact reaction (FT reaction) with The main purpose of the present invention is to provide a method for producing olefinic hydrocarbons, especially lower olefins such as C2 to C4 , with high selectivity.Another purpose of the present invention is to suppress the production of methane and to produce olefinic hydrocarbons with high selectivity. Another object of the present invention is to provide a method for producing olefin-rich hydrocarbons with a high conversion rate. That is, the gist of the present invention is to use γ-type manganese dioxide as a carrier in a method for producing hydrocarbons by contacting a ruthenium catalyst supported on a manganese oxide carrier with a mixed gas containing hydrogen and carbon monoxide. It is characterized by a method for producing olefins. The catalyst of the present invention is prepared by supporting ruthenium on a carrier made of γ-type manganese dioxide, but it may contain a carrier material and/or an activator if necessary. The manganese dioxide used for catalyst preparation is γ-type manganese dioxide, which belongs to a type with low crystallinity, which is similar to the layered lattice structure of the cadmium iodide type. The γ-type manganese dioxide used here belongs to the chemical oxidation method of manganese salt solution, for example.Synthesis method by adding KMnO4 solution to a boiling solution of neutral MnSO4.Mixed boiling aqueous solution of manganese sulfate () and sulfuric acid. A method of synthesis by adding ammonium persulfate to a method A method of synthesis by adding potassium permanganate to a mixed warm aqueous solution of manganese sulfate () and potassium nitrate A method of synthesizing by adding potassium permanganate to a mixed warm aqueous solution of manganese sulfate () and potassium nitrate A method of electrolytic oxidation of manganese salt solutions Using a graphite electrode of a thermally acidic MnSO 4 solution Synthesis method by anodic oxidation Belongs to the synthesis method by anodic oxidation with a platinum electrode of thermally acidic MnSO4 solution and the calcination and acid treatment method. β- MnO2 is heated to 600℃ and boiled with dilute H2SO4 .
Synthesis method by leaching MnCO 3 (added with 0.1% NaOH) in oxygen gas at 350 °C
It is synthesized by a synthesis method that involves calcination at ℃ and treatment with dilute sulfuric acid. γ-type manganese dioxide synthesized by other known γ-type manganese dioxide synthesis methods and modification methods may also be used. FT of Ruthenium supported on these materials
It is also possible to include other sparingly soluble substances in the catalyst as carrier substances that do not substantially inhibit the hydrocarbon synthesis properties. For example, TiO 2 , SiO 2 ,
Metal oxides such as Al 2 O 3 , Cr 2 O 3 , V 2 O 5 , WO 3 , MoO 3 and zeolites can also be homogeneously mixed with manganese dioxide as a carrier material. In the present invention, zeolite means crystalline aluminosilicate zeolite, examples of which include Y-type zeolite, X-type zeolite, A-type zeolite,
Mordenite, ZSM zeolite (ZSM zeolites include ZSM-4, ZSM-5,
ZSM-34, etc., published by Japan Technology and Economy Center Publishing Department, January 11, 1980, "Comprehensive Data Collection of Recent Advances in Zeolite Technology and Applications", pp. 46-57, edited by Hiroshi Takahashi et al., February 1, 1975. "Zeolite" published by Kodansha
It is described in detail on pages 46-47 and in the specification of JP-A-57-70828. )and so on. These zeolites are
It may be a metal-substituted type such as Na or K, but a hydrogen type is preferable, and it may be a synthetic product or a naturally occurring product. Additionally, dealuminated zeolites can also be used. One example of a dealumination method is to treat zeolite with an acid (either an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as acetic acid, oxalic acid, or adipic acid) or a chelating agent such as EDTA (sodium ethylenediaminetetraacetate). A portion of the aluminum in the zeolite is eluted by heat treatment in an aqueous solution. mordenite,
Acid-resistant zeolites such as ZSM-5 may be treated with acid, but zeolites with low acid resistance such as Y-type zeolite are treated with an aqueous chelating agent solution. There are no particular restrictions on the temperature, acid or chelating agent concentration, treatment time, etc. during treatment, but the concentration is usually around a few percent (for example, about 1 to 15 wt%), the temperature is the boiling temperature of the solution, and the time is about 30 minutes. Do this for about a few hours. After that, dry and bake if necessary. These carrier materials can be used by homogeneously mixing with γ-type manganese dioxide, or by physically mixing with γ-type manganese dioxide supporting ruthenium. The preferred loading of the carrier material is from about 0.01 to 90 wt%, especially from about 5 to 90 wt%, based on the total weight of the catalyst.
It is 60wt%. The carrier material is effective in increasing the surface area of the catalyst, increasing its mechanical strength, or reducing the cost of the catalyst. In particular, carrier materials such as zeolites and chromia are effective in oligomerizing the produced olefins, resulting in products with higher boiling points. If the amount of carrier material in the catalyst is too large, the selectivity of olefin production will deteriorate. The catalyst of the present invention supports ruthenium on a carrier made of γ-type manganese dioxide. The amount of ruthenium blended is preferably about 0.1 to 50 wt%, particularly about 0.1 to 30 wt% (in terms of Ru), based on the total weight of the catalyst. If the amount of ruthenium blended is too small, the catalyst activity will be low, and if it is too large, the selectivity for olefin production will be reduced. The majority of ruthenium in the catalyst is usually an elemental metal, but it may also be in the form of a compound such as an oxide. Further, the catalyst may further contain an activator to increase its activity. Examples of activators include magnesium, zinc, aluminum, cadmium, copper,
titanium, iron, cobalt, palladium, rhodium,
Examples include platinum, rhenium, iridium, nickel, lanthanum, silver, thorium, etc., and in the catalyst, they may be in the form of simple metals or in the form of compounds such as chlorides, ammonium salts, nitrates, and oxides. Examples of activator components used as raw materials during catalyst preparation are magnesium chloride, zinc chloride, aluminum chloride, cadmium chloride, copper chloride, titanium trichloride, titanium tetrachloride, iron chloride, cobalt chloride, palladium chloride, rhodium chloride, and chloride. platinum, rhenium chloride,
Examples include chlorides such as iridium chloride, their ammonium salts, and nitrates such as silver nitrate and thorium nitrate. The blending amount of the activator is about 0.01 to 35 wt%, especially about 0.1 to 35 wt% based on the total weight of the catalyst.
20wt% is preferred. (The preferred total amount of the activator and carrier material is about 0.01 to 90 wt%.) These activators may be added during the synthesis of manganese dioxide used as a carrier, or may be mixed with manganese dioxide, but preferably is preferably supported before, after, or simultaneously with ruthenium after manganese dioxide synthesis. If the amount of the activator in the catalyst is too large, the amount of ruthenium and manganese dioxide added will be relatively small, resulting in a decrease in catalyst activity and a decrease in selectivity for olefin production. The ruthenium catalyst used in carrying out the process of the invention can be prepared by techniques known in the art for the production of other catalyst systems such as ruthenium on alumina (Ru/Al 2 O 3 ). Manufactured.
Ruthenium can be supported on a carrier made of manganese dioxide by, for example, immersing the carrier in a solution of a ruthenium compound and adsorbing it onto the carrier, attaching it by ion exchange, or adding a precipitant such as an alkali to deposit it. The support can be carried out by bringing the support and the solution containing the ruthenium compound into contact, such as by evaporating the solution to dryness or dropping the solution onto the support. Examples of ruthenium compounds that can be used in these cases include those soluble in water such as ruthenium chloride, ruthenium nitrate, ruthenium acetate, and hexaammonium ruthenium chloride, and those soluble in organic solvents such as ruthenium carbonyl cluster. The product thus obtained is dried in a customary manner, with or without shaping. Drying can be carried out, for example, by holding at room temperature to 300°C for about 10 to 48 hours. The most preferred drying method is to dry at room temperature and then heat in air to about 90-110°C for several hours, or to immediately heat in air to about 90-110°C for several hours. The carrier material and activator are mixed with manganese dioxide, supported on a carrier, or mixed with ruthenium on manganese dioxide. The supported ruthenium/manganese dioxide-based catalyst used in the process of the present invention is prepared by calcining the catalyst in air at an elevated temperature prior to reduction with hydrogen gas and introduction of synthesis gas. The product distribution and the average particle size of the supported ruthenium vary depending on the method. The higher the firing temperature is, the larger the average particle size of ruthenium becomes, and the distribution of the generated hydrocarbons also increases to produce higher hydrocarbon components. When the objective is to obtain a C2 to C4 lower olefin, it is preferable to omit this in-air calcination treatment and directly lead to the reduction step using H2 gas.
In this case, the average ruthenium particle diameter is 2 nm or less. If it is desired to obtain an olefin that is richer in high-boiling components than lower olefins, it is calcined at a temperature of about 600°C or less, preferably about 300 to 600°C. Preferably, the firing time is about 30 minutes to 24 hours. Calcination may be performed by firing only the carrier before supporting ruthenium, by firing the catalyst after supporting ruthenium, or by firing only the carrier and also firing the catalyst, but the most preferable method is to perform calcination after supporting ruthenium. It is to be. If the calcination is carried out under high temperature conditions exceeding 600°C, the catalyst activity will be reduced and the selectivity for olefin production will be reduced. Carriers used in the practice of this invention include powders, granules,
It can be of any shape, such as extrusion or extrusion, and has a diameter of about 1 to
It may have a BET surface area of 200 m 2 /g, preferably about 10 to 100 m 2 /g, and most preferably about 25 to 100 m 2 /g. Ruthenium is approximately 0.1-50wt% on the selected carrier,
Preferably about 0.1-30wt%, most preferably 0.5-25wt
%, the percentage having an average particle size of about 0.1 to 20 nm, preferably about 0.1 to 10 nm, most preferably 0.1 to 5 nm, as determined by standard methods such as X-ray diffraction. (diameter assuming spherical shape) of the ruthenium-containing catalyst. In a preferred embodiment, the ruthenium catalyst prepared as described above or by a similar method is preferably heated to a temperature above about 300° C. in a reducing atmosphere such as hydrogen or carbon monoxide before loading with synthesis gas. Heat treatment is performed at a temperature of about 400°C or higher for about 0.5 to 4 hours. In this case it is preferred to maintain a pressure of about 1 atm atmospheric pressure. When performing reduction treatment with hydrogen, etc., catalyst surface treatment is carried out through a pretreatment step in which water, an oxygen-containing compound such as methanol or ethanol, or hydrogen sulfide, etc. is introduced simultaneously with hydrogen, and this activation and sulfurization treatment is performed to generate It is also possible to control the distribution of objects. This reduction step or pretreatment step that involves heat treatment does not necessarily need to be carried out as a separate step, since the FT synthesis reaction is carried out in a reducing atmosphere and will therefore have the same catalytic reduction effect as the above step. It should be noted that there is no The reaction operating conditions of the method of the invention are typical for FT synthesis. The pressure is between 0 and 100 Kg/cm 2 G, preferably between 0 and 30 Kg/cm 2 G, most preferably between 0 and 20 Kg/cm 2
It is in the range of G. It may also be carried out under reduced pressure. The temperature ranges from about 100-500°C, preferably from about 200-450°C, most preferably from about 250-400°C. The gas mixture has a hydrogen to carbon monoxide molar ratio ( H2 /CO ratio) of about 0.1 to 10, preferably about 0.5 to 4, most optimally 0.5 to 1, with a slight excess of carbon monoxide. The feed gas space velocity (GHSV) ranges from approximately 100 hr -1 to 50000 hr -1 . The gas mixture leaving the reaction chamber is fed completely or partially back into the device after removal of the hydrocarbon products formed. The catalyst used in the process of the invention is generally applied in fixed bed form. However, fluidized beds, suspended beds, etc., in which they are used in finely divided form, are also applicable. The catalyst may also be removed from the reaction vessel for continuous or discontinuous regeneration. For this purpose, they are burnt with air in special containers to remove impurities deposited on the catalyst surface and can be subsequently reduced and used in known manner. During the reduction step or reaction as pretreatment of the catalyst, most of the ruthenium compound in the catalyst becomes an elemental metal. In addition, the γ-type manganese dioxide used as a carrier during catalyst preparation is converted into other crystal forms such as Mn 2 O 3 and Mn 2 O 3 during the reaction.
Although it is thought that Mn 3 O 4 and other manganese oxides will gradually change to other manganese oxides, catalysts prepared from manganese oxides other than γ-type manganese dioxide have very low catalyst selectivity, and the object of the present invention cannot be achieved. The effects of the method of the present invention will be described. The method of the present invention uses a catalyst consisting of ruthenium supported on a carrier selected from the group consisting of sparingly soluble manganese dioxide and various metal oxides as an activator or carrier material, thereby reducing carbon monoxide. and selectively generate unsaturated hydrocarbons from hydrogen. In particular, gaseous lower olefins are used at reaction pressures of 0 to 5 Kg/cm 2 G, and higher unsaturated hydrocarbons are used at elevated temperatures and pressures, using carbon monoxide and hydrogen at about 5 Kg/cm 2 G or higher. It can be obtained in good yield by catalytic hydrogenation under
It was found that although Flory's rule is followed, in FT synthesis reactions using ruthenium catalysts, by-products are unavoidable, the amount of methane produced is extremely small, and unsaturated hydrocarbons of C2 or higher can be obtained in good yields. .
Furthermore, in the method of the present invention, olefins with a higher boiling point can be produced by changing the firing conditions during catalyst preparation or by incorporating a carrier material such as zeolite or chromia into the catalyst. Furthermore, the catalyst of the present invention has strong sulfur resistance, and raw material gas containing sulfur as an impurity can also be used. The present invention will be explained below with reference to Examples. In the following examples, the H 2 /CO molar ratio in the reaction conditions is 1.0 unless otherwise specified.
I did it at Reference Example 1 Various manganese oxides used in the examples of the present invention were synthesized by the following methods. γ-type manganese dioxide is produced by electrolyzing manganese dioxide (method A), which is produced on an electrode plate by electrolyzing a mixed warm aqueous solution (90°C) of manganese sulfate (2018) and sulfuric acid using carbon as an anode, and by manganese carbonate with 0.1% hydroxide. Manganese dioxide (B law). Manganese dioxide obtained by the above two methods both had poor crystallinity and exhibited an X-ray diffraction pattern as shown in FIG. The X-ray diffraction diagram in Figure 1 was measured using FaKα as a light source and Mn as a filter.
The horizontal axis represents the angle 2θ, and the vertical axis represents the X-ray intensity. Reference Example 2 Manganese oxide used in Comparative Example was synthesized by the following method. β-MnO 2 is obtained by heating manganese sulfate () hexahydrate in air at 150-190℃ for 2-3 days, then washing with boiling dilute nitric acid and then boiling water, and then heating it again at a temperature of 450-500℃. Synthesized by heating. In the following, MnO, Mn 2 O 3 and Mn 3 O 4 were synthesized by known methods or commercially available reagents were used. Example 1, Comparative Example 1 Ru/γ-MnO 2 (catalyst 1) was prepared and evaluated as follows. A mixed solution of 88.5 g of MnO 2 and 2.28 g of ruthenium chloride with equal volumes of water and ethanol 40
Impregnate into a solution dissolved in ml. After standing for a day and night, the solvent was removed using a water-aspirator and dried in an oven at 90 to 100°C to obtain Catalyst 1. Catalyst 1 thus prepared contained 1.0% by weight of Ru. A reaction vessel was filled with 2 ml (2.57 g) of this catalyst and subjected to reduction treatment at 400° C. for 2 hours in a hydrogen gas atmosphere. Then, after cooling in hydrogen gas to below the reaction temperature (approximately 100°C), it was exchanged with a reaction gas consisting of carbon monoxide and hydrogen.
It flowed into the catalyst layer. Similarly, ruthenium content
A 4.0 wt % catalyst 2 was prepared, and the reaction was also carried out with this catalyst through the passage of the reaction gas. The reaction conditions and product composition are specified in Table 1 and Figures 2-4. Second
~The reaction conditions in Figure 4 are normal pressure,
GHSV150hr -1 H 2 /CO molar ratio is 1. For comparison, Catalysts 3, 4, and 5 were prepared and evaluated by using MnO, Mn 2 O 3 , and Mn 3 O 4 as catalyst carriers using a method similar to that of Catalyst 1 above, in which the manganese charge number of manganese oxide was changed. did. Table 1 compares and illustrates the so-called selective characteristics (olefin characteristics) of Ru/Mn-based catalysts based on the difference in manganese charge number of manganese oxides used as catalyst carriers. Ru/
Note that MnO 2 -based catalysts produce significantly lower methane and have particularly high selectivity for C 2 -C 4 lower olefins compared to catalysts prepared from other manganese oxides presented therein. Should.
【表】【table】
【表】【table】
【表】
実施例２、比較例２
実施例１で用いた触媒１を電気炉で空気中450
℃で24hr焼成処理した触媒６を実施例１と同様に
反応器に充填し還元処理をほどこして評価した。
反応条件および生成物分布、組成は表２、３、第
５図に明記した。第５図の反応条件は温度300℃、
圧力10Kg／cm2Ｇ、GHSV300hr-1、H2／COモル
比１である。第５図はルテニウム担持後の空気焼
成の有無により、生成物分布は大きく変動するこ
とを示している。焼成することにより生成物の炭
素数は増加し、高沸点留分を生成する。またその
生成物分布は、シユルツ・フローリー分則に従う
ものの比較例として示したRu／γ−Al2O3触媒
７，８（いずれも450℃で焼成したもの。）に較べ
て、ルテニウム活性金属の特徴とも云える温度依
存性が少なく、かつオレフイン特性に優れている
ことに留意すべきである。[Table] Example 2, Comparative Example 2 Catalyst 1 used in Example 1 was heated in air at 450 °C in an electric furnace.
Catalyst 6, which had been calcined at ℃ for 24 hours, was charged into a reactor in the same manner as in Example 1, subjected to reduction treatment, and evaluated.
The reaction conditions, product distribution and composition are specified in Tables 2 and 3 and FIG. The reaction conditions in Figure 5 are a temperature of 300°C;
The pressure was 10 Kg/cm 2 G, GHSV 300 hr -1 , and the H 2 /CO molar ratio was 1. FIG. 5 shows that the product distribution varies greatly depending on the presence or absence of air calcination after supporting ruthenium. Calcining increases the carbon number of the product and produces a high-boiling fraction. In addition, the product distribution follows the Schurtz-Flory rule, but compared to Ru/γ-Al 2 O 3 catalysts 7 and 8 (both calcined at 450°C) shown as comparative examples, the product distribution is similar to that of ruthenium active metal. It should be noted that there is little temperature dependence, which can be said to be a characteristic, and that it has excellent olefin properties.
【表】【table】
【表】【table】
【表】【table】
【表】
実施例３、比較例３
実施例１に明示した触媒１の調製方法と同様に
して調製した、各種二酸化マンガンγ型、無定
形、β型を担体として用いた触媒９，１０，１
１，１２，１３，１４につき反応評価を実施し
た。表４、第６、７、８図はFT反応合成におけ
る触媒のオレフイン特性について、各種二酸化マ
ンガンの結晶構造の差異による評価結果を例示し
ている。第６〜８図の反応条件は圧力常圧、
GHSV150hr-1、H2／COモル比１である。C2〜
C4の低級オレフインの選択性は、低結晶性のγ
型を用いた時、結晶性の高い他の二酸化マンガン
（β−MnO2）および無形MnO2に較べて、有意に
高いことに注目すべきである。またルテニウムを
担持しないγ型二酸化マンガンのみからなる触媒
１５，１６についても評価したが、転化率が極端
に低く、触媒活性がほとんどないことがわかる。[Table] Example 3, Comparative Example 3 Catalysts 9, 10, 1 using various manganese dioxide γ-type, amorphous, and β-type as carriers prepared in the same manner as the preparation method of catalyst 1 specified in Example 1.
Reaction evaluation was carried out for 1, 12, 13, and 14. Table 4 and Figures 6, 7, and 8 exemplify the evaluation results of the olefin characteristics of the catalyst in FT reaction synthesis based on the differences in the crystal structure of various manganese dioxides. The reaction conditions in Figures 6 to 8 are normal pressure,
GHSV150hr -1 , H2 /CO molar ratio 1. C 2 ~
The selectivity of C4 lower olefins is due to the low crystallinity γ
It should be noted that when the mold is used, the crystallinity is significantly higher than that of other highly crystalline manganese dioxide (β-MnO 2 ) and amorphous MnO 2 . Catalysts 15 and 16 consisting only of γ-type manganese dioxide without supporting ruthenium were also evaluated, but it was found that the conversion rate was extremely low and the catalyst had almost no activity.
【表】【table】
【表】
実施例４、比較例４
γ型二酸化マンガン（Ａ法）を焼成するか焼成
せず、次に実施例１の触媒１と同様にしてルテニ
ウム担持（ルテニウムとして１重量％担持）し、
実施例１の触媒１と同様にして乾燥し、最後に焼
成するかもしくは焼成せずして触媒１７，１８，
１９，２０，２１を調製した。触媒１７はルテニ
ウムを担持前に450℃で８時間焼成しかつルテニ
ウム担持後に450℃で８時間焼成したものであり、
触媒１８はルテニウム担持前に550℃で８時間焼
成しかつルテニウム担持後に550℃で８時間焼成
したものであり、触媒２１はルテニウム担持前は
焼成せずルテニウム担持後に900℃で８時間焼成
したものであり、触媒１９はルテニウム担持前に
550℃で23時間焼成しルテニウム担持後は焼成し
なかつたものであり、触媒２０はγ型二酸化マン
ガンの代りに一酸化マンガンを使用した以外触媒
１９と同じ方法で調製したものである。
これらの触媒を実施例１と同様にして反応器へ
の充填、水素還元処理をし、反応を行なつた。表
５に反応条件および結果を示した。表５の結果か
ら、触媒の焼成温度が高いほどメタン生成率が高
くなること、焼成温度が600℃をこえるとC2〜C4
の低級オレフインの生成率が極端に低下するこ
と、担体にルテニウムを担持した後焼成すると生
成物分布がより高沸点成分へ移行すること、およ
び一酸化マンガンを担体として調製した触媒はオ
レフイン生成の選択性が非常に低いことがわか
る。
実施例５、比較例５
Ａ法により合成したγ−MnO210ml（22.79ｇ）
を、塩化ルテニウム（RuCl3・nH2O）2.28ｇを
エタノール−水の等容量混合液８mlに溶解させた
溶液中に含浸させる。一昼夜放置後、脱溶剤し、
90〜100℃のエヤーオーブン中で乾燥させる。次
いで生成物３ml（4.64ｇ）をとり塩化第二鉄
（FeCl3・6H2O）0.17ｇ[Table] Example 4, Comparative Example 4 γ-type manganese dioxide (method A) was calcined or not calcined, and then ruthenium was supported in the same manner as catalyst 1 of Example 1 (1% by weight of ruthenium supported),
The catalysts 17, 18,
19, 20, and 21 were prepared. Catalyst 17 was calcined at 450°C for 8 hours before supporting ruthenium, and calcined at 450°C for 8 hours after supporting ruthenium,
Catalyst 18 was fired at 550°C for 8 hours before supporting ruthenium and fired at 550°C for 8 hours after supporting ruthenium, and catalyst 21 was not fired before supporting ruthenium but was fired at 900°C for 8 hours after supporting ruthenium. The catalyst 19 was loaded with ruthenium before it was supported.
Catalyst 20 was prepared in the same manner as Catalyst 19 except that manganese monoxide was used instead of γ-type manganese dioxide. These catalysts were charged into a reactor, subjected to hydrogen reduction treatment, and reacted in the same manner as in Example 1. Table 5 shows the reaction conditions and results. From the results in Table 5, it can be seen that the higher the firing temperature of the catalyst, the higher the methane production rate, and that when the firing temperature exceeds 600 °C, the methane production rate increases
The production rate of lower olefins is extremely reduced, the product distribution shifts to higher boiling point components when ruthenium is supported on a carrier and then calcined, and catalysts prepared using manganese monoxide as a carrier are not suitable for olefin production. It can be seen that the quality is very low. Example 5, Comparative Example 5 γ-MnO 2 synthesized by method A 10ml (22.79g)
is impregnated in a solution of 2.28 g of ruthenium chloride (RuCl 3 .nH 2 O) dissolved in 8 ml of an equal volume mixture of ethanol and water. After leaving it for a day and night, remove the solvent,
Dry in an air oven at 90-100°C. Next, take 3 ml (4.64 g) of the product and add 0.17 g of ferric chloride (FeCl 3 6H 2 O).
【表】【table】
【表】【table】
【表】【table】
【表】
をエタノール−水等容量混合液８mlに溶解させた
溶液2.4mlに含浸させる。一昼夜放置後、脱溶剤
し、90〜100℃のエヤーオーブン中で乾燥するこ
とにより触媒２２を調製した。触媒２３は実施例
１の触媒１と同様にして調製したものである。触
媒２４はルテニウムと鉄とを順次でなく同時に担
持する以外は触媒２２と同様にして調製したもの
である。比較のため示した触媒２５は鉄のみを担
持する以外は触媒２２と同様にして調製したもの
である。
これらの触媒について実施例１と同様にして反
応を行なつた。その反応条件および結果を表６に
示す。表６の結果からルテニウムの代りに鉄を担
持した触媒を使用すると転化率が極端に低下し、
ほとんど触媒活性がないことがわかる。
実施例 ６
FeCl3・6H2Oの代りにそれぞれPdCl2、
RhCl3・3H2O、NiCl2・6H2O、CoCl2・6H2O、
CuCl2・2H2O、ReCl3、H2PtCl6・6H2O、
AgNO3、MgCl2、LaCl3・7H2O、TiCl3、TiCl4
およびAlCl3・6H2Oを使用する以外実施例５の
触媒２２と同様にしてγ−MnO2にルテニウムと
各種活性化剤との両者を担持した触媒２６〜３８
を調製した。
これらの触媒について実施例１と同様にして反
応を行なつた。その反応条件および結果を表７に
示す。表６、７の結果からRu金属と共に各種活
性化剤を同時担持することにより、助触媒として
の効果が出現し、希望する生成物分布および組成
は、目的とする各種金属活性化剤との任意の組み
合せで達せしめることを特徴としている。
実施例 ７
本例では実施例５、６の含浸担持と異なりイオ
ン交換でルテニウムを担体に担持した。Ａ法より
合成したγ−MnO210ml（17.74ｇ）を2N−
NH4Clおよび0.1N−MgCl2を含む水溶液500ml
（NH3でPH6.87に調整）に懸濁Impregnate with 2.4 ml of a solution of [Table] dissolved in 8 ml of an equal volume mixture of ethanol and water. After standing for a day and night, the solvent was removed and dried in an air oven at 90 to 100°C to prepare catalyst 22. Catalyst 23 was prepared in the same manner as Catalyst 1 of Example 1. Catalyst 24 was prepared in the same manner as catalyst 22, except that ruthenium and iron were supported simultaneously rather than sequentially. Catalyst 25 shown for comparison was prepared in the same manner as catalyst 22 except that only iron was supported. A reaction was carried out in the same manner as in Example 1 using these catalysts. The reaction conditions and results are shown in Table 6. The results in Table 6 show that when a catalyst supporting iron is used instead of ruthenium, the conversion rate is extremely reduced.
It can be seen that there is almost no catalytic activity. Example 6 PdCl 2 and PdCl 2 were used instead of FeCl 3 and 6H 2 O, respectively.
RhCl 3・3H 2 O, NiCl 2・6H 2 O, CoCl 2・6H 2 O,
CuCl2 ・ 2H2O , ReCl3 , H2PtCl6・6H2O ,
AgNO3 , MgCl2 , LaCl3・7H2O , TiCl3 , TiCl4
Catalysts 26 to 38 in which both ruthenium and various activators were supported on γ-MnO 2 in the same manner as catalyst 22 in Example 5 except that AlCl 3 .6H 2 O was used.
was prepared. A reaction was carried out in the same manner as in Example 1 using these catalysts. The reaction conditions and results are shown in Table 7. From the results in Tables 6 and 7, co-supporting Ru metal and various activators shows the effect as a co-catalyst, and the desired product distribution and composition can be adjusted arbitrarily with the desired various metal activators. It is characterized by being achieved by a combination of. Example 7 In this example, unlike the impregnated support in Examples 5 and 6, ruthenium was supported on the carrier by ion exchange. 10 ml (17.74 g) of γ-MnO 2 synthesized by method A was mixed with 2N-
500 ml of aqueous solution containing NH4Cl and 0.1N− MgCl2
Suspended in (adjusted to PH6.87 with NH3 )
【表】【table】
【表】
させ、30℃、17hr振とうした。その後過し風乾
した。さらに90℃エヤバス中で5hr乾燥後、
RuCl3・nH2O0.51ｇを含む水−エタノール等容
量混合溶液20ml中に含浸する。一昼夜放置後水ア
スピレーターで脱溶剤し、90〜100℃のオーブン
中で乾燥し、触媒３９とした。この様に調製した
触媒３９はRu1.0重量％、Mg0.6重量％を含んで
いた。
MgCl2の代りにZnCl2を使用する以外上記触媒
３９の製法と同様な方法で触媒４０を調製し実施
例１と同様にして評価した。表８に反応条件、生
成物組成等を明示している。また表８には触媒３
９を使用して空間速度を変えて反応を行なつた
例、およびH2／CO原料モル比を変えて反応を行
なつた例を示した。これらの結果から空間速度が
大となるほどオレフイン生成の選択性が向上する
こと、およびH2／CO比はCOがやや多い方がオ
レフイン生成の選択性が向上すること、反応圧力
が低いほどオレフイン生成の選択性が向上するこ
と[Table] Shake at 30°C for 17 hours. It was then air-dried. After further drying for 5 hours in a 90℃ air bath,
It is immersed in 20 ml of a mixed solution of water and ethanol in equal volumes containing 0.51 g of RuCl 3 .nH 2 O. After standing for a day and night, the solvent was removed using a water aspirator and dried in an oven at 90 to 100°C to obtain Catalyst 39. Catalyst 39 prepared in this manner contained 1.0% by weight of Ru and 0.6% by weight of Mg. Catalyst 40 was prepared in the same manner as for catalyst 39 above, except that ZnCl 2 was used instead of MgCl 2 , and evaluated in the same manner as in Example 1. Table 8 clearly shows the reaction conditions, product composition, etc. Table 8 also shows catalyst 3.
An example was shown in which the reaction was carried out by changing the space velocity using 9, and an example in which the reaction was carried out by changing the H 2 /CO raw material molar ratio. These results show that the selectivity for olefin production improves as the space velocity increases, that the selectivity for olefin production improves when the H 2 /CO ratio is slightly more CO, and that the lower the reaction pressure, the more olefin production increases. Improved selectivity of
【表】【table】
【表】
がわかる。
実施例８、比較例６
実施例５で調製した触媒２３を反応器に２ml
（2.60ｇ）充填し、水素ガス雰囲気下400℃×2hr
還元処理をした。その後反応温度以下に冷却した
のち、反応ガスと交換し、触媒層に流入した。所
定温度に達したのち、原料ガスと共に硫化水素ガ
スをシリンジより系内に注入する。所定量の硫化
水素を添加し、触媒表面を硫化処理をほどこした
のち触媒を評価した。反応条件および生成物分布
を表９に明記した。比較例としてあげたRu／γ
−Al2O3触媒７に較べて、対イオウ性に優れか
つ、硫化処理によりオレフインの選択性が向上す
ることに留意すべきである。
実施例 ９
触媒３９６ml（7.8ｇ）とモルデナイトを脱ア
ルミニウム処理（モルデナイトを沸とうしている
３規定塩酸水溶液中で３時間処理してSiO2／
Al2O3比15.0とした。）したもの６Understand [table]. Example 8, Comparative Example 6 2 ml of catalyst 23 prepared in Example 5 was placed in a reactor.
(2.60g) filled, 400℃×2hr under hydrogen gas atmosphere
I did the refund process. After that, the gas was cooled to below the reaction temperature, exchanged with the reaction gas, and then flowed into the catalyst layer. After reaching a predetermined temperature, hydrogen sulfide gas is injected into the system together with the raw material gas from a syringe. After adding a predetermined amount of hydrogen sulfide and subjecting the catalyst surface to sulfurization treatment, the catalyst was evaluated. The reaction conditions and product distribution are specified in Table 9. Ru/γ given as a comparative example
It should be noted that compared to -Al 2 O 3 Catalyst 7, it has excellent sulfur resistance and the sulfidation treatment improves olefin selectivity. Example 9 396 ml (7.8 g) of catalyst and mordenite were dealuminated (mordenite was treated in a boiling 3N hydrochloric acid aqueous solution for 3 hours to form SiO 2 /
The Al 2 O 3 ratio was set to 15.0. ) did 6
【表】【table】
【表】【table】
【表】【table】
【表】
ml（3.2ｇ）とをよく粉砕混合し、打錠機にてペ
レツトとし、20〜32メツシユのものを選粒して触
媒４１を得た。また触媒１８６ml（7.2ｇ）とク
ロミアCr2O36ml（9.6ｇ）とをよく粉砕混合し、
打錠機にてペレツトとし、20〜32メツシユのもの
を選粒して触媒４２を得た。これらの触媒につい
て実施例１と同様にして反応を行なつた。反応条
件および結果を表10に示す。生成物はより高沸点
成分のものが多いことがわかる。[Table] ml (3.2 g) were thoroughly ground and mixed, made into pellets using a tablet machine, and pellets of 20 to 32 meshes were selected to obtain catalyst 41. In addition, 186 ml (7.2 g) of catalyst and 6 ml (9.6 g) of Chromia Cr 2 O 3 were thoroughly ground and mixed.
The pellets were made into pellets using a tablet machine, and 20 to 32 meshes were selected to obtain catalyst 42. A reaction was carried out in the same manner as in Example 1 using these catalysts. The reaction conditions and results are shown in Table 10. It can be seen that the product contains many components with higher boiling points.
第１図は参考例１のＡ法によるγ型二酸化マン
ガンのＸ線回折図である。第２，３，４図は実施
例１および比較例１の生成炭化水素中のメタン重
量分率、エチレン／エタン生成比およびC2〜C4
合計生成量を示す。第５図は実施例２の生成炭化
水素中の炭素数分布を示す。第６〜８図は実施例
３および比較例３の生成炭化水素中のメタン重量
分率、エチレン／エタン生成比およびC2〜C4合
計生成量をあらわす。また図中カツコつきの数字
は触媒番号をあらわす。
FIG. 1 is an X-ray diffraction diagram of γ-type manganese dioxide obtained by method A of Reference Example 1. Figures 2, 3, and 4 show the methane weight fraction, ethylene/ethane production ratio, and C 2 to C 4 in the hydrocarbons produced in Example 1 and Comparative Example 1.
Shows the total production amount. FIG. 5 shows the carbon number distribution in the hydrocarbons produced in Example 2. 6 to 8 show the methane weight fraction in the hydrocarbons produced, the ethylene/ethane production ratio, and the total production amount of C 2 to C 4 in Example 3 and Comparative Example 3. In addition, the numbers in brackets in the figure represent the catalyst numbers.
Claims (1)
触媒に水素および一酸化炭素を含む混合ガスを接
触させて炭化水素類を製造する方法において、担
体としてγ型二酸化マンガンを用いることを特徴
とするオレフイン類の製造法。1. A method for producing hydrocarbons by contacting a ruthenium catalyst supported on a manganese oxide carrier with a mixed gas containing hydrogen and carbon monoxide, which uses γ-type manganese dioxide as a carrier. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58248035A JPS60146835A (en) | 1983-12-29 | 1983-12-29 | Preparation of olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58248035A JPS60146835A (en) | 1983-12-29 | 1983-12-29 | Preparation of olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60146835A JPS60146835A (en) | 1985-08-02 |
| JPH0370691B2 true JPH0370691B2 (en) | 1991-11-08 |
Family
ID=17172224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58248035A Granted JPS60146835A (en) | 1983-12-29 | 1983-12-29 | Preparation of olefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60146835A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009157260A1 (en) | 2008-06-24 | 2009-12-30 | コスモ石油株式会社 | Catalyst for fischer-tropsch synthesis, and process for production of hydrocarbon |
| WO2010055808A1 (en) | 2008-11-11 | 2010-05-20 | 新日本石油株式会社 | Method for manufacturing unsaturated hydrocarbon and oxygenated compound, catalyst, and manufacturing method therefor |
| WO2012102256A1 (en) | 2011-01-24 | 2012-08-02 | コスモ石油株式会社 | Catalyst for fischer-tropsch synthesis, and production method therefor, as well as hydrocarbon production method using fischer-tropsch synthesis catalyst |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6900151B2 (en) * | 2001-11-13 | 2005-05-31 | Exxonmobil Research And Engineering Company | In situ catalyst regeneration/activation process |
| JP5128526B2 (en) * | 2009-03-23 | 2013-01-23 | コスモ石油株式会社 | Fischer-Tropsch synthesis catalyst and method for producing hydrocarbons |
| JP5129037B2 (en) * | 2008-06-24 | 2013-01-23 | コスモ石油株式会社 | Fischer-Tropsch synthesis catalyst and method for producing hydrocarbons |
| JP5435275B2 (en) * | 2009-12-18 | 2014-03-05 | コスモ石油株式会社 | Process for producing hydrocarbons |
| US9656252B2 (en) | 2009-12-18 | 2017-05-23 | Cosmo Oil Co., Ltd. | Catalyst composition for producing hydrocarbons and method for producing hydrocarbons |
| JP5553880B2 (en) * | 2012-11-01 | 2014-07-16 | コスモ石油株式会社 | Method for producing catalyst for Fischer-Tropsch synthesis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4206134A (en) * | 1979-03-12 | 1980-06-03 | Exxon Research & Engineering Co. | Ruthenium supported on manganese oxide as hydrocarbon synthesis catalysts in CO/H2 reactions |
| JPS5867345A (en) * | 1981-08-05 | 1983-04-21 | シエ−リング・アクチエンゲゼルシヤフト | Catalyst for producing linear alpha- olefin from synthetic gas mainly and production of linear alpha-olefin |
-
1983
- 1983-12-29 JP JP58248035A patent/JPS60146835A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4206134A (en) * | 1979-03-12 | 1980-06-03 | Exxon Research & Engineering Co. | Ruthenium supported on manganese oxide as hydrocarbon synthesis catalysts in CO/H2 reactions |
| JPS5867345A (en) * | 1981-08-05 | 1983-04-21 | シエ−リング・アクチエンゲゼルシヤフト | Catalyst for producing linear alpha- olefin from synthetic gas mainly and production of linear alpha-olefin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009157260A1 (en) | 2008-06-24 | 2009-12-30 | コスモ石油株式会社 | Catalyst for fischer-tropsch synthesis, and process for production of hydrocarbon |
| US8598063B2 (en) | 2008-06-24 | 2013-12-03 | Cosmo Oil Co., Ltd. | Catalyst for Fischer-Tropsch synthesis and method for producing hydrocarbons |
| WO2010055808A1 (en) | 2008-11-11 | 2010-05-20 | 新日本石油株式会社 | Method for manufacturing unsaturated hydrocarbon and oxygenated compound, catalyst, and manufacturing method therefor |
| WO2012102256A1 (en) | 2011-01-24 | 2012-08-02 | コスモ石油株式会社 | Catalyst for fischer-tropsch synthesis, and production method therefor, as well as hydrocarbon production method using fischer-tropsch synthesis catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60146835A (en) | 1985-08-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |