JP2000104078A - Method for producing liquid hydrocarbon oil from lower hydrocarbon gas containing carbon dioxide - Google Patents
Method for producing liquid hydrocarbon oil from lower hydrocarbon gas containing carbon dioxideInfo
- Publication number
- JP2000104078A JP2000104078A JP10292930A JP29293098A JP2000104078A JP 2000104078 A JP2000104078 A JP 2000104078A JP 10292930 A JP10292930 A JP 10292930A JP 29293098 A JP29293098 A JP 29293098A JP 2000104078 A JP2000104078 A JP 2000104078A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- gas
- carbon dioxide
- carbon
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 114
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 114
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 105
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 71
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 239000007788 liquid Substances 0.000 title claims description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 229
- 239000007789 gas Substances 0.000 claims abstract description 196
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 114
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 114
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000000034 method Methods 0.000 claims abstract description 93
- 229910052751 metal Inorganic materials 0.000 claims abstract description 83
- 239000002184 metal Substances 0.000 claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 64
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 28
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 28
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 24
- 230000000694 effects Effects 0.000 claims abstract description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001868 water Inorganic materials 0.000 claims abstract description 19
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 99
- 230000015572 biosynthetic process Effects 0.000 claims description 93
- 238000006243 chemical reaction Methods 0.000 claims description 89
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 46
- 239000002994 raw material Substances 0.000 claims description 32
- 238000004821 distillation Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 9
- 239000003345 natural gas Substances 0.000 claims description 8
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 7
- 239000003350 kerosene Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 4
- 239000003502 gasoline Substances 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 abstract description 25
- 229910052703 rhodium Inorganic materials 0.000 abstract description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002253 acid Substances 0.000 description 33
- 239000003921 oil Substances 0.000 description 32
- 239000007864 aqueous solution Substances 0.000 description 31
- 239000000203 mixture Substances 0.000 description 21
- 238000000465 moulding Methods 0.000 description 18
- 238000010304 firing Methods 0.000 description 17
- 238000000151 deposition Methods 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 15
- 230000008021 deposition Effects 0.000 description 15
- 238000006057 reforming reaction Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 238000002407 reforming Methods 0.000 description 11
- 239000008188 pellet Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- -1 inorganic acid salts Chemical class 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000000629 steam reforming Methods 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000035425 carbon utilization Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 229910052914 metal silicate Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- BPEVHDGLPIIAGH-UHFFFAOYSA-N ruthenium(3+) Chemical compound [Ru+3] BPEVHDGLPIIAGH-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 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
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229940057952 methanol Drugs 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 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
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-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
- 239000012266 salt solution Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、炭酸ガスを含む低
級炭化水素ガスから液状炭化水素油を製造する方法に関
する。The present invention relates to a method for producing a liquid hydrocarbon oil from a lower hydrocarbon gas containing carbon dioxide.
【０００２】[0002]
【従来の技術】低級炭化水素ガスを、炭酸ガス存在下、
限定量のスチームでリフォーミング反応（合成ガス生成
反応）させて、水素と一酸化炭素からなる合成ガスに転
換し、この合成ガスからＦｉｓｃｈｅｒ−Ｔｒｏｐｓｃ
ｈ炭化水素合成反応により、燃料油として好適な炭素数
５以上の液状炭化水素油を製造する方法は知られてい
る。このような方法においては、そのリフォーミング工
程で炭素析出による触媒被毒の問題が生じる。このよう
な方法に関連する従来技術を示すと、以下の通りであ
る。 特開昭６０−２３５８８９、ＵＳ４６４０７６６ これらの文献には、リフォーミング工程でＮｉ含有触媒
を使用しており、触媒上への炭素析出の問題を解決でき
る技術の開示はない。 ＵＳ５６２１１５５、ＵＳ５６２０６７０ これらの文献に示された方法は、炭酸ガスの炭化水素へ
の転換をねらったものであるが、合成ガスの生産効率を
上げようとすると、やはりリフォーミング工程で炭素析
出に遭遇することになる。しかし、これらの方法も従来
のＮｉ含有触媒を使用しており、炭素析出防止に関する
技術開示はない。また、フィッシャー・トロプシュ（以
下、単にＦＴとも言う）合成工程で、ＣＯシフト活性の
高いＦｅ触媒を使用するので、一酸化炭素の約半分が炭
酸ガスの形で失われ、この工程での炭素変換効率は最大
でも５０％となり、全プロセスの炭素変換効率が低くな
る。2. Description of the Related Art Low-grade hydrocarbon gas is produced in the presence of carbon dioxide gas.
A reforming reaction (synthesis gas generation reaction) is performed with a limited amount of steam to convert the gas into a synthesis gas composed of hydrogen and carbon monoxide, and Fischer-Tropsc is converted from the synthesis gas.
A method for producing a liquid hydrocarbon oil having 5 or more carbon atoms suitable as a fuel oil by a hydrocarbon synthesis reaction is known. In such a method, a problem of catalyst poisoning due to carbon deposition occurs in the reforming step. The prior art related to such a method is as follows. JP-A-60-235889, U.S. Pat. No. 4,640,766 In these documents, a Ni-containing catalyst is used in the reforming step, and there is no disclosure of a technique capable of solving the problem of carbon deposition on the catalyst. US Pat. No. 5,621,155 and US Pat. No. 5,620,670 These methods aim at converting carbon dioxide into hydrocarbons. However, in order to increase the production efficiency of syngas, carbon deposition is also encountered in the reforming step. Will be. However, these methods also use a conventional Ni-containing catalyst, and there is no technical disclosure about carbon deposition prevention. In addition, since a Fe catalyst having a high CO shift activity is used in a Fischer-Tropsch (hereinafter also referred to simply as FT) synthesis process, about half of carbon monoxide is lost in the form of carbon dioxide gas, and carbon conversion in this process is performed. The efficiency is at most 50% and the carbon conversion efficiency of the whole process is low.
【０００３】前記のように、炭酸ガスを含む低級炭化水
素ガスをリフォーミング反応させて合成ガスとし、これ
をＦＴ炭化水素合成反応により液状炭化水素油を製造す
る方法は知られている。この方法の課題は、高いエネル
ギー消費と設備コストを要する合成ガス製造工程での生
産効率を上げることと、ＦＴ合成を含めた全炭素変換効
率を最大化することにある。合成ガス製造工程での生産
効率を上げることは、処理する低級炭化水素ガス、炭酸
ガス及びスチームの合計量に対して生産される合成ガス
の量を上げることに他ならない。それには、低級炭化水
素ガスのリフォーミング反応工程で、炭酸ガスが一酸化
炭素に変換される効率（炭素変換効率）が最大となる炭
酸ガス濃度で、さらにＦＴ合成に適する合成ガスを直接
製造するのに必要とする最低限のスチーム添加量で、リ
フォーミング反応を行うことが必要となる。しかしなが
ら、このような方法の場合、原料ガスである低級炭化水
素ガス中に混入させる炭酸ガスとスチームの量を低濃度
範囲に調節すると、その低級炭化水素ガスのリフォーミ
ング工程において触媒上に著量の炭素析出が起り、触媒
が短時間で失活してしまう。[0003] As described above, there is known a method of producing a liquid hydrocarbon oil by subjecting a lower hydrocarbon gas containing carbon dioxide gas to a reforming reaction to produce a synthesis gas and subjecting it to an FT hydrocarbon synthesis reaction. The problem of this method is to increase the production efficiency in the synthesis gas production process requiring high energy consumption and equipment cost, and to maximize the total carbon conversion efficiency including FT synthesis. Increasing the production efficiency in the synthesis gas production process is nothing less than increasing the amount of synthesis gas produced relative to the total amount of lower hydrocarbon gas, carbon dioxide gas and steam to be treated. In order to achieve this, in the reforming reaction step of lower hydrocarbon gas, a synthesis gas suitable for FT synthesis is directly produced at a carbon dioxide gas concentration at which the conversion efficiency of carbon dioxide gas to carbon monoxide (carbon conversion efficiency) is maximized. It is necessary to carry out the reforming reaction with the minimum amount of steam addition necessary for the reaction. However, in the case of such a method, when the amounts of carbon dioxide gas and steam mixed into the lower hydrocarbon gas as a raw material gas are adjusted to a low concentration range, a significant amount of the lower hydrocarbon gas is formed on the catalyst in the reforming step. , And the catalyst is deactivated in a short time.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、合成ガス生
成工程とフィッシャー・トロプシュ工程を含む低級炭化
水素からの液状炭化水素油の製造方法において、高い炭
素利用率でかつ触媒被毒の原因となる炭素析出を防止す
ることにより、液状炭化水素油を工業的に有利に製造す
る方法を提供することをその課題とする。SUMMARY OF THE INVENTION The present invention relates to a method for producing a liquid hydrocarbon oil from a lower hydrocarbon including a synthesis gas generation step and a Fischer-Tropsch step, which has a high carbon utilization rate and causes catalyst poisoning. An object of the present invention is to provide a method for industrially advantageously producing a liquid hydrocarbon oil by preventing carbon deposition.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、炭酸ガスを含む低級
炭化水素ガスを液状炭化水素油へ転換する方法におい
て、（ｉ）炭酸ガスを１０〜５０モル％含む原料低級炭
化水素ガスに、水及び又はスチームを添加して、各成分
が下記式を満たす混合ガスを調製する工程、 ０．５≦（［ＣＯ2］＋［Ｈ2Ｏ］／［Ｃ］≦２．５ （式中、［ＣＯ2］はＣＯ2のモル数、［Ｈ2Ｏ］はＨ2Ｏ
のモル数及び［Ｃ］は低級炭化水素ガス中に含まれる炭
素のモル数を示す）（ii）該混合ガス中に含まれる低級
炭化水素ガスを、主に酸化マグネシウムからなる担体に
ロジウム及び／又はルテニウムの触媒金属を担持させた
触媒であって、該触媒の比表面積が５ｍ2／ｇ以下で、
かつ触媒金属の担持量が金属原子基準で担体金属酸化物
に対して０．１０〜５０００重量ｐｐｍである触媒に、
１０〜７５気圧の圧力、６００〜１０００℃の温度で接
触させて、水素／一酸化炭素のモル比が１．５〜２．５
の合成ガスを生成させる工程、（iii）該合成ガスを、
低ＣＯシフト活性のフィッシャー・トロプシュ触媒の存
在下で反応させ液状炭化水素油を含む反応生成物を生成
させる工程、（iv）該反応生成物から炭化水素油を分離
する工程、からなることを特徴とする炭化水素油の製造
方法が提供される。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, in the method for converting a lower hydrocarbon gas containing carbon dioxide into liquid hydrocarbon oil, (i) water and / or steam are added to the raw material lower hydrocarbon gas containing 10 to 50 mol% of carbon dioxide. To prepare a mixed gas in which each component satisfies the following formula: 0.5 ≦ ([CO 2 ] + [H 2 O] / [C] ≦ 2.5 (where [CO 2 ] Is the number of moles of CO 2 and [H 2 O] is H 2 O
And [C] indicate the number of moles of carbon contained in the lower hydrocarbon gas.) (Ii) The lower hydrocarbon gas contained in the mixed gas is converted into rhodium and / or Or a catalyst carrying a ruthenium catalyst metal, wherein the specific surface area of the catalyst is 5 m 2 / g or less,
And a catalyst wherein the amount of the supported metal is 0.10 to 5000 ppm by weight based on the metal atom with respect to the carrier metal oxide,
Contacting at a pressure of 10 to 75 atm and a temperature of 600 to 1000 ° C., the hydrogen / carbon monoxide molar ratio is 1.5 to 2.5.
(Iii) generating the synthesis gas of
Reacting in the presence of a low CO shift activity Fischer-Tropsch catalyst to produce a reaction product containing a liquid hydrocarbon oil, and (iv) separating the hydrocarbon oil from the reaction product. And a method for producing a hydrocarbon oil.
【０００６】[0006]
【発明の実施の形態】本発明は、炭酸ガスを含む原料低
級状炭化水素ガスを水素と一酸化炭素へ転換するリフォ
ーミング反応が、より改善された炭素変換効率で促進さ
れるように、そのリフォーミング反応工程において、炭
酸ガスの十分な利用を図りつつ、フィイシャー・トロプ
シュ合成に必要とする水素／一酸化炭素比の合成ガスを
生産する。ＦＴ合成による液体燃料化法では、合成ガス
の組成はＨ2／ＣＯ比＝２が理想的であり、実際には、
１．５〜２．５近辺に調整する必要がある。軽質炭化水
素をＦＴ合成に要求される組成の合成ガスに転換させる
技術としては、大別すると部分酸化法、スチームリフォ
ーミング法及びそれらの組み合せ法がある。メタンのよ
うな炭化水素ガスと、限定量の酸素を使用する部分酸化
反応は、式（１）で示されるように、ＦＴ合成に適合す
る水素：一酸化炭素＝２：１（モル比）の合成ガスが生
成される。 ＣＨ4＋1/2Ｏ2 → ２Ｈ2＋ＣＯ （１） 部分酸化法は、軽質炭化水素から、ＦＴ合成に適す水素
／一酸化炭素比の合成ガス製造する際には優れた方法の
一つと言える。しかし、部分酸化法では、炭酸ガスの一
酸化炭素への実質的転換はほとんど期待できない。した
がって、炭酸ガスを含む軽質炭化水素を原料とする場合
には、部分酸化法では、原料中の炭酸ガスは不活性ガス
として処理され、一方合成ガス中の水素と一酸化炭素が
さらに酸化（燃焼）されて、いくらかの水と炭酸ガスが
常に副産される。この燃焼で発生した炭酸ガスが加わる
のでリアクター出口の合成ガス中の炭酸ガス濃度は供給
原料より高くなってしまう。したがって、ＦＴ合成リア
クターに供給される前に、合成ガスから炭酸ガスを除去
する必要性が生じ、このために追加の設備投資が必要と
なる。以上のことから、炭酸ガスを多く含む軽質炭化水
素ガスを原料とする場合には部分酸化法はＦＴ用合成ガ
スの製造には適さない。DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a reforming reaction for converting a raw material hydrocarbon gas containing carbon dioxide gas into hydrogen and carbon monoxide so as to be promoted with improved carbon conversion efficiency. In the reforming reaction step, a synthesis gas having a hydrogen / carbon monoxide ratio required for Fischer-Tropsch synthesis is produced while sufficiently utilizing carbon dioxide gas. In the liquid fuel conversion method by FT synthesis, the composition of the synthesis gas is ideally an H 2 / CO ratio = 2.
It is necessary to adjust to around 1.5 to 2.5. Techniques for converting light hydrocarbons into synthesis gas having a composition required for FT synthesis are roughly classified into a partial oxidation method, a steam reforming method, and a combination method thereof. The partial oxidation reaction using a hydrocarbon gas such as methane and a limited amount of oxygen can be carried out in a hydrogen: carbon monoxide = 2: 1 (molar ratio) suitable for FT synthesis as shown in equation (1). Syngas is generated. CH 4 + 1/2 O 2 → 2H 2 + CO (1) partial oxidation process may be said from light hydrocarbons, and a good way in the synthesis gas production of hydrogen / carbon monoxide ratio Suitable for FT synthesis . However, in the partial oxidation method, substantial conversion of carbon dioxide to carbon monoxide can hardly be expected. Therefore, when a light hydrocarbon containing carbon dioxide is used as a raw material, in the partial oxidation method, the carbon dioxide in the raw material is treated as an inert gas, while the hydrogen and carbon monoxide in the synthesis gas are further oxidized (combustion). ), And some water and carbon dioxide are always by-produced. Since the carbon dioxide gas generated by this combustion is added, the carbon dioxide gas concentration in the synthesis gas at the reactor outlet becomes higher than that of the feedstock. Therefore, there is a need to remove carbon dioxide from the synthesis gas before it is fed to the FT synthesis reactor, which requires additional capital investment. As described above, when a light hydrocarbon gas containing a large amount of carbon dioxide is used as a raw material, the partial oxidation method is not suitable for producing a synthesis gas for FT.
【０００７】一方、技術的に完成度の高いメタンのリフ
ォーミングでは、メタンはスチームと以下の反応式に従
って反応する。 ＣＨ4＋Ｈ2Ｏ＝３Ｈ2＋ＣＯ （２） しかし、スチームリフォーミングのみでは、水素／一酸
化炭素比が３の合成ガスとなり、ＦＴ合成反応にそのま
ま適用となれば水素の分離除去によるガス組成の調整が
必要となる。例えば、膜分離などにより過剰な水素を除
去することができるが、これには、追加の設備投資を必
要とするし、プロセスとして水素が損失するので、全プ
ロセスの液化炭化水素収率がその分低くなる。この欠点
を補うため、オートサーマル・リフォーミングで代表さ
れる、部分酸化とスチームリフォーミングを組み合わせ
た合成ガス製造法が提案されている。この場合にも前述
したように部分酸化で炭酸ガスを一酸化炭素に転換でき
ないので、結局、炭酸ガスを多く含む軽質炭化水素を原
料とする場合には、この組み合せ法もＦＴ用合成ガスの
製造には適さない。炭酸ガスを一酸化炭素に転換できる
のは、次式の炭酸ガスリフォーミング反応である。 ＣＨ4＋ＣＯ2→２Ｈ2＋２ＣＯ （３） しかし、この反応のみでは水素／一酸化炭素比が低く、
ＦＴ合成用としては不向きな合成ガスしか生成できな
い。このＨ2／ＣＯモル比の調節は、合成ガス生成工程
（リフォーミング工程）における原料炭化水素中に含ま
れる炭素と、スチーム及び／又はＣＯ2とのモル比によ
ってなされる。そこで、前記反応式（２）のスチームリ
フォーミングと前記反応式（３）の炭酸ガスリフォーミ
ングの両反応を同時に進行させ、水素／一酸化炭素のモ
ル比が１．５〜２．５の合成ガスを生成させるのが本発
明の基本反応原理である。ここで解決しなければならな
い課題は、高いエネルギー消費と設備コストを要する合
成ガス生成工程での生産効率を挙げることと、ＦＴ合成
を含めた全炭素の利用率を最大化することである。この
場合、合成ガス生成工程での生産効率を挙げることは下
記式で示される処理する低級炭化水素ガス、炭酸ガス及
びスチームの合計量に対する合成ガスの量の割合（合成
ガス生産効率）を上げることである。On the other hand, in methane reforming which is technically highly complete, methane reacts with steam according to the following reaction formula. CH 4 + H 2 O = 3H 2 + CO (2) However, only steam reforming results in a synthesis gas having a hydrogen / carbon monoxide ratio of 3. If the gas is directly applied to the FT synthesis reaction, the gas composition by separation and removal of hydrogen is reduced. Adjustments are required. For example, excess hydrogen can be removed by membrane separation or the like, but this requires additional capital investment and hydrogen is lost as a process, so the liquefied hydrocarbon yield of the entire process is reduced accordingly. Lower. In order to make up for this drawback, a synthesis gas production method combining partial oxidation and steam reforming, represented by autothermal reforming, has been proposed. Also in this case, as described above, carbon dioxide cannot be converted to carbon monoxide by partial oxidation. Therefore, when a light hydrocarbon containing a large amount of carbon dioxide is used as a raw material, this combination method also requires the production of FT synthesis gas. Not suitable for The conversion of carbon dioxide to carbon monoxide is a carbon dioxide reforming reaction of the following formula. CH 4 + CO 2 → 2H 2 + 2CO (3) However, this reaction alone has a low hydrogen / carbon monoxide ratio,
Only unsuitable synthesis gas can be generated for FT synthesis. This adjustment of the H 2 / CO molar ratio is achieved and the carbon contained in the hydrocarbon feedstock in the synthesis gas production step (reforming step), the molar ratio of steam and / or CO 2. Therefore, both the steam reforming of the reaction formula (2) and the carbon dioxide gas reforming of the reaction formula (3) proceed simultaneously, and the synthesis gas having a molar ratio of hydrogen / carbon monoxide of 1.5 to 2.5 is obtained. Is the basic reaction principle of the present invention. The issues to be solved here are to increase the production efficiency in the synthesis gas production process requiring high energy consumption and equipment cost, and to maximize the utilization rate of all carbon including FT synthesis. In this case, raising the production efficiency in the synthesis gas generation step means increasing the ratio of the amount of synthesis gas to the total amount of lower hydrocarbon gas, carbon dioxide gas and steam to be treated (syngas production efficiency) represented by the following formula. It is.
【０００８】 Ｒ(ＣＯ＋Ｈ2)＝{([ＣＯ]＋[Ｈ2]／([Ｃ]＋[ＣＯ2]＋[Ｈ2Ｏ])}×１００ (４ ) Ｒ(ＣＯ＋Ｈ2)：合成ガス生産効率（モル％） [ＣＯ]：ＣＯのモル数 [Ｈ2]：Ｈ2のモル数 [Ｃ]：低級炭化水素ガス中に含まれる炭素のモル数 [ＣＯ2]：ＣＯ2のモル数 [Ｈ2Ｏ]：スチームのモル数R (CO + H 2 ) = {([CO] + [H 2 ] / ([C] + [CO 2 ] + [H 2 O])} × 100 (4) R (CO + H 2 ): synthesis gas Production efficiency (mol%) [CO]: number of moles of CO [H 2 ]: number of moles of H 2 [C]: number of moles of carbon contained in lower hydrocarbon gas [CO 2 ]: number of moles of CO 2 [H 2 O]: mole number of steam
【０００９】合成ガスの生産効率Ｒ（ＣＯ＋Ｈ2）を向
上させるには、下記式（５）で示される、前記反応式
（３）のリフォーミング反応により炭酸ガスとメタンか
ら生成される一酸化炭素の割合（炭素変換効率）が最大
化される炭酸ガス濃度で、さらにＦＴ合成に適する組成
の合成ガスを製造するに必要とする最低限のスチーム添
加量で、リフォーミング反応を行う必要がある。要する
に、リフォーマーへの供給原料中の低級炭化水素ガスに
対する炭酸ガスと水蒸気及び水の供給量を、できるだけ
反応量論近くまでに減少させてリフォーミング反応する
のがその効率を最大化することになる。しかし、前記式
（２)、(３）の反応の両方とも大きな吸熱の可逆反応で
あり、反応の進行程度は反応条件（温度と圧力）に大き
く依存し、高温で低圧ほど、合成ガスの生産に好都合と
なる。In order to improve the production efficiency R (CO + H 2 ) of the synthesis gas, carbon monoxide produced from carbon dioxide and methane by the reforming reaction of the above reaction formula (3) represented by the following formula (5) It is necessary to carry out the reforming reaction at a carbon dioxide gas concentration at which the ratio (carbon conversion efficiency) is maximized, and at a minimum steam addition amount necessary for producing a synthesis gas having a composition suitable for FT synthesis. In short, the efficiency of the reforming reaction is maximized by reducing the supply of carbon dioxide, water vapor, and water to the lower hydrocarbon gas in the feed to the reformer as close as possible to the reaction stoichiometry. . However, both the reactions of the above formulas (2) and (3) are reversible reactions with large endotherms, and the degree of progress of the reaction greatly depends on the reaction conditions (temperature and pressure). It will be convenient.
【００１０】 Ｒ(ＣＯ)＝{([ＣＯ]／([Ｃ]＋[ＣＯ2])}×１００ （５） Ｒ(ＣＯ）：炭素変換効率（モル％） [ＣＯ]：ＣＯのモル数 [Ｃ]：低級炭化水素ガスに含まれる炭素のモル数 [ＣＯ2]：ＣＯ2のモル数R (CO) = {([CO] / ([C] + [CO 2 ])} × 100 (5) R (CO): carbon conversion efficiency (mol%) [CO]: number of moles of CO [C]: mole number of carbon contained in lower hydrocarbon gas [CO 2 ]: mole number of CO 2
【００１１】現在、工業的に採用されている実際のリフ
ォーマーは、６００〜１０００℃温度範囲で、スチーム
が大過剰（原料炭化水素の２〜５倍モル）で運転されて
いる。低い［Ｈ2Ｏ］／［Ｃ］比率はプロセス系内のス
チームをより少なくでき、よりよい熱経済性を与える
が、［Ｈ2Ｏ］／［Ｃ］比率を引き下げると触媒層への
カーボン析出が激しく、差圧増大による運転停止の危険
性があり、スチームリフォーミングでの限界［Ｈ2Ｏ］
／［Ｃ］比率は約１．５といわれている。また、このカ
ーボン析出の限界領域での運転を避けるには、原料中の
炭酸ガス濃度が高くなるほど［Ｈ2Ｏ］／［Ｃ］比を高
くする必要がある（“Ｓｔｕｄｉｅｓ ｉｎ Ｓｕｒｆ
ａｃｅ Ｓｃｉｅｎｃｅ ａｎｄ Ｃａｔａｌｙｓｉｓ
８１，Ｎａｔｕｒａｌ Ｇａｓ Ｃｏｎｖｅｒｓｉｏ
ｎ II”，ｅｄ． ｂｙ Ｈ．Ｅ．Ｃｕｒｒｙ−Ｈｙｄ
ｅ，Ｒ．Ｆ．Ｈｏｗｅ，ｐ．２５（１９９４），ＥＬＳ
ＥＶＩＥＲ）。At present, the actual reformer industrially employed is operated in a temperature range of 600 to 1000 ° C. with a large excess of steam (2 to 5 times the amount of the starting hydrocarbon). A low [H 2 O] / [C] ratio can result in less steam in the process system and give better thermoeconomics, but lowering the [H 2 O] / [C] ratio will result in carbon deposition on the catalyst layer. Severe, there is a risk of operation stop due to increased differential pressure, and the limit in steam reforming [H 2 O]
The / [C] ratio is said to be about 1.5. Further, in order to avoid operation in the limit region of carbon deposition, it is necessary to increase the [H 2 O] / [C] ratio as the concentration of carbon dioxide in the raw material increases (“Studies in Surf”).
ace Science and Catalysis
81, Natural Gas Conversio
n II ", ed. by HE Curry-Hyd
e, R. F. Howe, p. 25 (1994), ELS
EVIER).
【００１２】本発明で適用する炭酸ガスとスチームの限
定された濃度領域、すなわち炭酸ガスを１０から５０モ
ル％含む低級炭化水素ガスに、水及び／又はスチームを
添加し、（［ＣＯ2］＋［Ｈ2Ｏ］）／［Ｃ］が２．５〜
５の範囲に調整された原料ガスを既存のＮｉ系リフォー
ミング触媒で処理すると、触媒層に多量のカーボンが析
出して比較的短時間に運転不能となる。この深刻な問題
は、本発明による特定の触媒の使用により解決すること
ができる。本発明で用いる触媒は、主に酸化マグネシウ
ムからなる担体にロジウム及び／又はルテニウムの触媒
金属を担持させた触媒であって、該触媒の比表面積が５
ｍ2／ｇ以下で、かつ触媒金属の担持量が金属原子基準
で担体金属酸化物に対して０．１０〜５０００重量ｐｐ
ｍである触媒である。[0012] Water and / or steam are added to a limited concentration region of carbon dioxide and steam applied in the present invention, that is, a lower hydrocarbon gas containing 10 to 50 mol% of carbon dioxide, and ([CO 2 ] + [H 2 O]) / [C] is 2.5 to
When the raw material gas adjusted to the range of 5 is treated with the existing Ni-based reforming catalyst, a large amount of carbon is deposited on the catalyst layer, and operation becomes impossible in a relatively short time. This serious problem can be solved by using a specific catalyst according to the present invention. The catalyst used in the present invention is a catalyst in which a catalytic metal of rhodium and / or ruthenium is supported on a carrier mainly composed of magnesium oxide, and the specific surface area of the catalyst is 5%.
m 2 / g or less, and the supported amount of the catalyst metal is 0.10 to 5000 weight parts per hundred based on the metal oxide based on the metal atom.
m.
【００１３】本発明においては、原料低級炭化水素ガス
中の炭酸ガスの濃度を１０〜５０モル％、好ましくは２
０〜４０モル％である。低級炭化水素ガス中の炭酸ガス
が前記範囲外では、前記（５）式の炭素利用率をモル基
準で５０％以上に上げることができない。さらに、好ま
しくは炭酸ガスを２０〜４０モル％にすることにより、
さらに炭素利用率を向上させることができる。In the present invention, the concentration of carbon dioxide in the raw material lower hydrocarbon gas is 10 to 50 mol%, preferably 2 to 50 mol%.
0 to 40 mol%. If the carbon dioxide gas in the lower hydrocarbon gas is outside the above range, the carbon utilization rate of the above formula (5) cannot be increased to 50% or more on a molar basis. Further, preferably, the content of carbon dioxide is set to 20 to 40 mol%,
Further, the carbon utilization can be improved.
【００１４】水及び／又はスチーム添加量は、できるだ
け少ない方がエネルギー効率を高くでき好ましいが、合
成ガス中の水素／一酸化酸素のモル比を１．５〜２．５
に調整するのに必要な量としては、該低級炭化水素ガス
がＣＨ4である場合は、炭素原子に対してモル比で０．
４〜１．５添加する必要がある。また、合成ガスの原料
組成を、その（［ＣＯ2］＋［Ｈ2Ｏ］）／［Ｃ］比が
０．５〜２．５、好ましくは１〜２の範囲になるように
調整することにより、該合成ガス生成工程の合成ガス生
産効率を８０％以上という高いレベルが達成できる。さ
らに、（［ＣＯ2］＋［Ｈ2Ｏ］）／［Ｃ］比が１〜２の
混合ガスを用いると効率がより高められる。The amount of water and / or steam to be added is preferably as small as possible because the energy efficiency can be increased, but the molar ratio of hydrogen / oxygen monoxide in the synthesis gas is preferably 1.5 to 2.5.
When the lower hydrocarbon gas is CH 4 , the amount necessary for adjusting the concentration to 0.1 is adjusted to 0.1 in terms of a molar ratio to carbon atoms.
It is necessary to add 4-1.5. Further, the raw material composition of the synthesis gas is adjusted so that the ratio ([CO 2 ] + [H 2 O]) / [C] is in the range of 0.5 to 2.5, preferably 1 to 2. Thereby, a high level of synthesis gas production efficiency of 80% or more in the synthesis gas generation step can be achieved. Further, the efficiency is further improved by using a mixed gas having a ratio of ([CO 2 ] + [H 2 O]) / [C] of 1 to 2.
【００１５】本発明における出発原料は、低級炭化水素
ガス又は低級炭化水素ガスのほかに炭酸ガスを含むもの
である。低級炭化水素ガスとしては、メタン、エタン、
プロパン、ブタン、イソブタン等の炭素数１〜４の低級
炭化水素が用いられ、特に、メタンを主成分とし、それ
以外にエタン、プロパン、ブタン、イソブタン等の低級
炭化水素を含むものが用いられる。本発明では、原料ガ
スとしては、天然ガス、特に炭酸ガスを含む天然ガスが
好ましい。供給原料ガス中に過剰な炭酸ガスが含まれて
いる場合に、その濃度を調整する方法としては、操作圧
力１０〜８０気圧、より好ましくは操作圧力２０〜５０
気圧の加圧蒸留塔を用い、その塔底より主に炭酸ガスを
分離し、塔頂より所定の炭酸ガス濃度の原料ガスを得る
方法が有効である。操作圧力を上記範囲より低くする
と、蒸留塔内に炭酸ガスの凝固点以下の部分が生じ、炭
酸ガスの固体が析出して蒸留不能となる。また、塔頂温
度を−６０℃以上の操作条件にすると、炭酸ガスの固体
析出なく加圧蒸留ができる。一方、圧力が上記範囲を超
えると設備等のコストが高くなり不経済となる。炭酸ガ
スが多量に含まれる高圧の天然ガスを本発明の原料とす
る場合には、この加圧蒸留により回収される余剰の天然
ガスは高圧状態を保持しているので、そのま井戸元に戻
すことも可能である。The starting material in the present invention contains a lower hydrocarbon gas or carbon dioxide gas in addition to the lower hydrocarbon gas. Lower hydrocarbon gases include methane, ethane,
A lower hydrocarbon having 1 to 4 carbon atoms such as propane, butane, and isobutane is used. In particular, those containing methane as a main component and other lower hydrocarbons such as ethane, propane, butane, and isobutane are used. In the present invention, the raw material gas is preferably a natural gas, particularly a natural gas containing carbon dioxide gas. When an excessive amount of carbon dioxide gas is contained in the feed gas, a method for adjusting the concentration thereof may be an operating pressure of 10 to 80 atm, more preferably an operating pressure of 20 to 50 atm.
It is effective to use a pressure distillation column having a pressure of atmospheric pressure, mainly separate carbon dioxide from the bottom of the column, and obtain a raw material gas having a predetermined carbon dioxide concentration from the top of the column. If the operating pressure is lower than the above range, a portion below the freezing point of carbon dioxide gas is generated in the distillation column, and solid carbon dioxide gas precipitates and distillation becomes impossible. When the operation temperature is -60 ° C. or higher, pressure distillation can be performed without depositing carbon dioxide gas as a solid. On the other hand, if the pressure exceeds the above range, the cost of equipment and the like will increase, and it will be uneconomical. When high-pressure natural gas containing a large amount of carbon dioxide is used as the raw material of the present invention, the excess natural gas recovered by this pressure distillation is maintained at a high pressure, and is returned to the well. It is also possible.
【００１６】本発明の合成ガス生成工程で用いる触媒
（以下、本発明触媒とも言う）は、特定性状の担体金属
酸化物に、ロジウム（Ｒｈ）及びルテニウム（Ｒｕ）の
中から選択された少なくとも１種の触媒金属を担持させ
た触媒である。この場合、触媒金属は、金属状態で担持
されていてもよいし、酸化物等の金属化合物の状態で担
持されていてもよい。本発明触媒は炭酸ガスを含む低級
炭化水素ガスのリフォーミング反応に必要な活性は保有
し、且つ副反応である炭素析出反応を著しく抑制する作
用を有することを特徴とする。本発明で用いる炭素析出
反応を著しく抑制する触媒は、（ｉ）主に酸化マグネシ
ウムからなる担体であること、（ii）その触媒の比表面
積が５ｍ2／ｇ以下であること、（iii)該金属触媒の担
持量が該担持金属酸化物に対して０．１〜５０００重量
ｐｐ ｍであること、を特徴とする触媒である。こ
のような炭素析出活性の著しく抑制された触媒は、本発
明者らによって初めて見出されたものである。担体とし
ては、酸化マグネシウム（ＭｇＯ）の単一金属酸化物の
他、ＭｇＯ／ＣａＯ、ＭｇＯ／ＢａＯ、ＭｇＯ／Ｚｎ
Ｏ、ＭｇＯ／Ａｌ2Ｏ3、ＭｇＯ／ＺｒＯ2、ＭｇＯ／Ｌ
ａ2Ｏ3等の複合金属酸化物及び混合物が挙げられる。本
発明で用いる比表面積が５ｍ2／ｇ以下の触媒は、触媒
金属の担持前に担体金属酸化物を３００〜１３００℃、
好ましくは６５０〜１２００℃で焼成することによって
得ることができる。焼成温度の上限値は特に規定されな
いが、通常、１５００℃以下、好ましくは１３００℃以
下である。この場合、その焼成温度と焼成時間によっ
て、得られる触媒又は担体金属酸化物の比表面積をコン
トロールすることができる。本発明触媒又は本発明で用
いる担体の好ましい比表面積は５ｍ2／ｇ以下である。
その比表面積の下限値は、０．１ｍ2／ｇ程度である。
担体金属酸化物に対する触媒金属の担持量は、金属換算
量で、担体金属酸化物に対し、０．１重量ｐｐｍ以上
で、その上限値は５０００重量ｐｐｍ程度である。The catalyst used in the synthesis gas generation step of the present invention (hereinafter also referred to as the catalyst of the present invention) is a carrier metal oxide having a specific property and at least one selected from rhodium (Rh) and ruthenium (Ru). It is a catalyst that supports a certain kind of catalytic metal. In this case, the catalyst metal may be supported in a metal state, or may be supported in a state of a metal compound such as an oxide. The catalyst of the present invention is characterized in that it retains the activity necessary for the reforming reaction of lower hydrocarbon gas containing carbon dioxide gas and has an effect of remarkably suppressing the carbon deposition reaction which is a side reaction. The catalyst used in the present invention for remarkably suppressing the carbon deposition reaction is (i) a carrier mainly composed of magnesium oxide, (ii) the specific surface area of the catalyst is 5 m 2 / g or less, (iii) The catalyst is characterized in that the supported amount of the metal catalyst is 0.1 to 5,000 weight ppm with respect to the supported metal oxide. Such a catalyst in which the carbon deposition activity is significantly suppressed has been found for the first time by the present inventors. As the carrier, in addition to a single metal oxide of magnesium oxide (MgO), MgO / CaO, MgO / BaO, MgO / Zn
O, MgO / Al 2 O 3 , MgO / ZrO 2 , MgO / L
Composite metal oxides such as a 2 O 3 and mixtures thereof are mentioned. The catalyst having a specific surface area of 5 m 2 / g or less used in the present invention has a carrier metal oxide at 300 to 1300 ° C. before supporting the catalyst metal,
Preferably, it can be obtained by firing at 650 to 1200 ° C. The upper limit of the firing temperature is not particularly limited, but is usually 1500 ° C or lower, preferably 1300 ° C or lower. In this case, the specific surface area of the resulting catalyst or carrier metal oxide can be controlled by the firing temperature and the firing time. The preferred specific surface area of the catalyst of the present invention or the carrier used in the present invention is 5 m 2 / g or less.
The lower limit of the specific surface area is about 0.1 m 2 / g.
The amount of the catalyst metal supported on the carrier metal oxide is 0.1 ppm by weight or more, and the upper limit thereof is about 5000 ppm by weight based on the metal oxide.
【００１７】本発明の触媒において、その触媒の比表面
積と担体金属酸化物の比表面積とは実質的にはほぼ同じ
であり、本明細書中では、その触媒の比表面積と担体金
属酸化物の比表面積とは同義として用いた。なお、本明
細書中で触媒又は担体金属酸化物に関して言う比表面積
は「ＢＥＴ」法により、温度１５℃で測定されたもので
ある。その測定装置としては、柴田化学社製の「ＳＡ−
１００」が用いられた。In the catalyst of the present invention, the specific surface area of the catalyst and the specific surface area of the carrier metal oxide are substantially the same, and in this specification, the specific surface area of the catalyst and the specific surface area of the carrier metal oxide are used. The term "specific surface area" was used synonymously. In the present specification, the specific surface area of the catalyst or the support metal oxide is a value measured at a temperature of 15 ° C. by a “BET” method. As the measuring device, "SA- made by Shibata Chemical Co., Ltd."
100 "was used.
【００１８】本発明で用いるこのような触媒は、その結
晶化度が高いためにその触媒の比表面積が小さく、かつ
その触媒金属の担持量が非常に少量であるため、炭素析
出活性の著しく抑制されたものであり、且つ、原料低級
炭化水素ガスに対する炭酸ガス及びスチームによる充分
なリフォーミング活性を有するものである。本発明で用
いる触媒は、常法に従って調製することができる。本発
明触媒の１つの好ましい調製法は、含浸法である。この
含浸法により本発明触媒を調製するには、水中に分散さ
せた担体金属酸化物に触媒金属塩又はその水溶液を添
加、混合した後、その担体金属酸化物を水溶液から分離
し、次いで乾燥し、焼成する。また、担体金属酸化物を
排気後、細孔容積分の金属塩溶液を少量ずつ加え、担体
表面を均一に濡れた状態にした後、乾燥、焼成する方法
（ｉｎｃｉｐｉｅｎｔ−ｗｅｔｎｅｓｓ法）も有効であ
る。これらの方法の場合、その触媒金属塩としては、水
溶性塩がもちいられる。このような水溶性塩には、硝酸
塩、塩化物等の無機酸塩や、酢酸塩、シュウ酸塩等の有
機酸塩が包含される。また、金属のアセチルアセトナト
塩等をアセトン等の有機溶媒に溶解し、担体金属酸化物
に含浸させてもよい。触媒金属塩を水溶液として含浸さ
せた金属金属酸化物の乾燥温度は常温〜２００℃、好ま
しくは常温〜１５０℃である。本発明触媒を調製する場
合、その担体である金属酸化物は、市販の金属酸化物
や、市販の金属水酸化物を焼成して得られる金属酸化物
であることができる。この金属酸化物の純度は９７重量
％以上、好ましくは９８重量％以上であるが、炭素折出
活性を高める成分や高温、還元ガス雰囲気下で分解する
成分、例えば鉄、ニッケル等の金属や二酸化ケイ素（Ｓ
ｉＯ2）等の混入は好ましくなく、それらの不純物は、
金属酸化物中、１重量％以下、好ましくは０．１重量％
以下にするのがよい。Such a catalyst used in the present invention has a high specific crystallinity and a small specific surface area of the catalyst, and a very small amount of the catalyst metal carried thereon, so that the carbon deposition activity is significantly suppressed. It has sufficient reforming activity with carbon dioxide gas and steam for the raw material lower hydrocarbon gas. The catalyst used in the present invention can be prepared according to a conventional method. One preferred method of preparing the catalyst of the present invention is an impregnation method. To prepare the catalyst of the present invention by this impregnation method, after adding and mixing a catalyst metal salt or an aqueous solution thereof to a carrier metal oxide dispersed in water, the carrier metal oxide is separated from the aqueous solution, and then dried. And firing. In addition, a method in which a metal salt solution corresponding to the pore volume is added little by little after exhausting the carrier metal oxide to make the surface of the carrier uniformly wet, and then dried and fired (incipient-wetness method) is also effective. . In these methods, a water-soluble salt is used as the catalytic metal salt. Such water-soluble salts include inorganic acid salts such as nitrates and chlorides, and organic acid salts such as acetates and oxalates. Alternatively, a metal acetylacetonate salt or the like may be dissolved in an organic solvent such as acetone and impregnated into the carrier metal oxide. The drying temperature of the metal metal oxide impregnated with the catalyst metal salt as an aqueous solution is from room temperature to 200 ° C, preferably from room temperature to 150 ° C. In the case of preparing the catalyst of the present invention, the metal oxide serving as the carrier can be a commercially available metal oxide or a metal oxide obtained by calcining a commercially available metal hydroxide. The purity of the metal oxide is 97% by weight or more, and preferably 98% by weight or more. However, a component that enhances the activity of carbon separation or a component that decomposes at high temperatures and in a reducing gas atmosphere, such as metals such as iron and nickel, and dioxides Silicon (S
iO 2 ) and the like are not preferable, and their impurities are
1% by weight or less, preferably 0.1% by weight in metal oxide
It is better to:
【００１９】本発明触媒の好ましい調製方法を示すと、
以下の通りである。先ず、第１工程において、比表面積
が５ｍ2／ｇ以下の担体ＭｇＯを得る。工業触媒におい
ては、ペレット状やリング状等の形状に成形した担体が
好ましく用いられるが、このような形状のＭｇＯ成形体
を用いる場合、そのＭｇＯの比表面積が前記範囲より大
きくなり、結晶化度が低くなると、触媒金属の担持に際
してそのＭｇＯ成形体を水溶液中に浸した場合、そのＭ
ｇＯ成形体に割れを生じるという問題がある。また、工
業触媒の場合、通常、３０〜４０ｋｇ／個の半径方向の
圧縮強度を有する必要があるが、比表面積が前記範囲よ
り大きくなり、その結晶化度が低いＭｇＯ成形体ではこ
のような強度を得ることが困難になる。さらに、担体Ｍ
ｇＯの結晶化度が低くなると、触媒金属の担持量が多く
なり、また、触媒の酸強度が強くなりすぎて、触媒表面
の酸的特性が不満足のものとなる。一方、担体ＭｇＯの
結晶化度が大きくなりすぎると、触媒金属の担持量が少
なくなりすぎて、十分な活性を有する触媒が得られなく
なる。この点から、担体ＭｇＯの比表面積は０．０１ｍ
2／ｇ以上にするのが好ましい。A preferred method for preparing the catalyst of the present invention is as follows.
It is as follows. First, in the first step, a support MgO having a specific surface area of 5 m 2 / g or less is obtained. In an industrial catalyst, a support formed into a shape such as a pellet or a ring is preferably used.When an MgO shaped body having such a shape is used, the specific surface area of the MgO becomes larger than the above range, and the crystallinity becomes higher. When the MgO compact is immersed in an aqueous solution when the catalyst metal is supported, the M
There is a problem that cracks occur in the gO molded body. In the case of an industrial catalyst, it is usually necessary to have a compressive strength in the radial direction of 30 to 40 kg / piece. However, such a strength is required for an MgO molded body having a specific surface area larger than the above range and a low crystallinity. Will be difficult to obtain. Further, the carrier M
When the crystallinity of gO decreases, the amount of the supported catalyst metal increases, and the acid strength of the catalyst becomes too strong, resulting in unsatisfactory acid properties of the catalyst surface. On the other hand, if the crystallinity of the support MgO is too large, the amount of the supported catalyst metal is too small, and a catalyst having sufficient activity cannot be obtained. From this point, the specific surface area of the support MgO is 0.01 m
It is preferably at least 2 / g.
【００２０】前記範囲の比表面積を有する担体ＭｇＯを
得る１つの方法としては、水酸化マグネシウムを１００
０〜１５００℃、好ましくは１１００〜１３００℃で焼
成することにより製造することができる他、炭酸マグネ
シウム又は塩基性炭酸マグネシウムを１０００〜１５０
０℃、好ましくは１１００〜１３００℃で焼成すること
により製造することができる。また、１０００℃以下の
低い温度で焼成する場合も、焼成の際に副生する水の分
圧を高くしてＭｇＯの結晶化促進し、ＭｇＯの比表面積
を５ｍ2／ｇ以下の範囲に制御することによって所望の
担体ＭｇＯを得ることができる。さらに、市販のＭｇＯ
等のその比表面積が前記範囲より小さいものは、そのＭ
ｇＯを１０００〜１５００℃、好ましくは１１００〜１
３００℃で焼成することにより、所望の担体ＭｇＯを得
ることができる。さらに、低比表面積の担体ＭｇＯを得
る場合、１０００℃以下の温度でその焼成系に高い水の
分圧を形成することによりそのＭｇＯの結晶化を促進さ
せることができるが、この場合、水の分圧に代えて、Ｃ
Ｏ2のようなガス（気体）の高い分圧を形成することに
よっても、ＭｇＯの結晶化を促進させることができる。
前記焼成に際しての雰囲気としては、通常、空気雰囲気
が使用されるが、他のガス、例えば、窒素ガス等の不活
性ガスであってもよい。焼成時間は１時間以上、好まし
くは３時間以上であり、その上限値は特に制約されない
が、通常、７２時間程度である。また、焼成のみに限ら
ず、このような低比表面積のＭｇＯを得ることができれ
ば、いかなる方法を採用してもよい。One method of obtaining a carrier MgO having a specific surface area in the above range is as follows.
0 to 1500 ° C., preferably 1100 to 1300 ° C., and magnesium carbonate or basic magnesium carbonate of 1000 to 150 ° C.
It can be manufactured by baking at 0 ° C, preferably 1100 to 1300 ° C. Also, when firing at a low temperature of 1000 ° C. or less, the partial pressure of water produced as a by-product during firing is increased to promote crystallization of MgO, and the specific surface area of MgO is controlled to a range of 5 m 2 / g or less. Thus, a desired carrier MgO can be obtained. Furthermore, commercially available MgO
Etc. whose specific surface area is smaller than the above range,
gO is 1000-1500 ° C., preferably 1100-1
By firing at 300 ° C., a desired carrier MgO can be obtained. Further, when obtaining a carrier MgO having a low specific surface area, the crystallization of the MgO can be promoted by forming a high partial pressure of water in the calcination system at a temperature of 1000 ° C. or less. Instead of partial pressure, C
By forming a high partial pressure of a gas (gas) such as O 2 , crystallization of MgO can be promoted.
As the atmosphere for the firing, an air atmosphere is usually used, but another gas, for example, an inert gas such as a nitrogen gas may be used. The firing time is 1 hour or more, preferably 3 hours or more, and the upper limit is not particularly limited, but is usually about 72 hours. The method is not limited to firing, and any method may be employed as long as MgO having such a low specific surface area can be obtained.
【００２１】本発明による担体ＭｇＯは、高い結晶化度
を有し、そのＭｇＯの表面は安定化され、強酸点を極力
抑えたＭｇＯとなる。そして、このような安定化された
ＭｇＯでは、酸強度（Ｈｏ）が２以上の酸点のみを有
し、その量が０．０３ｍｍｏｌ／ｇより少ないＭｇＯが
得られる。従って、１０００℃以上の高温焼成された高
結晶化度のＭｇＯを触媒金属担持用担体として用いるこ
とにより、強酸点の発現を極力抑え、炭素析出反応が抑
制された安定した活性を有する触媒を得ることが可能と
なる。本発明で用いるＭｇＯの比表面積は０．０１〜５
ｍ2／ｇ、好ましくは０．０５〜３ｍ2／ｇである。担体
ＭｇＯの比表面積が前記範囲より高くなると、触媒金属
の担持量が多くなり、また、触媒の酸強度が強くなりす
ぎて、触媒表面の酸的特性が不満足のものとなる。一
方、担体ＭｇＯの比表面積が前記範囲より小さくなる
と、触媒金属の担持量が少なくなりすぎて、十分な活性
を有する触媒が得られなくなる。The carrier MgO according to the present invention has a high degree of crystallinity, the surface of the MgO is stabilized, and the MgO has a strong acid point suppressed as much as possible. And, with such stabilized MgO, MgO having only an acid point having an acid strength (Ho) of 2 or more and an amount of less than 0.03 mmol / g can be obtained. Therefore, by using MgO having a high degree of crystallinity, which has been calcined at a high temperature of 1000 ° C. or more, as a carrier for supporting a catalytic metal, the expression of strong acid sites is suppressed as much as possible, and a catalyst having a stable activity in which a carbon deposition reaction is suppressed is obtained. It becomes possible. The specific surface area of MgO used in the present invention is 0.01-5.
m 2 / g, preferably 0.05 to 3 m 2 / g. When the specific surface area of the support MgO is higher than the above range, the amount of the supported catalyst metal increases, and the acid strength of the catalyst becomes too strong, so that the acid properties of the catalyst surface become unsatisfactory. On the other hand, when the specific surface area of the support MgO is smaller than the above range, the amount of the supported catalyst metal is too small, and a catalyst having sufficient activity cannot be obtained.
【００２２】一般に、金属酸化物の表面積とその結晶子
サイズは、ほぼ反比例の関係にあることが良く知られて
いる。従って、本発明で規定しているＭｇＯの比表面積
は、その粒子サイズにより規定することも可能である。
例えば、比表面積が５ｍ2／ｇ以下のＭｇＯの結晶子サ
イズは、粒子を球形又は立方体の均一粒子と仮定するこ
とにより、ＭｇＯの密度、比表面積から算出することが
できる。この方法は、文献「触媒講座３（固体触媒のキ
ャラクタリゼーション）」（１９８５年出版、講談社サ
イエンティフィク、触媒学会編、Ｐ２０３）に記載され
ている。例えば、１０１０℃で焼成した比表面積５ｍ2
／ｇのＭｇＯの結晶子サイズは、３５００Åとなる。ま
た、ＭｇＯの結晶子サイズは、Ｘ線回折法を用いて測定
することもできる。本明細書中の比表面積が５ｍ2／ｇ
以下のＭｇＯの結晶子サイズを、Ｘ線回折法を用いた
「ラインブロードニング」法により測定すると、その値
は、９００Å以上となった。測定装置としては、島津製
作所のＸ線回折装置「ＸＲＤ−６０００」が用いられ
た。標準物質として、金属Ｓｉを用いて測定を行うと、
ＭｇＯの結晶子サイズは、ＭｇＯの２θ＝４２．７°の
回折ピークとＳｉのＭｇＯの２θ＝２８．４°の回折ピ
ークの半値幅から算出した。Ｘ線回折測定における測定
条件を以下に示す。 Ｘ線管球：Ｃｕ（λ＝１．５４０６Å） 管電圧：４０．０ｋＶ、管電流：３０．０ｍＡ 測定範囲：４０．０〜８０．０° ステップ幅：０．０２° 計数時間：０．６秒 スリット：ＤＳ（発散スリット）＝０．５°、ＳＳ（散
乱防止）＝０．５°、ＲＳ（受光）＝０．１５ｍｍ 標準物質：金属Ｓｉ このラインブロードニング法の詳細は、文献「実験化学
講座４（固体物理化学）」（１９５６年出版、丸善、日
本化学会編、Ｐ２３８〜Ｐ２５０）に記載されている。In general, it is well known that the surface area of a metal oxide and its crystallite size are substantially inversely proportional. Therefore, the specific surface area of MgO specified in the present invention can be specified by its particle size.
For example, the crystallite size of MgO having a specific surface area of 5 m 2 / g or less can be calculated from the density and specific surface area of MgO by assuming that the particles are spherical or cubic uniform particles. This method is described in the document "Catalyst Course 3 (Characterization of Solid Catalysts)" (published in 1985, Kodansha Scientific, edited by the Catalysis Society of Japan, p. 203). For example, a specific surface area of 5 m 2 fired at 1010 ° C.
/ G of MgO has a crystallite size of 3500 °. Further, the crystallite size of MgO can be measured by using an X-ray diffraction method. Specific surface area in this specification is 5 m 2 / g
When the following crystallite size of MgO was measured by the “line broadening” method using the X-ray diffraction method, the value was 900 ° or more. As a measuring device, an X-ray diffractometer “XRD-6000” manufactured by Shimadzu Corporation was used. When measurement is performed using metal Si as a standard substance,
The crystallite size of MgO was calculated from the half width of the diffraction peak of MgO 2θ = 42.7 ° and the diffraction peak of Si MgO 2θ = 28.4 °. The measurement conditions in the X-ray diffraction measurement are shown below. X-ray tube: Cu (λ = 1.5406 °) Tube voltage: 40.0 kV, tube current: 30.0 mA Measurement range: 40.0 to 80.0 ° Step width: 0.02 ° Counting time: 0.6 Second slit: DS (divergence slit) = 0.5 °, SS (anti-scattering) = 0.5 °, RS (light reception) = 0.15 mm Reference material: metal Si For details of this line broadening method, see the literature "Experiment Chemistry Course 4 (Solid State Physical Chemistry) "(published in 1956, Maruzen, edited by The Chemical Society of Japan, pp. 238-250).
【００２３】前記のようにして得た担体酸化マグネシウ
ムに対しては、第２工程（触媒金属担持工程）におい
て、触媒金属を含む水溶液を用い、平衡吸着法にてｐＨ
８以上のアルカリ領域でその触媒水溶液を担持させる。
本発明では、触媒金属としては、ロジウム及び／又はル
テニウムが用いられる。前記担持工程では、触媒金属は
水溶液状で担体酸化マグネシウムに担持されるが、この
場合の触媒金属は水溶性化合物の形態で用いられる。こ
のようなものとしては、ハロゲン化物、硝酸塩、硫酸
塩、有機酸塩（酢酸塩等）、錯塩（キレート）等が挙げ
られる。担体ＭｇＯに対する触媒金属水溶液の担持に
は、平衡吸着法が採用される。この方法は、担体を触媒
水溶液中に浸漬し、平衡条件下で水溶液中の触媒金属を
担体に吸着担持させる方法である。この場合、触媒金属
を担体に担持させる時間（浸漬時間）は１時間以上、好
ましくは３時間以上であり、その上限は、特に制約され
ないが、通常、４８時間程度である。この平衡吸着法の
詳細は、文献「触媒調製化学」（１９８０年出版、講談
社サイエンティフィク、Ｐ４９）に記載されている。In the second step (catalyst metal supporting step), the carrier magnesium oxide obtained as described above is subjected to an equilibrium adsorption method using an aqueous solution containing a catalytic metal.
The catalyst aqueous solution is supported in eight or more alkali regions.
In the present invention, rhodium and / or ruthenium are used as the catalyst metal. In the supporting step, the catalytic metal is supported on the carrier magnesium oxide in the form of an aqueous solution. In this case, the catalytic metal is used in the form of a water-soluble compound. Examples of such compounds include halides, nitrates, sulfates, organic acid salts (such as acetates), and complex salts (chelates). An equilibrium adsorption method is employed for supporting the catalyst metal aqueous solution on the carrier MgO. In this method, a carrier is immersed in a catalyst aqueous solution, and the catalyst metal in the aqueous solution is adsorbed and supported on the carrier under equilibrium conditions. In this case, the time for supporting the catalyst metal on the carrier (immersion time) is 1 hour or more, preferably 3 hours or more, and the upper limit is not particularly limited, but is usually about 48 hours. The details of this equilibrium adsorption method are described in the document "Catalyst Preparation Chemistry" (published in 1980, Kodansha Scientific, P49).
【００２４】前記のようにして触媒金属を担体ＭｇＯに
担持させる場合、その触媒水溶液のｐＨは８以上、好ま
しくは８．５以上のアルカリ領域とする。その上限値
は、特に制約されないが、通常、ｐＨ１３程度である。
その水溶液のｐＨ調節には、水酸化ナトリウムや水酸化
カリウム、水酸化カルシウム、水酸化マグネシウム等の
アルカリ性物質が用いられる。本発明においては、担体
ＭｇＯに対する触媒金属の担持量は、触媒金属換算量
で、担体ＭｇＯに対して１０〜５０００ｗｔｐｐｍ、好
ましくは１００〜２０００ｗｔｐｐｍの割合に規定す
る。触媒金属担持量が前記範囲より多くなると、触媒コ
ストが高くなるとともに、触媒の炭素析出活性が高くな
り、触媒の使用に際し、炭素析出量が多くなる。一方、
前記範囲より少ないと、十分な触媒活性が得られなくな
る。触媒金属担持量の調節は、担体ＭｇＯに対して触媒
金属水溶液を担持する際の条件、例えば、水溶液中の触
媒金属濃度や、担体ＭｇＯの表面積等によって行うこと
ができる。When the catalyst metal is carried on the carrier MgO as described above, the pH of the catalyst aqueous solution is set to an alkaline region of 8 or more, preferably 8.5 or more. The upper limit is not particularly limited, but is usually about pH 13.
To adjust the pH of the aqueous solution, an alkaline substance such as sodium hydroxide, potassium hydroxide, calcium hydroxide, or magnesium hydroxide is used. In the present invention, the supported amount of the catalyst metal on the carrier MgO is defined as a ratio of 10 to 5,000 wtppm, preferably 100 to 2,000 wtppm, based on the catalyst metal in terms of the catalyst metal. When the amount of the supported catalyst metal is larger than the above range, the cost of the catalyst is increased, and the carbon deposition activity of the catalyst is increased, and the amount of deposited carbon is increased when the catalyst is used. on the other hand,
If it is less than the above range, sufficient catalytic activity cannot be obtained. The adjustment of the amount of the supported catalyst metal can be performed by adjusting the conditions for supporting the aqueous solution of the catalyst metal on the carrier MgO, for example, the concentration of the catalyst metal in the aqueous solution, the surface area of the carrier MgO, and the like.
【００２５】前記のようにして、担体ＭｇＯに触媒金属
を水溶液状で担持させることによって得られた触媒金属
担持ＭｇＯは、第３工程（乾燥工程）において、３５℃
以下の温度で６時間以上保持して乾燥させる。好ましい
乾燥温度は１０〜２５℃である。乾燥時間は６時間以上
であればよく、好ましくは１２時間以上であり、その上
限値は、特に制約されないが、通常、約７２時間程度で
ある。このような乾燥処理により、ＭｇＯからの急激な
水分の蒸発が回避され、その結果、触媒金属は凝集する
ことなく担体ＭｇＯに高分散状態で担持される。乾燥温
度や乾燥時間が前記範囲を逸脱すると、高分散性の触媒
金属を含む触媒を得ることができなくなる。In the third step (drying step), the catalyst metal-supported MgO obtained by supporting the catalyst metal in the form of an aqueous solution on the carrier MgO as described above is subjected to 35 ° C.
Hold at the following temperature for 6 hours or more and dry. The preferred drying temperature is from 10 to 25C. The drying time may be at least 6 hours, preferably at least 12 hours, and the upper limit is not particularly limited, but is usually about 72 hours. By such a drying treatment, rapid evaporation of water from MgO is avoided, and as a result, the catalyst metal is supported on the carrier MgO in a highly dispersed state without agglomeration. If the drying temperature and the drying time deviate from the above ranges, a catalyst containing a highly dispersible catalytic metal cannot be obtained.
【００２６】前記のようにして得られた乾燥物は、これ
を第４工程において、２００℃以上の高温で焼成する。
この場合、焼成雰囲気としては、通常、空気が用いられ
るが、他のガス（不活性ガス等）であってもよい。焼成
温度は２００℃以上であり、好ましくは５００℃以上で
あり、その上限値は、特に制約されないが、通常、１１
００℃程度である。好ましい焼成時間は２時間以上であ
り、より好ましくは３時間以上であり、その上限値は、
特に制約されないが、通常２４時間程度である。この２
次焼成により、触媒金属の熱安定性が高められ、熱安定
性の良い触媒を得ることができる。The dried product obtained as described above is fired at a high temperature of 200 ° C. or more in the fourth step.
In this case, air is usually used as the firing atmosphere, but another gas (such as an inert gas) may be used. The sintering temperature is 200 ° C. or higher, preferably 500 ° C. or higher, and the upper limit is not particularly limited.
It is about 00 ° C. A preferred firing time is 2 hours or more, more preferably 3 hours or more, and the upper limit is
Although not particularly limited, it is usually about 24 hours. This 2
By the subsequent calcination, the thermal stability of the catalyst metal is enhanced, and a catalyst with good thermal stability can be obtained.
【００２７】触媒コストの低減化を図るには、担体に担
持させる触媒金属の担持量をできるだけ低減化させると
同時に、十分な反応活性を発現するように、担体に担持
された触媒金属粒子の凝集化をできるだけ抑制して微粒
子化することが必要となる。本発明者らの研究によれ
ば、担体ＭｇＯの結晶化を高めてその比表面積を５ｍ2
／ｇ以下に保持するとともに、その担体ＭｇＯに対する
触媒金属の担持量を１０〜５０００ｗｔｐｐｍと極く少
量に保持し、かつその触媒金属を担体ＭｇＯに担持させ
るに際し、平衡吸着法により触媒金属を平衡条件下で長
時間をかけてゆっくりと水溶液状で担持させ、その担持
後においては、３５℃以下の温度でゆっくりと乾燥する
ときには、触媒金属は均一に担持され、炭化水素改質用
触媒として十分な活性を有する安価な触媒が得られるこ
とが見出された。In order to reduce the catalyst cost, the amount of the catalyst metal supported on the carrier is reduced as much as possible, and at the same time, the catalyst metal particles supported on the carrier are aggregated so as to exhibit a sufficient reaction activity. It is necessary to reduce the particle size as much as possible and to make the particles fine. According to the study of the present inventors, the crystallization of the carrier MgO was enhanced to increase its specific surface area to 5 m 2.
/ G or less, the supported amount of the catalyst metal on the carrier MgO is kept to a very small amount of 10 to 5000 wtppm, and when the catalyst metal is supported on the carrier MgO, the catalyst metal is equilibrated by the equilibrium adsorption method. Under a long period of time, the catalyst metal is supported slowly in an aqueous solution state, and after the support, when slowly dried at a temperature of 35 ° C. or less, the catalyst metal is uniformly supported and sufficient as a catalyst for hydrocarbon reforming. It has been found that an inexpensive catalyst having activity can be obtained.
【００２８】前記した触媒の調製方法においては、種々
の変更が可能である。例えば、担体酸化マグネシウムに
触媒金属を担持させる方法としては、平衡吸着法に限ら
ず、他の方法、例えば、慣用の含浸法や、浸漬法、イオ
ン交換法等を用いることができる。また、触媒金属を含
む水溶液を担体酸化マグネシウムに担持させた後、乾燥
する場合には、場合によっては３５〜２００℃程度の加
温条件を採用するし、また、その乾燥物の焼成は、場合
によっては、２００〜８００℃程度の温度で行うことも
可能である。Various changes can be made in the above-described method for preparing the catalyst. For example, the method for supporting the catalyst metal on the carrier magnesium oxide is not limited to the equilibrium adsorption method, and other methods such as a conventional impregnation method, an immersion method, and an ion exchange method can be used. In addition, in the case of drying after supporting the aqueous solution containing the catalyst metal on the carrier magnesium oxide, a heating condition of about 35 to 200 ° C. may be employed in some cases. Depending on the case, it may be performed at a temperature of about 200 to 800 ° C.
【００２９】本発明により触媒を調整する場合、その触
媒担体形成用酸化マグネシウムは、酸化マグネシウムに
成形助剤を配合して形成した酸化マグネシウム成形体と
して用いるのが好ましい。この成型助剤を用いることに
よって、成形時の作業性が向上すると共に得られた成形
体の強度は向上する。この場合の成形助剤としては、
（ｉ）炭素（カーボン）、（ii）炭素１２〜２２の脂肪
酸又はそのマグネシウム塩、（iii）カルボキシルメチ
ルセルロース（ＣＭＣ）又はそのマグネシウム塩及び
（iV）ポリビニルアルコールの中から選ばれる少なくと
も１種の化合物を用いるのが好ましい。これらの成形助
剤は、通常、粉末状で用いられる。前記カーボンとして
は、グラファイト、カーボンブラック、活性炭などが用
いられる。前記脂肪酸としては、ラウリン酸、ミリスチ
ン酸、パルミチン酸、ステアリン酸、ベヘン酸等が挙げ
られる。When the catalyst is prepared according to the present invention, the magnesium oxide for forming the catalyst carrier is preferably used as a magnesium oxide compact formed by mixing a molding aid with magnesium oxide. By using this molding aid, the workability during molding is improved and the strength of the obtained molded body is improved. As a molding aid in this case,
(I) at least one compound selected from the group consisting of (i) carbon (carbon), (ii) a fatty acid having 12 to 22 carbon atoms or a magnesium salt thereof, (iii) carboxymethyl cellulose (CMC) or a magnesium salt thereof, and (iV) polyvinyl alcohol. It is preferable to use These molding aids are usually used in powder form. As the carbon, graphite, carbon black, activated carbon and the like are used. Examples of the fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and the like.
【００３０】前記触媒担体用酸化マグネシウム成形体を
製造するには、粉末状の酸化マグネシウムに成形助剤を
添加し、均一に混合した後、この混合物を所要形状に成
形する。粉末状酸化マグネシウムの平均粒径は１〜１０
００μｍ、好ましくは１０〜１００μｍである。一方、
成形助剤の平均粒径は１〜１０００μｍ、好ましくは１
０〜１００μｍである。酸化マグネシウムに添加する成
形助剤の量は、酸化マグネシウムと成形助剤の合計量に
対し、０．１〜５重量％、好ましくは０．５〜３．０重
量％である。前記酸化マグネシウムと成形助剤との混合
物を形成する場合、その成形条件としては、通常、常温
で３０００〜１００ｋｇ／ｃｍ2Ｇ、好ましくは２００
０〜２００ｋｇ／ｃｍ2の圧力が採用される。成形方法
としては、プレス成形法が採用されるが、その他、打錠
成形法等も採用することができる。成形体の形状は、特
に制約されず、通常の触媒に採用されている形状であれ
ばよい。このような形状には、タブレット状、円柱状、
リング状、中空円筒状等が包含される。その成形体の寸
法は、通常、その長軸長さで、３〜３０ｍｍ、好ましく
は５〜２５ｍｍであるが、触媒床に応じて適宜の寸法を
採用すればよい。In order to manufacture the magnesium oxide compact for a catalyst carrier, a molding aid is added to powdered magnesium oxide, and the mixture is uniformly mixed, and then the mixture is formed into a required shape. The average particle size of the powdered magnesium oxide is 1 to 10
It is 00 μm, preferably 10 to 100 μm. on the other hand,
The molding aid has an average particle size of 1 to 1000 μm, preferably 1 to 1000 μm.
0 to 100 μm. The amount of the molding aid added to the magnesium oxide is 0.1 to 5% by weight, preferably 0.5 to 3.0% by weight, based on the total amount of the magnesium oxide and the molding aid. When forming a mixture of the magnesium oxide and the molding aid, the molding conditions are usually 3000 to 100 kg / cm 2 G at room temperature, preferably 200 to 200 kg / cm 2 G.
A pressure of 0-200 kg / cm 2 is employed. As a molding method, a press molding method is adopted, but a tableting method or the like can also be adopted. The shape of the molded body is not particularly limited, and may be any shape as long as it is used for a normal catalyst. Such shapes include tablets, cylinders,
A ring shape, a hollow cylindrical shape and the like are included. The size of the formed body is usually 3 to 30 mm, preferably 5 to 25 mm in terms of its major axis, but an appropriate size may be adopted according to the catalyst bed.
【００３１】本発明による前記酸化マグネシウム成形体
は、焼成後の機械的強度にすぐれ、通常、３０〜７０ｋ
ｇ／個の半径方向の圧縮強度を有する。従って、このよ
うな成形体は、取扱い性の良好なもので、その焼成に際
して、容易に破壊されるようなことはない。また、この
酸化マグネシウム成形体は、そのＭｇＯの結晶化度が低
いときには、所望する担体酸化マグネシウムを得るため
に、通常、１０００℃以上の高温で一次焼成されるが、
この一次焼成により、成形体中の成形助剤は酸化除去さ
れる。このようにして得られる酸化マグネシウムは、本
発明触媒の調製に用いる担体酸化マグネシウムとして好
適のものである。The magnesium oxide molded article according to the present invention has excellent mechanical strength after firing, and is usually 30 to 70 k.
g / piece radial compressive strength. Therefore, such a molded body has good handleability and is not easily broken during firing. In addition, when the crystallinity of MgO is low, the magnesium oxide compact is usually first fired at a high temperature of 1000 ° C. or higher to obtain a desired carrier magnesium oxide.
By this primary firing, the molding aid in the molded body is oxidized and removed. The magnesium oxide thus obtained is suitable as a carrier magnesium oxide used for preparing the catalyst of the present invention.
【００３２】前記のようにして得られる本発明触媒にお
いて、その触媒金属担持量は、担体ＭｇＯに対して、１
０〜５０００ｗｔｐｐｍ、好ましくは１００〜２０００
ｗｔｐｐｍであり、その比表面積は０．０１〜５ｍ2／
ｇ、好ましくは０．０５〜３ｍ2／ｇである。In the catalyst of the present invention obtained as described above, the amount of the supported catalyst metal is 1 to the support MgO.
0 to 5000 wtppm, preferably 100 to 2000
wt ppm, and its specific surface area is 0.01 to 5 m 2 /
g, preferably 0.05 to 3 m 2 / g.
【００３３】前記のようにして得られる本発明の触媒
は、炭化水素改質用触媒として好ましい酸的性質を有す
る。触媒表面に強い酸点が多量に存在すると、その酸点
上で副反応である炭素析出反応が促進され、炭素が析出
し、この析出炭素によって触媒被毒が生じるようにな
る。The catalyst of the present invention obtained as described above has preferable acidic properties as a catalyst for hydrocarbon reforming. When a large number of strong acid sites are present on the catalyst surface, a carbon deposition reaction, which is a side reaction, is promoted on the acid sites, carbon is deposited, and the deposited carbon causes catalyst poisoning.
【００３４】本発明の触媒は、一般的には、その酸強度
（Ｈｏ）は２より大きい、好ましくは３．３以上の酸点
のみからなり、その含量は０．０３ｍｍｏｌ／ｇより少
なく、好ましくは０．０２ｍｍｏｌ／ｇ以下である。酸
強度（Ｈｏ）の調節は、担体ＭｇＯを１次焼成する際の
温度及び時間により行うことができる。本発明の触媒
は、強酸点の発現が抑制され、炭素析出活性が大きく抑
制されたものである。The catalyst of the present invention generally has only an acid strength (Ho) of more than 2, preferably at least 3.3 or more, and has a content of less than 0.03 mmol / g, preferably less than 0.03 mmol / g. Is 0.02 mmol / g or less. The adjustment of the acid strength (Ho) can be performed by adjusting the temperature and the time when the support MgO is subjected to the first firing. In the catalyst of the present invention, the expression of strong acid sites is suppressed, and the carbon deposition activity is greatly suppressed.
【００３５】なお、本明細書で言う酸強度（Ｈｏ）は、
触媒が塩基性指示薬（Ｂ-）にプロトンを与える能力と
して表示され、次式で表される。 Ｈｏ＝ｐＫａ（＝ｐＫB - H +）＋ｌｏｇ［Ｂ］／［Ｂ-Ｈ+］ （１） 前記式中、ＫB - H +は、塩基性指示薬Ｂ-と酸性点Ｈ+Ｂと
を反応させて、塩基性指示薬の酸性体（Ｂ-Ｈ+）を生成
させる反応におけるその酸性体Ｂ-Ｈ+の解離定数を示
す。［Ｂ］／［Ｂ-Ｈ+］は、Ｂ-とＢ-Ｈ+の濃度比を示
す。強酸点ほど、ｐＫB - H +の小さな指示薬をより多くプ
ロトン化するのでそのＨｏ値は小さくなる。The acid strength (Ho) referred to in this specification is:
It is expressed as the ability of the catalyst to give a proton to the basic indicator (B − ) and is expressed by the following formula. Ho = pKa (= pK B - H +) + log [B] / [B - H +] (1) In the formula, K B - H + is a basic indicator B - the reaction of the acid point H + B Thus, the dissociation constant of the acidic form B - H + in the reaction for producing the acidic form (B - H + ) of the basic indicator is shown. [B] / [B - H +] is, B - and B - shows the H + concentration ratio of. As strong acid sites, pK B - the Ho value because more protonate a small indicator H + decreases.
【００３６】本明細書における酸強度は以下のようにし
て測定されたものである。 （酸強度の測定方法）本明細書における酸強度Ｈｏ（ハ
メット指数）関数は、酸強度関数で、触媒学会編「触媒
実験ハンドブック」（１９８６年出版、講談社サイエン
ティフィク）、ｐ．１７２に記載の「Ｂｅｎｅｓｉ法」
により測定されたものである。触媒にｐＫａが分かって
いる指示薬を添加し、変色すると、ＨｏがそのｐＫａよ
り小さい酸点があることを示す。塩基性分子であるブチ
ルアミンを酸点に所定量吸着させ、ｐＫａの異なる指示
薬で滴定すると、ブチルアミンの量から酸点の数が、ｐ
Ｋａの値から酸強度が測定できる。測定温度は室温であ
る。The acid strength in the present specification is measured as follows. (Method of Measuring Acid Strength) The acid strength Ho (Hammett index) function in this specification is an acid strength function, which is described in “Catalyst Experiment Handbook” edited by the Catalysis Society of Japan (published in 1986, Kodansha Scientific), p. 172 “Benesi method”
Is measured by Addition of an indicator whose pKa is known to the catalyst and discoloration indicate that Ho has an acid point less than its pKa. When a predetermined amount of butylamine, which is a basic molecule, is adsorbed to acid sites and titrated with an indicator having a different pKa, the number of acid sites is determined from the amount of butylamine as p
The acid strength can be measured from the value of Ka. The measurement temperature is room temperature.
【００３７】本発明触媒は、粉末状、顆粒状、球形状、
円柱状、円筒状等の各種の形状で用いられ、その形状は
使用される触媒床の方式に応じて適宜選定される。The catalyst of the present invention may be in the form of powder, granule, sphere,
It is used in various shapes such as a columnar shape and a cylindrical shape, and the shape is appropriately selected according to the type of the catalyst bed used.
【００３８】本発明により合成ガスを製造するには、前
記触媒の存在下において、低級炭化水素ガスと炭酸ガス
及びスチームとリフォーミング反応させればよい。その
反応温度は６００〜１０００℃、好ましくは６５０〜９
５０℃である。その反応圧力は加圧であり、１０〜７０
気圧、好ましくは１５〜４０気圧である。また、この反
応を固定床方式で行う場合、そのガス空間速度（ＧＨＳ
Ｖ）は１，０００〜１０，０００ｈｒ-1、好ましくは
２，０００〜８，０００ｈｒ-1である。本発明の合成ガ
ス生成工程は、固定床方式、流動床方式、懸濁床方式、
移動床方式等の各種の触媒方式で実施されるが、好まし
くは固定床方式で実施される。また、反応は１段階に限
らず複数段で行うこともできる。In order to produce a synthesis gas according to the present invention, a reforming reaction between a lower hydrocarbon gas, a carbon dioxide gas, and steam may be performed in the presence of the catalyst. The reaction temperature is 600-1000 ° C, preferably 650-9.
50 ° C. The reaction pressure is pressurized,
Atmospheric pressure, preferably 15 to 40 atm. When this reaction is carried out in a fixed bed system, the gas space velocity (GHS
V) is 1,000~10,000hr -1, preferably 2,000~8,000hr -1. The synthesis gas generation step of the present invention includes a fixed bed system, a fluidized bed system, a suspension bed system,
Although it is carried out by various catalyst systems such as a moving bed system, it is preferably carried out by a fixed bed system. Further, the reaction is not limited to one stage, but can be performed in a plurality of stages.
【００３９】本発明においては、前記合成ガス生成工程
で得られた合成ガスは、水素／一酸化炭素のモル比が
１．５〜２．５の組成のＦＴ合成用原料ガスとして用い
られる。本発明では、合成ガスは、これを水素及び／又
は炭酸ガスを分離して合成ガスの組成を調整する工程を
経ずに、直接ＦＴ反応工程に導入し得るが、このことも
本発明の優位となる点である。本発明では、前記合成ガ
スを、ＦＴ触媒の存在下で反応させて液状炭化水素油を
含む反応生成物を生成させる。ＦＴ反応に対する触媒系
は、ＣＯシフト活性が低い触媒系とシフト活性が高い触
媒系の２つに大別される。前者の代表は、触媒金属がコ
バルト又は／及びルテニウムからなる触媒で、後者は鉄
系の触媒である。本発明では以下の理由により、ＣＯシ
フト活性が低い触媒、代表的には主触媒金属がコバルト
又は／及びルテニウムからなる触媒の使用が好ましい。
ＣＯシフト活性が低いＦＴ触媒では、下記反応式（６）
のＦＴ合成反応により炭化水素油（−ＣＨ2で示す）が
選択的に生成される。 ＣＯ ＋ ２Ｈ2Ｏ → （−ＣＨ2） ＋ Ｈ2Ｏ （６）In the present invention, the synthesis gas obtained in the synthesis gas generation step is used as a raw material gas for FT synthesis having a composition in which the molar ratio of hydrogen / carbon monoxide is 1.5 to 2.5. In the present invention, the synthesis gas can be directly introduced into the FT reaction step without going through the step of adjusting the composition of the synthesis gas by separating hydrogen and / or carbon dioxide gas, which is also an advantage of the present invention. This is the point. In the present invention, the synthesis gas is reacted in the presence of an FT catalyst to generate a reaction product containing a liquid hydrocarbon oil. The catalyst system for the FT reaction is roughly classified into a catalyst system having a low CO shift activity and a catalyst system having a high shift activity. A representative of the former is a catalyst in which the catalyst metal comprises cobalt and / or ruthenium, and a latter is an iron-based catalyst. In the present invention, it is preferable to use a catalyst having a low CO shift activity, typically a catalyst whose main catalyst metal is cobalt and / or ruthenium for the following reasons.
In an FT catalyst having a low CO shift activity, the following reaction formula (6)
FT synthesis reaction by a hydrocarbon oil (indicated by -CH 2) is selectively produced. CO + 2H 2 O → (-CH 2 ) + H 2 O (6)
【００４０】一方、高い水性ガスシフト活性を持つ鉄系
ＦＴ触媒を用いると、前記（６）のＦＴ反応と同時に下
記（７）式のＣＯシフト反応が起き、総括反応は（８）
の反応となる。 ＣＯ ＋ Ｈ2Ｏ → Ｈ2 ＋ ＣＯ2 （７） ２ＣＯ ＋ Ｈ2Ｏ → （−ＣＨ2） ＋ ＣＯ2 （８） 鉄系触媒はＦＴ合成反応と同時に、反応（７）でＣＯ2
の形で炭素を失うので、ＦＴ合成工程での炭素変換効率
は最大でも５０％となり、プロセスの全炭素変換効率が
著しく低下される。そして、ＦＴリアクターへ導入され
るガス流れから水素を除かないと、未反応水素が過剰に
蓄積され、反応器内の滞留時間を十分に長く保持する必
要から大きい反応器が必要となる。On the other hand, when an iron-based FT catalyst having high water gas shift activity is used, a CO shift reaction of the following formula (7) occurs simultaneously with the FT reaction of the above (6), and the overall reaction is represented by the following (8)
Reaction. CO + H 2 O → H 2 + CO 2 (7) 2CO + H 2 O → (-CH 2) + CO 2 (8) an iron-based catalyst at the same time as the FT synthesis reaction, CO in the reaction (7) 2
, Carbon conversion efficiency in the FT synthesis step is at most 50%, and the total carbon conversion efficiency of the process is significantly reduced. If hydrogen is not removed from the gas stream introduced into the FT reactor, unreacted hydrogen is excessively accumulated, and a large reactor is required because the residence time in the reactor needs to be maintained sufficiently long.
【００４１】一方、コバルトもしくはルテニウム系の触
媒は、鉄系の触媒より高い転換収率が達成でき、理論的
には、１００％の炭素変換効率に近づけることができ
る。したがって、コバルト、ルテニウム系の触媒を使用
するプロセスは、炭化水素油への全炭素変換効率が高い
プロセスとなる。これが、本発明でＦＴ触媒として、コ
バルト、ルテニウム系の触媒を用いる理由である。この
ＦＴ工程で用いられる低シフト活性のＦＴ触媒は、主金
属成分としては、Ｃｏ、Ｒｕのいずれか、もしくは両成
分を含み、さらに、１種もしくはそれ以上の助触媒もし
くは促進剤が含まれる。助触媒としては、少量の貴金
属、特にレニウム、白金又はパラジウムを添加した触媒
が本発明に有効である。また、上記成分に、さらに促進
剤（プロモーター）としてＩＡ，ＩＩＡ，ＩＩＩＡ，Ｉ
ＩＩＢ，ＩＶＡ，ＩＶＢ，ＶＡ族，ＶＢ及びＶＩＢ族か
ら選択される金属の酸化物やアクチニドもしくはランタ
ニドを加えたＦＴ触媒も本発明に使用される。好ましい
促進剤としては、元素周期律表第ＩＩＡ，周期律表第Ｉ
ＶＢ族からの金属、特にチタンおよびジルコニウムの酸
化物が最適である。促進剤の添加は、選択性を高分子量
炭化水素側にシフトさせるのに必須である。担体として
は、当業界で知られた多孔質の耐火性金属酸化物もしく
は珪酸塩又はその組合せから選択することができる。好
適な多孔質担体としては、シリカ、シリカアルミナ、ア
ルミナ、各種合成ゼオライト及びその混合物などが好適
な材料である。担体に対する触媒活性金属の量は、好ま
しくは担体１００重量部当り５〜４０重量部の範囲であ
る。ＦＴ触媒の調整法としては、公知の沈降法、溶融
法、及び含浸法のいずれかにの方法によってもよい。On the other hand, a cobalt or ruthenium-based catalyst can achieve a higher conversion yield than an iron-based catalyst, and can theoretically approach a carbon conversion efficiency of 100%. Therefore, a process using a cobalt- or ruthenium-based catalyst is a process in which the total carbon conversion efficiency into hydrocarbon oil is high. This is the reason why a cobalt or ruthenium-based catalyst is used as the FT catalyst in the present invention. The low shift activity FT catalyst used in this FT step contains, as a main metal component, either Co or Ru, or both components, and further contains one or more cocatalysts or promoters. As a cocatalyst, a catalyst to which a small amount of a noble metal, particularly rhenium, platinum or palladium is added is effective in the present invention. In addition, IA, IIA, IIIA, I
An FT catalyst to which an oxide of a metal selected from IIB, IVA, IVB, Group VA, Group VB and Group VIB or an actinide or lanthanide is added is also used in the present invention. Preferred accelerators include Periodic Table IIA and Periodic Table I
Metals from the group VB, especially oxides of titanium and zirconium, are optimal. The addition of an accelerator is essential to shift the selectivity towards higher molecular weight hydrocarbons. The support can be selected from porous refractory metal oxides or silicates known in the art or combinations thereof. Suitable porous carriers include silica, silica alumina, alumina, various synthetic zeolites, and mixtures thereof. The amount of catalytically active metal per support is preferably in the range of 5 to 40 parts by weight per 100 parts by weight of support. The method for preparing the FT catalyst may be any of the known sedimentation, melting, and impregnation methods.
【００４２】本発明に使用するに適するＦＴ触媒の製造
方法は当業界で周知されている以下の方法で製造でき
る。例えば、ヨーロッパ特許出願ＥＰ０１０４６７２
号、ＥＰ０１１０４４９号、ＥＰ０１２７２２０号、Ｅ
Ｐ０１６７２１５号、ＥＰ０１８０２６９号、ＥＰ０２
２１５９８号及びＥＰ０４２８２２３号、日本特許 特
公平５−３４０５６号、特開平５−１４６６７９号、特
開平４−２２８４２８号などの各公報記載された方法に
よれば良い。また、ＦＴ触媒の特性に関しては以下の文
献に詳細に記載されている。 （「Ｆｉｓｃｈｅｒ−Ｔｒｏｐｓｈ ａｎｄ Ｍｅｔｈ
ａｎｏｌ Ｓｙｎｔｈｅｓｉｓ」ｅｄｉｔｏｒｓ：Ｒ．
Ａ．Ｆｉａｔｏ，Ｅ．Ｉｇｌｅｓｉａ ａｎdＧ．Ａ．
Ｓｏｍｏｒｊａｉ，Ｔｏｐｉｃｓ ｉｎ Ｃａｔａｌｙ
ｓｉｓ，ｖｏｌｕｍｅ ２，Ｎｏ．１−４，１９９５，
Ｂａｌｔｚｅｒ Ｓｃｉｅｎｃｅ Ｐｕｂｌｉｓｈｅｒ
ｓ） （「Ｔｈｅ Ｆｉｓｃｈｅｒ−Ｔｒｏｐｓｃｈ Ｓｙｎ
ｔｈｅｓｉｓ」ｅｄｉｔｏｒｓ：Ｒ．Ｂ．Ａｎｄｅｒｓ
ｏｎ，１９８４，Ａｃａｄｅｍｉｃ Ｐｒｅｓｓ，ｉｎ
ｃ．）A method for producing an FT catalyst suitable for use in the present invention can be produced by the following method known in the art. For example, European Patent Application EP 0 104 672
No., EP0110449, EP0127220, E
P0167215, EP0180269, EP02
The methods described in JP-A Nos. 21598 and EP 0428223, Japanese Patent Publication No. 5-34056, JP-A-5-146679, and JP-A-4-228428 may be used. Further, the characteristics of the FT catalyst are described in detail in the following documents. ("Fischer-Tropsh and Meth
anol Synthesis "editors: R.
A. Fiato, E .; Iglesia and G .; A.
Somorjay, Topics in Catalyst
sis, volume 2, No. 1-4, 1995,
Baltzer Science Publisher
s) ("The Fischer-Tropsch Syn
thesis "editors: R. B. Anders
on, 1984, Academic Press, in
c. )
【００４３】ＦＴ合成反応は、一酸化炭素と水素との混
合物を高められた温度及び圧力にてＦＴ合成触媒と接触
させることにより行われる。合成のための典型的な反応
条件としては、１２５〜３５０℃、好ましくは１７５〜
３００℃の範囲の温度及び５〜１００気圧、好ましくは
１０〜３０気圧の反応圧が示される。このＦＴ反応は、
固定床や流動床及びスラリー方式の反応器により実施す
ることができる。ＦＴ合成反応器については、例えば、
「触媒講座９巻、工業触媒反応II」、Ｐ８４〜１２９触
媒学会編、講談社サイエンティフィク（１９８９）及び
“Ｆｉｓｃｈｅｒ−Ｔｒｏｐｓｃｈ Ｓｙｎｔｈｅｓｉ
ｓ ｉｎ Ｓｌｕｒｒｙ Ｐｈａｓｅ ｂｙ Ｍ．Ｄ．
Ｓｃｈｌｅｓｉｎｇｅｒ，Ｊ．Ｈ．Ｃｒｏｗｅｌｌ，Ｍ
ａｘ Ｌｅｖａ ａｎｄ Ｈ．Ｈ．Ｓｔｏｒｃｈ，ＥＮ
ＧＩＮＥＥＲＩＮＧ ＡＮＤ ＰＲＯＣＥＳＳ ＤＥＶ
ＥＬＯＰＭＥＮＴ，Ｖｏｌ．４３，Ｎｏ．６（Ｊｕｎ
ｅ，１９５１）ｐｐ．１４７４−１４７９などに詳しく
記載されている。The FT synthesis reaction is carried out by bringing a mixture of carbon monoxide and hydrogen into contact with an FT synthesis catalyst at an elevated temperature and pressure. Typical reaction conditions for the synthesis are 125-350 ° C., preferably 175-350 ° C.
Temperatures in the range of 300 ° C. and reaction pressures of 5 to 100 atm, preferably 10 to 30 atm, are indicated. This FT reaction is
It can be carried out by a fixed bed, a fluidized bed and a slurry type reactor. For the FT synthesis reactor, for example,
"Catalyst Course 9 Volume, Industrial Catalysis II", pp. 84-129, edited by The Catalysis Society of Japan, Kodansha Scientific (1989) and "Fischer-Tropsch Synthesis"
s in Slurry Phase by M.S. D.
Schlesinger, J. et al. H. Crowell, M
ax Leva and H.A. H. Storch, EN
GINEERING AND PROCESS DEV
ELOPMENT, Vol. 43, no. 6 (Jun
e, 1951) pp. 1474-1479.
【００４４】ＦＴ工程で得られた反応生成物は、その反
応により生成した炭化水素油の他、未反応の水素、一酸
化炭素、水、その他のガス（例えば、ＣＯ2、Ｎ2等）等
が含まれる。The reaction product obtained in the FT step is not limited to hydrocarbon oil produced by the reaction, but also unreacted hydrogen, carbon monoxide, water, other gases (eg, CO 2 , N 2, etc.), etc. Is included.
【００４５】この反応生成物は、それに含まれる炭化水
素油を分離回収するために、分離工程において分離処理
される。この場合の分離方法としては、高温（温度：１
２５〜３５０℃）のガス状の反応生成物からそれに含ま
れる炭化水素油を分離し得る方法であればどのようなも
のでもよい。例えば、はじめに高温高圧の気液分離槽で
反応性生物中のＨ2、ＣＯ、ＣＯ2等のガスと、軽質炭化
水素油成分及び水などからなるガス状生成物と重質炭化
水素留分（ワックス）とを分離し、ついで該ガス状生成
物を低温高圧分離槽に導きＨ2、ＣＯ、ＣＯ2等のガス
と、軽質炭化水素油成分及び水を分離する方法が良く採
用される。このようにして、ＦＴ工程で得られた反応生
成物から分離回収される炭化水素油は、広範囲の分子量
を有する炭化水素成分からなっている。通常、ＦＴ合成
で生成する炭化水素の分子量分布は、連鎖成長確率αで
決まるシュルツ・フローリー分布に従うことが知られて
いる。（「Ｃ1ケミストリー」、Ｐ３７〜Ｐ７５、触媒
学会編、講談社サイエンティフィク（１９８４））。こ
の確率αは、使用触媒と反応条件で０から１の間で変わ
るが、αが決まれば転化率によらず炭素分布はほぼ一義
的に決められる。αが大きくなるほど、生成物分布がよ
り長鎖状分子に移行する。したがって、炭素数の低い軽
質ガスの副生を少なくするには、できるだけαが大きい
方が望ましく、具体的にはα値は０．９以上になるよう
に設定される。いずれにせよ、ＦＴ合成では幅広い炭素
分布の生成物が得られる。ＦＴ合成で得られた生成物か
ら分離された炭化水素の一部はそのまま製品として生産
されるが、大半は炭化水素留分中のオレフィン、含酸素
化合物を水添し安定化させたり、水素化異性化し、イソ
パラフィンリッチにさせたり、重質留分を水素化分解し
て高品質の中間留分を製造する目的で接触水素化処理さ
れる。本発明では、該ＦＴ反応生成物から炭化水素油を
分離し、さらにそれを高圧高温で接触水素化処理し、高
品質のガソリン、灯油、軽油を製造することをその実施
態様の一つとしている。The reaction product is separated in a separation step in order to separate and recover the hydrocarbon oil contained therein. In this case, the separation method may be a high temperature (temperature: 1).
Any method can be used as long as it can separate the hydrocarbon oil contained therein from the gaseous reaction product at 25 to 350 ° C). For example, first, a gas such as H 2 , CO, CO 2 , a gaseous product comprising light hydrocarbon oil components and water, and a heavy hydrocarbon fraction in a reaction product in a high-temperature, high-pressure gas-liquid separation tank. Wax), and then introducing the gaseous product into a low-temperature and high-pressure separation tank to separate a gas such as H 2 , CO, CO 2 from a light hydrocarbon oil component and water. In this manner, the hydrocarbon oil separated and recovered from the reaction product obtained in the FT step is composed of hydrocarbon components having a wide range of molecular weights. Generally, it is known that the molecular weight distribution of hydrocarbons generated by FT synthesis follows a Schulz-Flory distribution determined by the chain growth probability α. ( "C 1 Chemistry", P37~P75, catalyst Society of Japan, Kodansha Scientific (1984)). The probability α varies between 0 and 1 depending on the catalyst used and the reaction conditions. However, if α is determined, the carbon distribution is almost uniquely determined regardless of the conversion. As α increases, the product distribution shifts to longer chain molecules. Therefore, in order to reduce by-products of light gas having a low carbon number, it is desirable that α be as large as possible. Specifically, the α value is set to be 0.9 or more. In any case, FT synthesis gives products with a wide distribution of carbon. Some of the hydrocarbons separated from the products obtained by the FT synthesis are directly produced as products, but most of them are hydrogenated olefins and oxygenated compounds in hydrocarbon fractions for stabilization or hydrogenation. It is subjected to catalytic hydrogenation for the purpose of isomerization to make it isoparaffin-rich or to hydrocrack heavy fractions to produce high-quality middle distillates. One of the embodiments of the present invention is to separate a hydrocarbon oil from the FT reaction product and further subject it to catalytic hydrogenation at high pressure and high temperature to produce high-quality gasoline, kerosene, and gas oil. .
【００４６】また、該反応生成物から炭化水素油を分離
し、該炭化水素油中の重質留分を高圧高温で接触水素化
分解処理し、高品質のガソリン、灯油、軽油を製造する
ことも本発明の好ましい実施態様に包含される。中間留
分は、沸点範囲が原油の常圧蒸留において得られ灯油と
軽油留分にほぼ相当する炭化水素混合油であり、中間留
分の範囲は実質的に約１００ないし３６０℃にあり、そ
の内で約２００ないし３６０℃で沸騰する留分は通常軽
油と云われる。Further, a hydrocarbon oil is separated from the reaction product, and a heavy fraction in the hydrocarbon oil is subjected to catalytic hydrocracking at high pressure and high temperature to produce high quality gasoline, kerosene and gas oil. Are also included in the preferred embodiment of the present invention. The middle distillate is a hydrocarbon blended oil whose boiling point range is obtained by atmospheric distillation of crude oil and substantially corresponds to kerosene and gas oil fractions, the middle distillate being substantially at a temperature of about 100 to 360 ° C. The fraction boiling within about 200 to 360 ° C is usually referred to as light oil.
【００４７】接触水素化処理用原料としては、ＦＴ合成
触媒上で製造された生成物で炭素数５以上、好ましくは
炭素数９以上の全留分を使用するのが好ましい。接触水
素化処理工程での主たる反応は、水素化、水添異性化及
び重質成分の水素化分解であるが、本工程で使用される
触媒は、当業界では周知されており、多種類の組成物で
市販入手することができる。典型的な水素化分解触媒
は、触媒金属成分として、元素周期列表第ＶＩＢ族及び
第ＶＩＩＩ族から選択される１種もしくはそれ以上の金
属、特にモリブデン、タングステン、コバルト、ニッケ
ル、ルテニウム、イリジウム、オスミウム、白金及びパ
ラジウムから選択される１種もしくはそれ以上の金属を
含む。好ましい触媒は、ニッケル、白金及びパラジウム
から選択される１種もしくはそれ以上の金属を触媒活性
として含む。触媒担体としては、耐火性金属酸化物もし
くは珪酸塩を含む。担体材料は非晶質もしくは結品質と
することができる。適する担体は、シリカ、アルミナ、
シリカーアルミナ、ジルコニア、チタニア及びその混合
物を包含する。担体は１種もしくはそれ以上のゼオライ
トを単独で或いは上記キャリヤ材料の１種もしくはそれ
以上と組合せて含むことができる。触媒は、全触媒１０
０重量部当りの金属として換算し、０．０５〜８０重量
部、好ましくは０．１〜７０重量部の量の触媒活性成分
を含むことができる。触媒中に存在させる触媒活性金属
の量は用いる特定金属に応じて変化する。特に好適な触
媒は、全触媒１００重量部当りの金属として換算し、
０．０５〜２重量部、より好ましくは０．１〜１重量部
の範囲の量の白金を含む。As the raw material for the catalytic hydrotreating, it is preferable to use all the fractions having 5 or more carbon atoms, preferably 9 or more carbon atoms, in the product produced on the FT synthesis catalyst. The main reactions in the catalytic hydrotreating step are hydrogenation, hydroisomerization and hydrocracking of heavy components, and the catalyst used in this step is well known in the art, and various kinds of catalysts are used. It is commercially available as a composition. Typical hydrocracking catalysts comprise, as catalytic metal components, one or more metals selected from Groups VIB and VIII of the Periodic Table of the Elements, especially molybdenum, tungsten, cobalt, nickel, ruthenium, iridium, osmium , Platinum and palladium. Preferred catalysts contain one or more metals selected from nickel, platinum and palladium as catalytic activity. Catalyst supports include refractory metal oxides or silicates. The carrier material can be amorphous or crystalline. Suitable carriers are silica, alumina,
Includes silica-alumina, zirconia, titania and mixtures thereof. The carrier may comprise one or more zeolites, alone or in combination with one or more of the above carrier materials. The catalyst is a total of 10 catalysts.
The catalytically active component may be contained in an amount of 0.05 to 80 parts by weight, preferably 0.1 to 70 parts by weight, calculated as metal per 0 parts by weight. The amount of catalytically active metal present in the catalyst will vary depending on the particular metal used. Particularly preferred catalysts are calculated as metal per 100 parts by weight of total catalyst,
It contains platinum in an amount ranging from 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight.
【００４８】接触水素化処理は、たとえば流動床、移動
床、スラリー床または固定床のような任意の種類の触媒
床反応装置を用いて行うことができるが、好ましくは固
定触媒床が用いられる。水素化処理条件としては、典型
的には、１７５〜４００℃、好ましくは２５０〜３７５
℃の反応温度及び１０〜２５０気圧、好ましくは２５〜
１５０気圧の水素分圧が用いられる。固定触媒床を用い
る場合、好ましくは０．１〜５ｋｇｈ-1の重量空時速
度、より好ましくは０．２５〜２ｋｇｈ-1の重量空時速
度で原料が供給される。水素は１００〜１００００Ｎｌ
ｈ-1、好ましくは５００〜５０００Ｎｌｈ-1のガス空時
速度で供給することができる。水素と供給物との比は１
００〜５０００Ｎｌ／ｋｇの範囲とすることができ、好
ましくは２５０〜２５００Ｎｌ／ｋｇである。接触水素
化処理後の炭化水素留分は、通常蒸留により軽質留分、
中間留分、残留重質留分とに分けられる。そして、該残
留重質留分の一部もしくは全量は接触水素化処理工程へ
再循環させ、中間留分へ再分解させることができる。本
発明の実施態様には、ＦＴ反応の選択性をより高分子量
化合物にシフトさせるため、オレフィン、アルコール、
アルデヒドを含む軽質炭化水素留分の一部もしくは全量
を、該ＦＴ反応工程へ再循環し、有用な中間留分の得率
を向上させることも包含される。リサイクルされたオレ
フィン、アルコール及びアルデヒドは、触媒上に再吸着
して、更なる連鎖成長にあずかる。また、本発明の実施
態様には、ＦＴ合成の反応生成物から炭化水素油を分離
した後の、メタン水素、炭酸ガスを含むガス状生成物の
一部もしくは全量を、原料ガス中の炭酸ガス濃度を調整
する低温加圧蒸留工程へ循環し、炭酸ガスの活用を図る
ことも包含される。本発明の更なる実施態様には、ＦＴ
反応生成物から炭化水素油を分離した後の、メタン、水
素、炭酸ガスを含む低いＢ．Ｔ．Ｕ．ガス状生成物の一
部もしくは全量を、合成ガスを製造するリフォーマーの
燃料として使用することや、触媒燃焼して発生する高温
ガスでガスタービン発電するなどにより、エネルギー利
用効率の向上を図ること等も包含される。The catalytic hydrotreating can be carried out using any type of catalyst bed reactor such as a fluidized bed, a moving bed, a slurry bed or a fixed bed, but preferably a fixed catalyst bed is used. Hydrotreating conditions are typically 175 to 400 ° C, preferably 250 to 375.
° C reaction temperature and 10-250 atm, preferably 25-
A hydrogen partial pressure of 150 atm is used. When using a fixed catalyst bed, preferably the weight hourly space velocity of 0.1～5Kgh -1, raw material is supplied more preferably at a weight hourly space velocity of 0.25~2kgh -1. Hydrogen is 100-10000Nl
h -1 , preferably at a gas hourly space velocity of 500 to 5000 Nlh -1 . The ratio of hydrogen to feed is 1
It can be in the range of 00 to 5000 Nl / kg, preferably 250 to 2500 Nl / kg. The hydrocarbon fraction after the catalytic hydrogenation is usually a light fraction by distillation,
It is divided into middle distillate and residual heavy distillate. Then, a part or the whole amount of the residual heavy fraction can be recycled to the catalytic hydrotreating step to be decomposed into an intermediate fraction. Embodiments of the present invention include an olefin, an alcohol,
Recycling some or all of the aldehyde-containing light hydrocarbon fraction to the FT reaction step also improves the yield of useful middle distillates. The recycled olefins, alcohols and aldehydes re-adsorb on the catalyst and participate in further chain growth. Further, in an embodiment of the present invention, a part or all of a gaseous product containing methane hydrogen and carbon dioxide gas after separating hydrocarbon oil from a reaction product of FT synthesis is converted into carbon dioxide gas in the raw material gas. It also includes circulating to a low-temperature pressure distillation step for adjusting the concentration to utilize carbon dioxide gas. In a further embodiment of the present invention, the FT
After separating hydrocarbon oil from the reaction product, low B.I. containing methane, hydrogen and carbon dioxide gas. T. U. Improve energy utilization efficiency by using part or all of the gaseous products as fuel for reformers that produce synthesis gas, and generating gas turbines using high-temperature gas generated by catalytic combustion Are also included.
【００４９】[0049]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。Next, the present invention will be described in more detail with reference to examples.
【００５０】触媒調製例１ 市販の純度９８．１ｗｔ％の酸化マグネシウム（Ｍｇ
Ｏ）の粉末に成形助剤としてカーボン３．０ｗｔ％を混
合してタブレット成形した１／８インチペレットを、空
気中に於いて１１００℃にて３ｈ焼成した後、含浸法で
０．０７５ｗｔ％Ｒｈを維持し、更に空気中に於いて９
００℃で焼成することによりＲｈ担持ＭｇＯ触媒を得
た。この含浸体は、焼成ＭｇＯペレットをロジウム(II
I）アセテート塩の水溶液中に約１２時間浸した後ろ過
し、空気中に於いて常温にて２４ｈ乾燥、同雰囲気中９
００℃にで３ｈ焼成し、Ｒｈ担持ＭｇＯ触媒(比表面積
０．６ｍ2／ｇ)とした。Catalyst Preparation Example 1 Commercially available magnesium oxide (Mg) having a purity of 98.1 wt%
O) powder was mixed with 3.0 wt% of carbon as a molding aid, and tablet-formed 1/8 inch pellets were fired in air at 1100 ° C. for 3 h and then impregnated with 0.075 wt% Rh. And in the air, 9
By baking at 00 ° C., a Rh-supported MgO catalyst was obtained. The impregnated body is obtained by converting the baked MgO pellets to rhodium (II
I) Immersion in an aqueous solution of acetate salt for about 12 hours, followed by filtration, drying in air at room temperature for 24 hours,
It was calcined at 00 ° C. for 3 hours to obtain a Rh-supported MgO catalyst (specific surface area: 0.6 m 2 / g).
【００５１】触媒調製例２ 市販の純度９８．１ｗｔ％の酸化マグネシウム（Ｍｇ
Ｏ）の粉末に成形助剤としてステアリン酸マグネシウム
を２．０ｗｔ％を混合してタブレット成形した１／８イ
ンチペレットを空気中に於いて１０５０℃にて３ｈ焼成
した後、含浸法で０．１ｗｔ％Ｒｕを維持し、更に空気
中に於いて８００℃で焼成することによりＲｈ担持Ｍｇ
Ｏ触媒を得た。この含浸体は、焼成ＭｇＯペレットをル
テニウム（III）アセトナト塩のメタノール溶液中に約
１２時間浸した後ろ過し、空気中に於いて常温にて２４
ｈ乾燥、同雰囲気中８００℃にで３ｈ焼成し、Ｒｕ担持
ＭｇＯ触媒（表面積１．１ｍ2／ｇ）とした。Catalyst Preparation Example 2 A commercially available magnesium oxide (Mg) having a purity of 98.1 wt%
O) powder was mixed with 2.0% by weight of magnesium stearate as a molding aid, and tablet-formed 1/8 inch pellets were fired in air at 1050 ° C. for 3 hours and then impregnated with 0.1% by weight. % Ru, and calcined at 800 ° C. in air to obtain Rh-supported Mg.
An O catalyst was obtained. This impregnated body is obtained by immersing the calcined MgO pellets in a methanol solution of ruthenium (III) acetonate for about 12 hours, filtering, and then immersing in air at room temperature for 24 hours.
After drying for 3 h at 800 ° C. for 3 h in the same atmosphere, a Ru-supported MgO catalyst (surface area: 1.1 m 2 / g) was obtained.
【００５２】触媒調製例３ 市販の純度９８．７ｗｔ％の酸化マグネシウム（Ｍｇ
Ｏ）の粉末に成形助剤として３．０ｗｔ％のカーボンを
混合し、タブレット形成した１／８インチペレットを空
気中で１０６０℃で３ｈ（時間）焼成し、これを触媒担
体ＭｇＯ（Ａ）として用いた。次に、３．９ｗｔ％のＲ
ｈを含むロジウム（III）アセテート水溶液に２６ｈ
（時間）浸漬した。その水溶液は水酸化マグネシウム水
溶液を用い、ｐＨは９．７に調整した。このようにし
て、Ｒｈを触媒担体ＭｇＯ（Ａ）に平衡吸着させた後、
濾過して、Ｒｈを水溶液状で吸着した触媒担体ＭｇＯ
（Ａ）を得た。この場合のＲｈ担持量は、Ｒｈ金属換算
量で、担体ＭｇＯ（Ａ）に対して、３７５０ｗｔｐｐｍ
である。次に、Ｒｈを吸着した担体ＭｇＯ（Ａ）を空気
中において３５℃の温度で５２ｈ乾燥した後、空気中に
おいて８５０℃で３ｈ焼成し、本発明触媒（Ａ）を得
た。この触媒（Ａ）はＲｈをＲｈ金属として担体ＭｇＯ
に対し３７５０ｗｔｐｐｍ含有するもので、その表面積
は１．２ｍ2／ｇであった。また、その酸点は、酸強度
（Ｈｏ）が３．３以上の酸点のみからなり、その含量は
０．０１ｍｍｏｌ／ｇであった。Catalyst Preparation Example 3 A commercially available magnesium oxide (Mg) having a purity of 98.7 wt%
O) powder was mixed with 3.0 wt% of carbon as a molding aid, and 1/8 inch pellets formed as tablets were fired in air at 1060 ° C. for 3 hours (hours), and this was used as a catalyst carrier MgO (A). Using. Next, 3.9 wt% R
26h in rhodium (III) acetate aqueous solution containing
(Time) Dipped. The pH of the aqueous solution was adjusted to 9.7 using an aqueous solution of magnesium hydroxide. Thus, after Rh is equilibrium-adsorbed on the catalyst support MgO (A),
Filtration, catalyst support MgO adsorbing Rh in aqueous solution
(A) was obtained. The amount of Rh supported in this case is 3750 wtppm relative to the carrier MgO (A) in terms of Rh metal.
It is. Next, the MgO (A) carrier to which Rh was adsorbed was dried in air at a temperature of 35 ° C. for 52 hours, and then calcined in air at 850 ° C. for 3 hours to obtain a catalyst (A) of the present invention. This catalyst (A) uses Rh as Rh metal and supports MgO
And the surface area was 1.2 m 2 / g. The acid sites consisted only of acid sites having an acid strength (Ho) of 3.3 or more, and the content was 0.01 mmol / g.
【００５３】触媒調製例４ 市販の純度９９．９ｗｔ％以上の酸化マグネシウム（Ｍ
ｇＯ）を用いて形成したＭｇＯの１／８インチペレット
を空気中で１０００℃にて２ｈ（時間）焼成し、これを
触媒担体ＭｇＯ（Ｂ）として用いた。次に、０．１ｗｔ
％のＲｕを含むルテニウム（III）クロライド水溶液に
１９ｈ（時間）浸漬した。その水溶液は水酸化マグネシ
ウム水溶液を用い、ｐＨは９．７に調整した。このよう
にしてＲｕを触媒担体ＭｇＯ（Ｂ）に平衡吸着させた
後、濾過して、Ｒｕを水溶液状で吸着した触媒担体Ｍｇ
Ｏ（Ｂ）を得た。この場合のＲｕ担持量は、Ｒｕ金属換
算量で担体ＭｇＯ（Ｂ）に対して、１２５ｗｔｐｐｍで
ある。次に、Ｒｕを吸着した担体ＭｇＯ（Ｂ）を空気中
において３０℃の温度で７２ｈ乾燥した後、空気中にお
いて８６０℃で２．５ｈ焼成し、本発明触媒（Ｂ）を得
た。この触媒（Ｂ）はＲｕをＲｕ金属として担体ＭｇＯ
（Ｂ）に対し１２５ｗｔｐｐｍの割合で含有するもの
で、その表面積は４．８ｍ2／ｇであった。また、その
酸点は、酸強度（Ｈｏ）が３．３以上の酸点のみからな
り、その含量は０．０３ｍｍｏｌ／ｇであった。Catalyst Preparation Example 4 A commercially available magnesium oxide having a purity of 99.9 wt% or more (M
A 1/8 inch pellet of MgO formed using gO) was fired in air at 1000 ° C. for 2 hours (hour), and this was used as a catalyst support MgO (B). Next, 0.1wt
% Ruthenium (III) chloride aqueous solution for 19 h (hour). The pH of the aqueous solution was adjusted to 9.7 using an aqueous solution of magnesium hydroxide. After Ru is equilibrium-adsorbed on the catalyst carrier MgO (B) in this way, the catalyst carrier Mg on which Ru is adsorbed in the form of an aqueous solution is filtered.
O (B) was obtained. In this case, the amount of supported Ru is 125 wtppm in terms of the amount of Ru metal with respect to the carrier MgO (B). Next, the MgO (B) carrier on which Ru was adsorbed was dried in air at a temperature of 30 ° C. for 72 hours, and then calcined in air at 860 ° C. for 2.5 hours to obtain a catalyst (B) of the present invention. This catalyst (B) uses Ru as Ru metal and supports MgO
It was contained at a rate of 125 wtppm with respect to (B), and its surface area was 4.8 m 2 / g. The acid sites consisted only of acid sites having an acid strength (Ho) of 3.3 or more, and the content was 0.03 mmol / g.
【００５４】触媒調製例５ 市販の純度９８．０ｗｔ％の酸化マグネシウム（Ｍｇ
Ｏ）を用いて形成したＭｇＯの１／８インチペレットを
空気中で１２００℃にて２．５ｈ（時間）焼成し、これ
を触媒担体ＭｇＯ（Ｃ）として用いた。次に、２．６ｗ
ｔ％のＲｈを含むロジウム（III）アセテート水溶液に
２６ｈ（時間）浸漬した。その水溶液は水酸化マグネシ
ウム水溶液を用い、ｐＨは９．７に調整した。このよう
にしてＲｈを触媒担体ＭｇＯ（Ｃ）に平衡吸着させた
後、濾過して、Ｒｈを水溶液状で吸着した触媒担体Ｍｇ
Ｏ（Ｃ）を得た。この場合のＲｈ担持量は、Ｒｈ金属換
算量で、担体ＭｇＯ（Ｃ）に対して、１７５０ｗｔｐｐ
ｍである。次に、Ｒｈを吸着した担体ＭｇＯ（Ｃ）を空
気中において２０℃の温度で３４ｈ乾燥した後、空気中
において９５０℃で３．５ｈ焼成し、本発明触媒（Ｃ）
を得た。この触媒（Ｃ）はＲｈをＲｈ金属として担体Ｍ
ｇＯに対し１７５０ｗｔｐｐｍ含有するもので、その表
面積は０．２ｍ2／ｇであった。また、その酸点は、酸
強度（Ｈｏ）が３．３以上の酸点のみからなり、その含
量は０．００２ｍｍｏｌ／ｇであった。Catalyst Preparation Example 5 Commercially available magnesium oxide (Mg) having a purity of 98.0 wt%
A 1 / 8-inch pellet of MgO formed using O) was fired in air at 1200 ° C. for 2.5 hours (hour), and this was used as a catalyst support MgO (C). Next, 2.6w
It was immersed in a rhodium (III) acetate aqueous solution containing t% Rh for 26 h (hour). The pH of the aqueous solution was adjusted to 9.7 using an aqueous solution of magnesium hydroxide. In this manner, the Rh is equilibrium-adsorbed on the catalyst support MgO (C), and then filtered, and the Rh is adsorbed in the form of an aqueous solution.
O (C) was obtained. The amount of Rh supported in this case is 1750 wtpp with respect to the support MgO (C) in terms of Rh metal.
m. Next, the MgO (C) carrier on which Rh was adsorbed was dried in air at a temperature of 20 ° C. for 34 hours, and then calcined in air at 950 ° C. for 3.5 hours to obtain the catalyst (C) of the present invention.
I got This catalyst (C) uses Rh as Rh metal and the carrier M
It contained 1750 wtppm based on gO and had a surface area of 0.2 m 2 / g. The acid sites consisted only of acid sites having an acid strength (Ho) of 3.3 or more, and the content was 0.002 mmol / g.
【００５５】比較触媒調製例１ 空気中に於いて３７０℃にて３ｈ焼成した酸化マグネシ
ウムを０．２７〜０．７５ｍｍに整粒後、含浸法でＲｈ
を担持し、更に空気中に於いて３７０℃で焼成すること
によりＲｈ担持ＭｇＯ触媒（ＲｈはＭｇ１ｇに対して
２．６×１０-3ｇ担持されており、ｍｏｌ換算の担持量
は０．１０ｍｏｌ％）を得た。この含浸体は焼成ＭｇＯ
にロジウム（III）アセテート水溶液を極めて少量ずつ
滴下、滴下毎に混振することにより得られる。滴下した
ロジウム（III）アセテート水溶液中のＲｈ濃度は１．
７ｗｔ％である。この含浸体を空気中に於いて１２０℃
にて２．５ｈ乾燥、同雰囲気中３７０℃にて３ｈ焼成
し、Ｒｈ担持ＭｇＯ触媒（表面積９８ｍ2／ｇ）とし
た。Comparative Catalyst Preparation Example 1 Magnesium oxide calcined at 370 ° C. for 3 hours in air was sized to 0.27 to 0.75 mm, and Rh was impregnated.
And further calcined in air at 370 ° C. to obtain a Rh-supported MgO catalyst (Rh is supported at 2.6 × 10 −3 g per gram of Mg, and the supported amount in terms of mol is 0.10 mol. %). This impregnated body is calcined MgO
An aqueous solution of rhodium (III) acetate is dropped by a very small amount, and the mixture is shaken for each drop. The Rh concentration in the aqueous rhodium (III) acetate solution dropped was 1.
7 wt%. This impregnated body is in air at 120 ° C.
For 2.5 h, and calcined at 370 ° C. for 3 h in the same atmosphere to obtain a Rh-supported MgO catalyst (surface area 98 m 2 / g).
【００５６】炭酸ガス蒸留例１ 原料として、炭酸ガス５０．２ｍｏｌ％、メタン４４．
７ｍｏｌ％、エタン４．５ｍｏｌ％、プロパン０．６ｍ
ｏｌ％を含む天然ガスより、蒸留により炭酸ガスを分離
した。蒸留塔の理論段は１０段であり、圧力３０Ｋｇ／
ｃｍ2Ｇ、塔頂温度−４５．４℃、塔底温度−５．０
℃、還流比＝１．０の条件で蒸留を行い、塔頂より炭酸
ガス３０．０ｍｏｌ％、メタン．６３．８ｍｏｌ％、エ
タン６．１ｍｏｌ％、プロパン０．１ｍｏｌ％の組成の
ガスを得た。Carbon Dioxide Distillation Example 1 As raw materials, carbon dioxide 50.2 mol%, methane
7 mol%, ethane 4.5 mol%, propane 0.6 m
Carbon dioxide gas was separated from natural gas containing ol% by distillation. The theoretical stage of the distillation column is 10 stages, and the pressure is 30 kg /
cm 2 G, tower top temperature −45.4 ° C., tower bottom temperature −5.0
Distillation was carried out under the conditions of C. and a reflux ratio of 1.0, and 30.0 mol% of carbon dioxide gas and methane. A gas having a composition of 63.8 mol%, 6.1 mol% of ethane and 0.1 mol% of propane was obtained.
【００５７】実施例１ （１）合成ガス生成工程 前記炭酸ガス蒸留例１より得られた、炭酸ガス３０．０
ｍｏｌ％含む塔頂ガスを原料として用い、触媒調製例１
に示した触媒を用いて、合成ガス製造試験を行った。触
媒は予め９００℃で約１．５ＨＲ還元後、原料ガス中の
低級炭化水素全モル数に対する水のモル比が、１：０．
９９になるようにＨ2Ｏを加え（ＣＯ2＋Ｈ2Ｏ／低級炭
化水素の炭素原子＝１．３８）、触媒層出口温度を９０
０℃とし、圧力２０ｋｇ／ｃｍ2Ｇ、入口ガス全量基準
のＧＨＳＶを４５００ＨＲ-1とした。反応でのＣＨ4の
転化率は６７％であり、得られた合成ガスの組成は、Ｈ
2＝５０．０ｍｏｌ％、ＣＯ＝２４．９ｍｏｌ％（Ｈ2／
ＣＯ＝２．０）、ＣＨ4＝７．５ｍｏｌ％、ＣＯ2＝４．
８ｍｏｌ％、Ｈ2Ｏ＝１２．８ｍｏｌ％であった。Example 1 (1) Synthesis gas generation step Carbon dioxide gas 30.0 obtained from carbon dioxide distillation example 1
Catalyst preparation example 1 using a top gas containing mol% as a raw material
A synthesis gas production test was carried out using the catalyst shown in (1). After reducing the catalyst by about 1.5 HR at 900 ° C. in advance, the molar ratio of water to the total number of lower hydrocarbons in the raw material gas is 1: 0.
H 2 O was added so as to be 99 (CO 2 + H 2 O / carbon atom of lower hydrocarbon = 1.38), and the catalyst layer outlet temperature was set to 90.
The temperature was 0 ° C., the pressure was 20 kg / cm 2 G, and the GHSV based on the total amount of the inlet gas was 4500 HR −1 . The conversion of CH 4 in the reaction was 67%, and the composition of the resulting synthesis gas was H
2 = 50.0 mol%, CO = 24.9 mol% (H 2 /
CO = 2.0), CH 4 = 7.5 mol%, CO 2 = 4.
8 mol% and H 2 O = 12.8 mol%.
【００５８】（２）ＦＴ工程 前記合成ガス生成工程で得られた合成ガスを冷却し、Ｈ
2Ｏを除去した後、ＦＴ合成用原料ガスとしてＦＴ合成
試験を実施した。触媒としては、１５ｗｔ％ＣＯをＳｉ
Ｏ2に担持し、さらにプロモーターとしてＺｒを１．２
ｗｔ％添加した触媒を１５ｃｃ反応器に充填し、反応温
度２２０℃、反応圧力２０ｋｇ／ｃｍ2Ｇ、原料ガス基
準のＧＨＳＶ＝１５００ＨＲ-1の条件で液体燃料油を製
造した。反応条件下でのＣＯ転化率は７５％であり、以
下に示す反応生成物を得た。(2) FT Step The synthesis gas obtained in the above synthesis gas generation step is cooled,
After removing 2 O, an FT synthesis test was carried out as a raw material gas for FT synthesis. As a catalyst, 15 wt% CO
Supported on O 2, and Zr as a promoter
A 15 cc reactor was charged with the catalyst to which wt% was added, and a liquid fuel oil was produced under the conditions of a reaction temperature of 220 ° C., a reaction pressure of 20 kg / cm 2 G, and GHSV = 1500 HR −1 based on the raw material gas. The CO conversion under the reaction conditions was 75%, and the following reaction products were obtained.
【表１】 炭化水素分類 組 成 軽質ガス（炭素数：４以下） ２．５ｗｔ％ ナフサ（炭素数：５〜１１） ４８．８ｗｔ％ 灯軽油（炭素数：１２〜２２） ２１．１ｗｔ％ ワックス（炭素数：２３以上） ２７．６ｗｔ％[Table 1] Hydrocarbon classification Composition Light gas (carbon number: 4 or less) 2.5 wt% Naphtha (carbon number: 5 to 11) 48.8 wt% Kerosene light oil (carbon number: 12 to 22) 21.1 wt% wax (Carbon number: 23 or more) 27.6 wt%
【００５９】（３）ＦＴ生成物の水素化分解反応工程 前記ＦＴ工程で得られた炭化水素を蒸留し、炭素数２３
以上の炭化水素を分離し、水素化分解反応の原料とし
た。水素化分解触媒としては、５．１ｗｔ％Ｍｏ、２．
８ｗｔ％ＷがＳｉＯ2・Ａｌ2Ｏ3に担持された触媒を用
い、反応温度３２０℃、圧力４５ｋｇ／ｃｍ2Ｇ、ＬＨ
ＳＶ＝０．５ＨＲ-1、Ｈ2／Ｏｉｌ比＝２０００Ｎｌ／
ｌで反応を行った。以下に、原料及び生成物組成を示
す。(3) FT Product Hydrocracking Reaction Step The hydrocarbon obtained in the FT step is distilled to obtain a product having 23 carbon atoms.
The above hydrocarbons were separated and used as raw materials for the hydrocracking reaction. As the hydrocracking catalyst, 5.1 wt% Mo, 2.
Using a catalyst in which 8 wt% W is supported on SiO 2 · Al 2 O 3 , a reaction temperature of 320 ° C., a pressure of 45 kg / cm 2 G, and an LH
SV = 0.5 HR −1 , H 2 / Oil ratio = 2000 Nl /
The reaction was performed at 1 l. The raw materials and product compositions are shown below.
【表２】 炭化水素分類 原 料 生成物 軽質ガス（炭素数：４以下） − ２．３ｗｔ％ ナフサ（炭素数：５〜１１） − ２２．５ｗｔ％ 灯軽油（炭素数：１２〜２２） ４．２ｗｔ％ ４３．３ｗｔ％ ワックス（炭素数：２３以上） ９５．８ｗｔ％ ３１．９ｗｔ％[Table 2] Hydrocarbon classification Raw material Product Light gas (carbon number: 4 or less)-2.3 wt% Naphtha (carbon number: 5 to 11)-22.5 wt% Kerosene light oil (carbon number: 12 to 22) 4 0.2 wt% 43.3 wt% wax (carbon number: 23 or more) 95.8 wt% 31.9 wt%
【００６０】合成ガス生成反応例１ 触媒調製例１で調製した触媒３０ｃｃを、反応器に充填
し、メタンからの合成ガス製造試験を実施した。触媒
は、予めＨ2気流中９００℃で１ｈ還元処理を行った
後、ＣＨ４4ＣＯ2：Ｈ2Ｏモル比＝１：０．３３：０．
７（原料（ＣＯ2＋Ｈ2Ｏ）／ＣＨ4＝１．０２）の原料
ガスを圧力２０ｋｇ／ｃｍ2Ｇ、触媒層出口温度８５０
℃、原料ガス基準のＧＨＳＶ＝５０００ｈｒ-1の条件で
処理した。生成ガスＨ2／ＣＯモル比は、２．０であ
り、反応開始から５ｈ経過後の合成ガス生産効率は１０
２％、炭素変換効率は５２％であり、また、反応開始か
ら３０００ｈ経過後の合成ガス生産効率は１０１％、炭
素変換効率は５２％であった。Synthesis Gas Production Reaction Example 1 30 cc of the catalyst prepared in Catalyst Preparation Example 1 was charged into a reactor, and a synthesis gas production test from methane was performed. The catalyst was previously subjected to a reduction treatment in an H 2 gas stream at 900 ° C. for 1 hour, and then a CH 4 4 CO 2 : H 2 O molar ratio = 1: 0.33: 0.
7 (raw material (CO 2 + H 2 O) / CH 4 = 1.02) at a pressure of 20 kg / cm 2 G and a catalyst layer outlet temperature of 850.
The treatment was performed under the conditions of C ° C. and GHSV = 5000 hr −1 based on the raw material gas. The H 2 / CO molar ratio of the generated gas was 2.0, and the synthesis gas production efficiency after 10 hours from the start of the reaction was 10%.
The carbon conversion efficiency was 2%, the carbon conversion efficiency was 52%, the synthesis gas production efficiency after 3000 hours from the start of the reaction was 101%, and the carbon conversion efficiency was 52%.
【００６１】合成ガス生成反応例２ 触媒調製例２で調製した触媒３０ｃｃを、反応器に充填
した以外は、実施例１で示した条件とまったく同一条件
で、合成ガス製造試験を実施した。生成ガスＨ２／ＣＯ
モル比は、２．０であり、反応開始から５ｈ経過後の合
成ガス生産効率は１０３％、炭素変換効率は５３％であ
り、また、反応開始から４０００ｈ経過後の合成ガス生
産効率は１０３％、炭素変換効率は５３％であった。Synthesis Gas Production Reaction Example 2 A synthesis gas production test was carried out under exactly the same conditions as in Example 1 except that 30 cc of the catalyst prepared in Catalyst Preparation Example 2 was charged into the reactor. Generated gas H2 / CO
The molar ratio was 2.0, the synthesis gas production efficiency after 5 hours from the start of the reaction was 103%, the carbon conversion efficiency was 53%, and the synthesis gas production efficiency after 4000 hours from the start of the reaction was 103%. And the carbon conversion efficiency was 53%.
【００６２】合成ガス生成反応例３ 触媒調製例２で調製した触媒３０ｃｃを反応器に充填
し、メタンに種々の混合比のＨ2Ｏ、ＣＯ2を加え合成ガ
ス製造試験を行った。触媒は予め９００℃で約２．０Ｈ
Ｒ還元処理を行い、触媒層出口温度を８５０℃、圧力２
０ｋｇ／ｃｍ2Ｇ、入口ガス組成全量基準のＧＨＳＶを
４０００ＨＲ-1として、生成物中のＨ２／ＣＯ比がほぼ
２．０となるよう、原料ＣＨ4、ＣＯ2、Ｈ2Ｏ比を調整
し、反応試験を実施した。試験結果を下表に示した。Synthesis Gas Production Reaction Example 3 30 cc of the catalyst prepared in Catalyst Preparation Example 2 was charged into a reactor, and various mixing ratios of H 2 O and CO 2 were added to methane to conduct a synthesis gas production test. The catalyst is about 2.0H at 900 ° C in advance.
R reduction treatment, the catalyst layer outlet temperature is 850 ° C., pressure 2
The raw material CH 4 , CO 2 , and H 2 O ratios were adjusted so that the H2 / CO ratio in the product was approximately 2.0, with the GHSV based on 0 kg / cm 2 G and the total inlet gas composition being 4000 HR −1. A reaction test was performed. The test results are shown in the table below.
【表３】 [Table 3]
【００６３】比較反応例１ 実施例１の（１）合成ガス生成工程において、触媒とし
て比較触媒調製例１で得た触媒を用いた以外は同様にし
て実験を行った。この場合の反応開始から５ｈ経過後の
ＣＨ4転化率は６６％であった。また、反応開始から５
００ｈ経過後のＣＨ4の転化率は、４０．０％であっ
た。Comparative Reaction Example 1 An experiment was conducted in the same manner as in Example 1 except that the catalyst obtained in Comparative Catalyst Preparation Example 1 was used in the synthesis gas generation step (1). In this case, the conversion of CH 4 after 5 hours from the start of the reaction was 66%. In addition, 5 minutes from the start of the reaction
After a lapse of 00 h, the conversion of CH 4 was 40.0%.
【００６４】[0064]
【発明の効果】本発明によれば、メタンや天然ガス等の
低級炭化水素ガスを出発原料として用い、長時間にわた
って安定的にかつ経済的に炭素数１２〜２２の炭化水素
油を収率よく製造することができる。According to the present invention, a lower hydrocarbon gas such as methane or natural gas is used as a starting material to stably and economically produce a hydrocarbon oil having 12 to 22 carbon atoms with a high yield over a long period of time. Can be manufactured.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１１年３月１日（１９９９．３．１）[Submission date] March 1, 1999 (1999.3.1)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００５１[Correction target item name] 0051
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００５１】触媒調製例２ 市販の純度９８．１ｗｔ％の酸化マグネシウム（Ｍｇ
Ｏ）の粉末に成形助剤としてステアリン酸マグネシウム
を２．０ｗｔ％を混合してタブレット成形した１／８イ
ンチペレットを空気中に於いて１０５０℃にて３ｈ焼成
した後、含浸法で０．１ｗｔ％Ｒｕを維持し、更に空気
中に於いて８００℃で焼成することによりＲｕ担持Ｍｇ
Ｏ触媒を得た。この含浸体は、焼成ＭｇＯペレットをル
テニウム（III）アセトナト塩のメタノール溶液中に約
１２時間浸した後ろ過し、空気中に於いて常温にて２４
ｈ乾燥、同雰囲気中８００℃にで３ｈ焼成し、Ｒｕ担持
ＭｇＯ触媒（表面積１．１ｍ2／ｇ）とした。Catalyst Preparation Example 2 A commercially available magnesium oxide (Mg) having a purity of 98.1 wt%
O) powder was mixed with 2.0% by weight of magnesium stearate as a molding aid, and tablet-formed 1/8 inch pellets were fired in air at 1050 ° C. for 3 hours and then impregnated with 0.1% by weight. % maintaining Ru, further Ru supporting Mg by baking at 800 ° C. in air
An O catalyst was obtained. This impregnated body is obtained by immersing the calcined MgO pellets in a methanol solution of ruthenium (III) acetonate for about 12 hours, filtering, and then immersing in air at room temperature for 24 hours.
After drying for 3 h at 800 ° C. for 3 h in the same atmosphere, a Ru-supported MgO catalyst (surface area: 1.1 m 2 / g) was obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田内 正人 神奈川県横浜市鶴見区鶴見中央二丁目12番 １号 千代田化工建設株式会社内 (72)発明者 志村 光則 神奈川県横浜市鶴見区鶴見中央二丁目12番 １号 千代田化工建設株式会社内 Ｆターム(参考） 4G040 EA03 EA06 EB16 EB43 EC03 EC08 4H029 CA00 DA00 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masato Tauchi 2-1-1, Tsurumichuo, Tsurumi-ku, Yokohama-shi, Kanagawa Prefecture Inside Chiyoda Kako Construction Co., Ltd. (72) Inventor Mitsunori Shimura Tsurumi-chuo, Tsurumi-ku, Yokohama-shi, Kanagawa Prefecture 1-chome No. 1 F-term in Chiyoda Kako Construction Co., Ltd. (reference) 4G040 EA03 EA06 EB16 EB43 EC03 EC08 4H029 CA00 DA00
Claims (15)
液状炭化水素油へ転換する方法において、（ｉ）炭酸ガ
スを１０〜５０モル％含む低級炭化水素ガスに、水及び
／又はスチームを添加して、各成分が下記式を満たす混
合ガスを調製する工程、 ０．５≦（［ＣＯ2］＋［Ｈ2Ｏ］）／［Ｃ］≦２．５ （式中、［ＣＯ2］はＣＯ2のモル数、［Ｈ2Ｏ］はＨ2Ｏ
のモル数及び［Ｃ］は低級炭化水素ガス中に含まれる炭
素のモル数を示す）（ii）該混合ガス中に含まれる低級
炭化水素ガスを、主に酸化マグネシウムからなる担体
に、ロジウム及び／又はルテニウムの触媒金属を担持さ
せた触媒であって、該触媒の比表面積が５ｍ2／ｇ以下
で、かつ触媒金属の担持量が金属原子基準で担体金属酸
化物に対して０．１０〜５０００重量ｐｐｍである触媒
に、１０〜７５気圧の圧力、６００〜１０００℃の温度
で接触させて、水素／一酸化炭素のモル比が１．５〜
２．５の合成ガスを生成させる工程、（iii）該合成ガ
スを、低ＣＯシフト活性のフィッシャー・トロプシュ触
媒の存在下で反応させ液状炭化水素油を含む反応生成物
を生成させる工程、（iv）該反応生成物から炭化水素油
を分離する工程、からなることを特徴とする炭化水素油
の製造方法。1. A method for converting a raw material lower hydrocarbon gas containing carbon dioxide into a liquid hydrocarbon oil, wherein (i) adding water and / or steam to the lower hydrocarbon gas containing 10 to 50 mol% of carbon dioxide. Then, a step of preparing a mixed gas in which each component satisfies the following formula: 0.5 ≦ ([CO 2 ] + [H 2 O]) / [C] ≦ 2.5 (where [CO 2 ] is The number of moles of CO 2 , [H 2 O] is H 2 O
And [C] indicate the number of moles of carbon contained in the lower hydrocarbon gas.) (Ii) transferring the lower hydrocarbon gas contained in the mixed gas to a carrier mainly composed of magnesium oxide; And / or a catalyst carrying a ruthenium catalyst metal, wherein the specific surface area of the catalyst is 5 m 2 / g or less, and the amount of the catalyst metal carried is 0.10 to 0.10 with respect to the carrier metal oxide on a metal atom basis. Contacting the catalyst at 5000 ppm by weight at a pressure of 10 to 75 atm and a temperature of 600 to 1000 ° C., the molar ratio of hydrogen / carbon monoxide is 1.5 to
(Iii) reacting the synthesis gas in the presence of a low CO shift activity Fischer-Tropsch catalyst to produce a reaction product containing a liquid hydrocarbon oil, (iv) A) separating the hydrocarbon oil from the reaction product.
を２０〜４０モル％含む低級炭化水素ガスに、水及び／
又はスチームを添加して、各成分が下記式を満足する混
合ガスを調製する請求項１に記載の方法。 １≦（［ＣＯ2］＋［Ｈ2Ｏ］）／［Ｃ］≦２ （式中、［ＣＯ2］はＣＯ2のモル数、［Ｈ2Ｏ］はＨ2Ｏ
のモル数及び［Ｃ］は低級炭化水素ガス中に含まれる炭
素のモル数を示す）2. In the mixed gas preparation step, water and / or water is added to a lower hydrocarbon gas containing 20 to 40 mol% of carbon dioxide gas.
2. The method according to claim 1, wherein steam is added to prepare a mixed gas in which each component satisfies the following formula. 1 ≦ ([CO 2 ] + [H 2 O]) / [C] ≦ 2 (where [CO 2 ] is the number of moles of CO 2 and [H 2 O] is H 2 O
And [C] indicate the number of moles of carbon contained in the lower hydrocarbon gas.)
わされる合成ガス生産効率がモル基準で８０％以上であ
る請求項１又は２に記載の方法。 {(［ＣＯ］＋［Ｈ2］)／(［Ｃ］＋［ＣＯ2］＋［Ｈ
2Ｏ］)}×１００％ （式中、［ＣＯ］はＣＯのモル数、［Ｈ2］はＨ2のモル
数、［Ｃ］は低級炭化水素ガス中に含まれる炭素のモル
数、［ＣＯ2］はＣＯ2のモル数及び［Ｈ2Ｏ］はＨ2Ｏの
モル数を示す）3. The method according to claim 1, wherein in the syngas generation step, the synthesis gas production efficiency represented by the following formula is 80% or more on a molar basis. {([CO] + [H 2 ]) / ([C] + [CO 2 ] + [H
2 O])} × 100% ( wherein, [CO] is the number of moles of CO, [H 2] is the number of moles of H 2, [C] is the number of moles of carbon contained in the lower hydrocarbon gas, [ [CO 2 ] indicates the number of moles of CO 2 and [H 2 O] indicates the number of moles of H 2 O.)
わされる炭素変換効率がモル基準で５０％以上である請
求項１〜３のいずれかに記載の方法。 {［ＣＯ］／(［Ｃ］＋［ＣＯ2］)}×１００％ （式中、［ＣＯ］はＣＯのモル数、［Ｃ］は低級炭化水
素ガス中に含まれる炭素のモル数及び［ＣＯ2］はＣＯ2
のモル数を示す）4. The method according to claim 1, wherein in the synthesis gas producing step, the carbon conversion efficiency represented by the following formula is 50% or more on a molar basis. {[CO] / ([C] + [CO 2 ])} × 100% (where [CO] is the number of moles of CO, [C] is the number of moles of carbon contained in the lower hydrocarbon gas and [ CO 2 ] is CO 2
Shows the number of moles)
求項１〜４のいずれかに記載の方法。5. The method according to claim 1, wherein the lower hydrocarbon gas is natural gas.
濃度を調整するために、該低級炭化水素を、操作圧力１
０〜８０気圧の低温加圧蒸留塔を用いて蒸留し、塔底よ
り炭酸ガスを分離し、塔頂より所定の炭酸ガス濃度の低
級炭化水素ガス得る請求項１〜５のいずれかに記載の方
法。6. In order to adjust the concentration of excess carbon dioxide in the lower hydrocarbon gas, the lower hydrocarbon is subjected to an operating pressure of 1%.
The method according to any one of claims 1 to 5, wherein the distillation is performed using a low-temperature pressure distillation column having a pressure of 0 to 80 atm, carbon dioxide is separated from the bottom of the column, and a lower hydrocarbon gas having a predetermined carbon dioxide concentration is obtained from the top of the column. Method.
０気圧である請求項６に記載の方法。7. The low pressure distillation column has an operating pressure of 30-5.
7. The method of claim 6, wherein the pressure is zero atmosphere.
以上の温度である請求項６又は７に記載の方法。8. A low-temperature pressure distillation column having an overhead temperature of -60 ° C.
The method according to claim 6, wherein the temperature is the above temperature.
水素及び／又は炭酸ガスの分離工程を経ずに、直接フィ
ッシャー・トロプシュ反応工程に導入する請求項１〜８
のいずれかに記載の方法。9. The synthesis gas from the synthesis gas generation step,
9. The method according to claim 1, wherein the hydrogen and / or carbon dioxide gas is directly introduced into the Fischer-Tropsch reaction step without going through a separation step.
The method according to any of the above.
又はＲｕからなる低シフト活性のフィッシャー・トロプ
シュ触媒の存在下で反応させ液状炭化水素油を含む反応
生成物を生成させる請求項１〜９のいずれかに記載の方
法。10. The synthesis gas, wherein the metal component is Co and / or
The method according to any one of claims 1 to 9, wherein the reaction is carried out in the presence of a low shift activity Fischer-Tropsch catalyst comprising Ru to produce a reaction product containing a liquid hydrocarbon oil.
から炭化水素油を分離し、さらにそれを高圧高温で接触
水素化処理し、高品質のガソリン、灯油、軽油を製造す
ることを特徴とする請求項１〜１０のいずれかに記載の
方法。11. A high-quality gasoline, kerosene or light oil is produced by separating a hydrocarbon oil from the Fischer-Tropsch reaction product and subjecting it to catalytic hydrogenation at a high pressure and a high temperature. The method according to any one of 1 to 10.
から炭化水素油を分離し、該炭化水素油中の重質留分を
高圧高温で接触水素化分解処理し、高品質のガソリン、
灯油、軽油を製造することを特徴とする請求項１〜１０
のいずれかに記載の方法。12. A hydrocarbon oil is separated from the Fischer-Tropsch reaction product, and a heavy fraction in the hydrocarbon oil is subjected to catalytic hydrocracking at a high pressure and a high temperature to produce a high-quality gasoline,
11. Kerosene and light oil are manufactured.
The method according to any of the above.
から炭化水素油を分離した後の、メタン、水素、炭酸ガ
スを含むガス状生成物の一部もしくは全量を、原料低級
炭化水素ガス中の炭酸ガス濃度を調整する低温加圧蒸留
塔へ循環することを特徴とする請求項５に記載の方法。13. The method according to claim 1, wherein a part or all of the gaseous product containing methane, hydrogen, and carbon dioxide after separating the hydrocarbon oil from the Fischer-Tropsch reaction product is converted into carbon dioxide in the raw material lower hydrocarbon gas. 6. The process according to claim 5, wherein the solution is recycled to a low-temperature pressure distillation column for adjusting the concentration.
から炭化水素油を分離した後の、メタン、水素、炭酸ガ
スを含むガス状生成物の一部もしくは全量を、合成ガス
を製造する際の熱エネルギー源として使用することを特
徴とする請求項１〜１３のいずれかに記載の方法。14. A method according to claim 1, wherein after the separation of the hydrocarbon oil from the Fischer-Tropsch reaction product, a part or all of the gaseous product containing methane, hydrogen and carbon dioxide is converted into heat energy for producing synthesis gas. 14. The method according to claim 1, wherein the method is used as a source.
中のオレフィンを含む軽質炭化水素留分の一部もしくは
全量を、該フィシャー・トロプシュ反応工程へ再循環す
ることを特徴とする請求項１〜１４のいずれかに記載の
方法。15. The fischer-Tropsch reaction product according to claim 1, wherein a part or all of an olefin-containing light hydrocarbon fraction in the Fischer-Tropsch reaction product is recycled to the Fischer-Tropsch reaction step. The method according to any of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29293098A JP4132295B2 (en) | 1998-09-30 | 1998-09-30 | Method for producing liquid hydrocarbon oil from lower hydrocarbon gas containing carbon dioxide gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29293098A JP4132295B2 (en) | 1998-09-30 | 1998-09-30 | Method for producing liquid hydrocarbon oil from lower hydrocarbon gas containing carbon dioxide gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000104078A true JP2000104078A (en) | 2000-04-11 |
| JP4132295B2 JP4132295B2 (en) | 2008-08-13 |
Family
ID=17788258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29293098A Expired - Fee Related JP4132295B2 (en) | 1998-09-30 | 1998-09-30 | Method for producing liquid hydrocarbon oil from lower hydrocarbon gas containing carbon dioxide gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4132295B2 (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001342003A (en) * | 2000-05-30 | 2001-12-11 | Mitsubishi Heavy Ind Ltd | Method of production for gasoline, gas oil and synthesis gas for kerosene |
| JP2002060762A (en) * | 2000-08-22 | 2002-02-26 | Mitsubishi Heavy Ind Ltd | Method of producing synthesis gas for synthesizing gasoline, lamp oil and gas oil |
| WO2005037962A1 (en) * | 2003-10-16 | 2005-04-28 | Japan Gas Synthesize, Ltd. | Method for producing liquefied petroleum gas containing propane or butane as main component |
| JP2007513887A (en) * | 2003-11-25 | 2007-05-31 | シェブロン ユー．エス．エー． インコーポレイテッド | Reduction of CO2 in gas to liquid by using H2 as fuel |
| JP2007297443A (en) * | 2006-04-28 | 2007-11-15 | Chiyoda Corp | Method for producing syngas in kerosene/gas oil producing process from natural gas |
| WO2009008092A1 (en) * | 2007-07-10 | 2009-01-15 | Chiyoda Corporation | Process for produciton of synthesis gas in the process of manufacturing kerosene and gas oil from natural gas |
| JP2010526759A (en) * | 2007-05-11 | 2010-08-05 | ビーエーエスエフ ソシエタス・ヨーロピア | Syngas production method |
| US7863340B2 (en) | 2005-03-16 | 2011-01-04 | Fuelcor Llc | Systems, methods, and compositions for production of synthetic hydrocarbon compounds |
| JP2013538772A (en) * | 2010-07-09 | 2013-10-17 | エコ テクノル プロプライエタリー リミテッド | Generation of syngas by using membrane technology |
| KR20140019589A (en) * | 2012-08-06 | 2014-02-17 | 삼성전자주식회사 | Method of preparing syngas and method of preparing liquid fuel |
| KR20190027763A (en) | 2017-09-07 | 2019-03-15 | 한국화학연구원 | Bilayered catalytic reactor and system for producing the synthesis gas using the same |
| JP2021503034A (en) * | 2017-11-15 | 2021-02-04 | ガス、テクノロジー、インスティチュートＧａｓ Ｔｅｃｈｎｏｌｏｇｙ Ｉｎｓｔｉｔｕｔｅ | Processes and systems for reforming methane and light hydrocarbons into liquid hydrocarbon fuels |
| JP2022033893A (en) * | 2017-11-15 | 2022-03-02 | ガス、テクノロジー、インスティチュート | Process and system for reforming methane and light hydrocarbons into liquid hydrocarbon fuel |
| WO2022080088A1 (en) * | 2020-10-14 | 2022-04-21 | 国立研究開発法人産業技術総合研究所 | Method for producing hydrocarbon |
| US11667853B2 (en) | 2017-11-15 | 2023-06-06 | Gti Energy | Processes and systems for reforming of methane and light hydrocarbons to liquid hydrocarbon fuels |
-
1998
- 1998-09-30 JP JP29293098A patent/JP4132295B2/en not_active Expired - Fee Related
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001342003A (en) * | 2000-05-30 | 2001-12-11 | Mitsubishi Heavy Ind Ltd | Method of production for gasoline, gas oil and synthesis gas for kerosene |
| JP4681101B2 (en) * | 2000-05-30 | 2011-05-11 | 三菱重工業株式会社 | Method for producing synthesis gas for gasoline, light oil and kerosene |
| JP2002060762A (en) * | 2000-08-22 | 2002-02-26 | Mitsubishi Heavy Ind Ltd | Method of producing synthesis gas for synthesizing gasoline, lamp oil and gas oil |
| CN1867652B (en) * | 2003-10-16 | 2010-04-07 | 日本气体合成株式会社 | Method for producing liquefied petroleum gas containing propane and butane as main component |
| WO2005037962A1 (en) * | 2003-10-16 | 2005-04-28 | Japan Gas Synthesize, Ltd. | Method for producing liquefied petroleum gas containing propane or butane as main component |
| JP2007513887A (en) * | 2003-11-25 | 2007-05-31 | シェブロン ユー．エス．エー． インコーポレイテッド | Reduction of CO2 in gas to liquid by using H2 as fuel |
| US8114916B2 (en) | 2005-03-16 | 2012-02-14 | Fuelcor, Llc | Systems, methods, and compositions for production of synthetic hydrocarbon compounds |
| US7863340B2 (en) | 2005-03-16 | 2011-01-04 | Fuelcor Llc | Systems, methods, and compositions for production of synthetic hydrocarbon compounds |
| US8093305B2 (en) | 2005-03-16 | 2012-01-10 | Fuelcor, Llc | Systems, methods, and compositions for production of synthetic hydrocarbon compounds |
| US8168143B2 (en) | 2005-03-16 | 2012-05-01 | Fuelcor, Llc | Systems, methods, and compositions for production of synthetic hydrocarbon compounds |
| JP2007297443A (en) * | 2006-04-28 | 2007-11-15 | Chiyoda Corp | Method for producing syngas in kerosene/gas oil producing process from natural gas |
| JP2010526759A (en) * | 2007-05-11 | 2010-08-05 | ビーエーエスエフ ソシエタス・ヨーロピア | Syngas production method |
| WO2009008092A1 (en) * | 2007-07-10 | 2009-01-15 | Chiyoda Corporation | Process for produciton of synthesis gas in the process of manufacturing kerosene and gas oil from natural gas |
| AU2007356234B2 (en) * | 2007-07-10 | 2011-06-16 | Chiyoda Corporation | Synthesis Gas Production Method in a Process for Producing Kerosene and Gas Oil from Natural Gas |
| JP2013538772A (en) * | 2010-07-09 | 2013-10-17 | エコ テクノル プロプライエタリー リミテッド | Generation of syngas by using membrane technology |
| KR20140019589A (en) * | 2012-08-06 | 2014-02-17 | 삼성전자주식회사 | Method of preparing syngas and method of preparing liquid fuel |
| KR101964767B1 (en) | 2012-08-06 | 2019-04-02 | 연세대학교 원주산학협력단 | Method of preparing syngas and method of preparing liquid fuel |
| KR20190027763A (en) | 2017-09-07 | 2019-03-15 | 한국화학연구원 | Bilayered catalytic reactor and system for producing the synthesis gas using the same |
| JP2021503034A (en) * | 2017-11-15 | 2021-02-04 | ガス、テクノロジー、インスティチュートＧａｓ Ｔｅｃｈｎｏｌｏｇｙ Ｉｎｓｔｉｔｕｔｅ | Processes and systems for reforming methane and light hydrocarbons into liquid hydrocarbon fuels |
| JP2022033893A (en) * | 2017-11-15 | 2022-03-02 | ガス、テクノロジー、インスティチュート | Process and system for reforming methane and light hydrocarbons into liquid hydrocarbon fuel |
| US11667853B2 (en) | 2017-11-15 | 2023-06-06 | Gti Energy | Processes and systems for reforming of methane and light hydrocarbons to liquid hydrocarbon fuels |
| JP7331070B2 (en) | 2017-11-15 | 2023-08-22 | ガス、テクノロジー、インスティチュート | Process and system for reforming methane and light hydrocarbons to liquid hydrocarbon fuels |
| JP7398370B2 (en) | 2017-11-15 | 2023-12-14 | ジーティーアイ エナジー | Processes and systems for reforming methane and light hydrocarbons into liquid hydrocarbon fuels |
| EP4265705A3 (en) * | 2017-11-15 | 2024-04-03 | Gas Technology Institute | Process for reforming of methane and light hydrocarbons to liquid hydrocarbon fuels |
| WO2022080088A1 (en) * | 2020-10-14 | 2022-04-21 | 国立研究開発法人産業技術総合研究所 | Method for producing hydrocarbon |
| JP7549872B2 (en) | 2020-10-14 | 2024-09-12 | 国立研究開発法人産業技術総合研究所 | Hydrocarbon Production Methods |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4132295B2 (en) | 2008-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6806296B2 (en) | Process of producing liquid hydrocarbon oil or dimethyl ether from lower hydrocarbon gas containing carbon dioxide | |
| US6749828B1 (en) | Process for reforming hydrocarbon | |
| US4499209A (en) | Process for the preparation of a Fischer-Tropsch catalyst and preparation of hydrocarbons from syngas | |
| US7368625B2 (en) | Catalysts with high cobalt surface area | |
| EP2197816B1 (en) | Method of direct synthesis of light hydrocarbons from natural gas | |
| EA016492B1 (en) | Catalytic hydrogenation of carbon dioxide into syngas mixture | |
| KR20100014012A (en) | Catalyst for the preparation of synthesis gas from natural gas with carbon dioxide and the preparation method there of | |
| JP4132295B2 (en) | Method for producing liquid hydrocarbon oil from lower hydrocarbon gas containing carbon dioxide gas | |
| WO2011061484A2 (en) | Fischer-tropsch synthesis | |
| KR101437072B1 (en) | Catalyst for efficient co2 conversion and method for preparing thereof | |
| EP2293875A1 (en) | Bimetallic mo/co catalyst for producing of alcohols from hydrogen and carbon monoxide containing gas | |
| JP2000084410A (en) | Preparation of autothermal reforming catalyst and production of hydrogen or synthesis gas | |
| CA1200561A (en) | Catalytic process for the production of methanol | |
| US7169376B2 (en) | Method for making hydrogen using a gold containing water-gas shift catalyst | |
| JPS60208930A (en) | Manufacture of hydrocarbon | |
| KR102092736B1 (en) | Preparation Method of Reduced Carbon Poisoning Perovskite Catalyst Impregnated with Metal Ion, and Methane Reforming Method Threrewith | |
| WO2017085603A2 (en) | Methods for the conversion of co2 into syngas for use in the production of olefins | |
| US4022810A (en) | Metal chrysotile methane synthesis catalyst | |
| JP4833856B2 (en) | Method for converting synthesis gas to hydrocarbons in the presence of β-SiC | |
| KR102073959B1 (en) | Catalyst for synthesizing synthetic natural gas and manufacturing method for high calorific synthetic natural gas using the same | |
| KR20150129566A (en) | Ni-based catalysts for combined steam and carbon dioxide reforming with natural gas | |
| US3947483A (en) | Metal chrysotile methane synthesis catalyst | |
| AU764183B2 (en) | Improved fischer-tropsch activity for "non-promoted" cobalt-on-alumina catalysts | |
| JPS5857494A (en) | Preparation of aromatic-rich hydrocarbon from synthetic gas | |
| JP2000103757A (en) | Production of dimethyl ether from lower hydrocarbon gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20040723 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050420 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080219 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080418 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080520 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080602 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110606 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110606 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120606 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130606 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |