WO2002102932A1 - Method for producing hydrocarbons by fischer-tropsch process - Google Patents
Method for producing hydrocarbons by fischer-tropsch process Download PDFInfo
- Publication number
- WO2002102932A1 WO2002102932A1 PCT/JP2002/006015 JP0206015W WO02102932A1 WO 2002102932 A1 WO2002102932 A1 WO 2002102932A1 JP 0206015 W JP0206015 W JP 0206015W WO 02102932 A1 WO02102932 A1 WO 02102932A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- reaction
- mass
- hydrogen
- carbon dioxide
- Prior art date
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 87
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 42
- 230000008569 process Effects 0.000 title description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 216
- 238000006243 chemical reaction Methods 0.000 claims abstract description 206
- 239000007789 gas Substances 0.000 claims abstract description 155
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 154
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 103
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 98
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 94
- 239000001257 hydrogen Substances 0.000 claims abstract description 90
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 77
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 77
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 230000009467 reduction Effects 0.000 claims abstract description 44
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 43
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 40
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 description 75
- 230000015572 biosynthetic process Effects 0.000 description 71
- 239000002245 particle Substances 0.000 description 63
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- 150000001336 alkenes Chemical class 0.000 description 35
- 238000009826 distribution Methods 0.000 description 31
- 239000002002 slurry Substances 0.000 description 30
- 239000012188 paraffin wax Substances 0.000 description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 24
- 230000007423 decrease Effects 0.000 description 24
- 239000002904 solvent Substances 0.000 description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 20
- 239000000843 powder Substances 0.000 description 20
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 19
- 239000003921 oil Substances 0.000 description 19
- 229910052786 argon Inorganic materials 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 17
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 17
- 239000001307 helium Substances 0.000 description 16
- 229910052734 helium Inorganic materials 0.000 description 16
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 16
- 239000003350 kerosene Substances 0.000 description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 description 13
- 239000011734 sodium Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000003345 natural gas Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 239000001993 wax Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- -1 this "Leto Chemical compound 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 238000006114 decarboxylation reaction Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 150000003304 ruthenium compounds Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 101001012040 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Immunomodulating metalloprotease Proteins 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003303 ruthenium Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002453 autothermal reforming Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 150000003388 sodium compounds Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 241000705939 Shortia uniflora Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- AYRBBDWFLGUINX-UHFFFAOYSA-N acetyl acetate;ruthenium Chemical compound [Ru].CC(=O)OC(C)=O AYRBBDWFLGUINX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical group [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/31—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
Definitions
- the present invention relates to a method for producing hydrocarbons such as mixed gas (hereinafter, referred to as “synthesis gas”) containing hydrogen and carbon monoxide as main components. More specifically, the synthesis gas is brought into contact with a ruthenium-based catalyst using a carrier composed of aluminum oxide and manganese oxide dispersed in liquid hydrocarbons, and the hydrocarbons, especially a light gas oil fraction
- synthesis gas such as mixed gas (hereinafter, referred to as “synthesis gas”) containing hydrogen and carbon monoxide as main components. More specifically, the synthesis gas is brought into contact with a ruthenium-based catalyst using a carrier composed of aluminum oxide and manganese oxide dispersed in liquid hydrocarbons, and the hydrocarbons, especially a light gas oil fraction
- the present invention relates to a process for producing hydrocarbons rich in olefins together with wax components that can be easily converted into olefins. Background art
- Fischer 'Tropsch reaction Fischer- Tropsch reaction, hereinafter referred to as "FT reaction”
- methanol synthesis reaction C 2 oxygenated (ethanol, ⁇ acetaldehyde)
- synthesis Well known Fischer- Tropsch reaction, hereinafter referred to as "FT reaction”
- FT reaction is iron
- this "Leto, iron-based catalysts such as ruthenium, methanol synthesis reaction with a copper-based catalyst, C 2 oxygenates synthesis reaction is known you to proceed with rhodium-based catalyst
- the catalytic activity of the catalyst used for synthesizing these hydrocarbons is strongly related to the dissociative adsorption ability of carbon monoxide (for example, “homogeneous catalyst and heterogeneous catalyst”, Hatsutai, co-authored by Ichikawa, Maruzen, published in Showa 58).
- GTL a technology that synthesizes liquid fuels such as kerosene and light oil from natural gas (mainly methane), which is said to have recoverable reserves equivalent to crude oil in terms of energy. (gas to liquid).
- FT method a method for producing hydrocarbons from synthesis gas by the FT reaction
- the carbon number distribution of hydrocarbon products in the FT reaction is assumed to follow the Shultz-Flory law. According to the Schultz-Flory law, the chain growth probability ( ⁇ ) increases with the reaction temperature. It states that the number of carbon atoms in the produced hydrocarbons tends to decrease when the reaction temperature rises.
- the synthesis gas which is a raw material for the production of hydrocarbons by the FT method in the GTL process
- the synthesis gas is mainly composed of natural gas obtained by autothermal reforming or steam reforming. It is obtained by reforming into a mixed gas containing hydrogen and carbon monoxide as main components by the reforming method.
- the resulting synthesis gas in addition to the reforming reaction of the following formula (I), the following formula (I) Since the water gas shift reaction of II) occurs in parallel, the resulting synthesis gas necessarily contains carbon dioxide gas. Furthermore, many of the unused natural gas fields contain carbon dioxide gas. If natural gas containing such carbon dioxide is used as a raw material, the carbon dioxide content of the resulting synthesis gas is further increased.
- liquid hydrocarbons are synthesized from synthesis gas as shown by the following formula (III).
- carbon dioxide gas is contained in the reaction system, there is a tendency that the synthesis of hydrocarbons is hindered.
- the partial pressure of hydrogen in the reaction system decreases in addition to the above-described inhibition of the reaction of carbon dioxide gas, and this situation is also unfavorable for the FT reaction.
- n CO + 2 nH 2 (CH 2 ) n + nH z O (III) Therefore, conventionally, in the GTL process, it is essential to incorporate a decarboxylation step to remove carbon dioxide in synthesis gas between the step of producing synthesis gas from natural gas and the step of synthesizing liquid hydrocarbons from synthesis gas. Becomes In this decarboxylation process, usually, amine absorption or pressure swing adsorption (PSA) is used, but in any case, the decarboxylation process increases construction costs and operating costs. It is not preferable, such as inviting.
- PSA pressure swing adsorption
- the FT reaction can be suitably performed in the coexistence of carbon dioxide gas, and the above-mentioned decarboxylation step can be simplified or omitted, it can greatly contribute to reducing the production cost of liquid hydrocarbons in the GTL process. .
- the above-mentioned ruthenium-based catalyst is a catalyst developed mainly for use in a fixed-bed type.
- the chain growth probability of this ruthenium-based catalyst is Not only ( ⁇ ), etc., but in the fixed-bed type reaction system, when a large amount of wax is generated, the generated wax adheres to and covers the active sites of the catalyst, and the activity of the catalyst decreases.
- Another object of the present invention is to provide an FT method which can stably and smoothly carry out a reaction and which can carry out such a desired reaction in the selective coexistence of carbon dioxide gas.
- By hydrogenolysis of distillate and dimerization and trimerization of generated olefins can contribute more to the increase in production of kerosene and gas oil fractions than before, and simplify the decarbonation process of removing carbon dioxide from synthesis gas.
- the present invention provides a carrier containing an aluminum oxide and a manganese oxide having an average charge number of manganese exceeding Mn 2+ , wherein the carrier is selected from alkali metals, alkaline earth metals, rare earths, and Group III of the periodic table. 0 the catalyst relative to the at least one metal. 1-1 and 0 wt% supported further, ruthenium was supported 1-3 0% by weight in the catalyst basis, the specific surface area 6 0 ⁇ 3 5 0 m 2 _ g , The bulk density of 0.8 to: A catalyst exhibiting I.8 g / m 1 is reduced,
- a mixed gas containing hydrogen and carbon monoxide is supplied to the catalyst at a pressure of 1 to 10 M P &
- the present invention relates to a method for producing hydrocarbons.
- the present inventors have conducted intensive studies to achieve the above object, and as a result, as a catalyst, a fixed amount of a fixed metal such as an alkali metal and a fixed amount of ruthenium are supported on a support composed of aluminum oxide and a fixed manganese oxide. After using a catalyst having a relatively large constant specific surface area and a relatively small constant bulk density, the catalyst is subjected to a reduction treatment in advance, and then is dispersed in a liquid hydrocarbon at a constant concentration. By bringing the raw material synthesis gas into contact with the catalyst in a state, the FT reaction can be performed with a high chain growth probability (h) even in the absence of carbon dioxide (carbon dioxide) or in the presence of carbon dioxide.
- the specific reaction type in which the catalyst is dispersed in liquid hydrocarbons at a constant concentration and brought into contact with the raw material synthesis gas as described above It is possible to prevent a decrease in catalytic activity due to the attachment of pettas to the catalytically active sites, and to suppress the generation of heat spots, thereby making it possible to carry out the reaction stably and smoothly.
- the catalyst having the above specific composition and physical properties is the most suitable catalyst for the above specific reaction mode, and has a high chain growth probability (H), and is excellent in olefin selectivity and C 5 + productivity.
- Reaction can be realized And a catalyst capable of realizing such a suitable FT reaction substantially in the absence of carbon dioxide or in the presence of a certain amount of carbon dioxide. In order to further promote the FT reaction and further improve the conversion of carbon monoxide, it is preferable to carry out the reaction in the presence of a certain amount of carbon dioxide.
- the object of the present invention can be achieved simply by reducing the bulk density of the catalyst.
- the conventionally known catalyst in which sodium and ruthenium are supported on an alumina carrier having a low bulk density has low C 5 + productivity and a chain growth probability ( ⁇ )
- the object of the present invention cannot be achieved due to low selectivity to olefins, whereas a carrier such as an alkali metal and ruthenium is added to a carrier comprising an aluminum oxide and a certain manganese oxide used in the present invention.
- the C 5 + productivity can be increased by keeping the bulk density within a relatively small range, and a high chain growth probability ( ⁇ and olefin selectivity) can be obtained.
- a support made of a manganese oxide having an average charge number of aluminum oxide and manganese exceeding Mn 2 + is added to an alkali metal, an alkaline earth metal, a rare earth and an elemental periodic law.
- neutral alumina or alkaline alumina is preferably used as an aluminum oxide as one component of the carrier in order to obtain a high chain growth probability ( ⁇ ) and stable reaction activity. If acidic alumina is used, the chain growth probability ( ⁇ ) may decrease and the reaction activity may decrease. Cost.
- a manganese oxide having an average charge number of manganese exceeding Mn 2 + is used as the manganese oxide as another component of the carrier.
- a manganese oxide having an average charge number of manganese of Mn 2+ or less is, for example, a gaseous hydrocarbon (C 2 to C 4 ) olefin as shown in U.S. Pat. It is not suitable for producing liquid hydrocarbons, which is the object of the present invention.
- Examples of the manganese oxide having an average number of charges of manganese exceeds Mn 2 +, Mn0 2, such as Mn 2 0 3, Mn 3 ⁇ 4 are preferably exemplified. It is also possible to use a manganese oxide in which a salt other than an oxide such as manganese nitrate is used as a starting material and the average charge number of manganese obtained therefrom exceeds Mn 2 + . For example, it can be preferably used, such as Mn 2 0 3 obtained by firing manganese nitrate in air.
- the ratio of aluminum oxide to manganese oxide in the carrier is generally 5 to 160 parts by mass of manganese oxide with respect to 10 parts by mass of aluminum oxide, preferably 10 to 10 parts by mass. To 110 parts by mass.
- the proportion of the manganese oxide is less than 5 parts by mass, the interaction between the manganese oxide and the metal and the metal decreases, and the chain growth probability (a) and the C 5 + selectivity are reduced. / Paraffin ratio may decrease, and may not be suitable for production of liquid hydrocarbons.On the other hand, if it exceeds 160 parts by mass, the bulk density or specific surface area of the catalyst may not satisfy the suitable range There is fear.
- the preparation of the carrier can be carried out according to a conventional method, and can be carried out by mixing and firing a predetermined ratio of an aluminum oxide raw material and a manganese oxide raw material.
- the carrier may be in any shape such as a powder, a granule, a tablet, and an extruded product.
- the amount of supported metal or ruthenium is related to the number of active points.
- the amount of the metal supported on the catalyst used in the present invention is 0.1 to 10% by mass, preferably 0.2 to 7% by mass, and more preferably 0.2 to 3% by mass, based on the catalyst.
- the supported amount of ruthenium is 1 to 30% by mass, preferably 1 to 20% by mass, and more preferably 1.5 to 10% by mass based on the catalyst. You. If the supported amount of metal or ruthenium is less than the above range, the number of active points may be insufficient and sufficient catalytic activity may not be obtained.
- metal species such as metal and ruthenium and carrier components (aluminum, No synergistic effect with manganese) is obtained, and the degradation gradient and catalyst stability (life) are lacking.
- the supported amount of each metal element exceeds the above range, the metal and ruthenium are not sufficiently supported on the carrier, and the dispersibility and the metal species having no interaction with the carrier component are reduced. Since ruthenium species are expressed, the activity and selectivity tend to be remarkably reduced, which is not preferable.
- the chemical composition of the catalyst was determined by inductively coupled plasma mass spectrometry (ICP method).
- the specific surface area of the catalyst used in the present invention is a 60 ⁇ 350m 2 Zg, preferably 80 to 30 Om 2 Zg, more preferably 100 to 250 m 2 Zg.
- the specific surface area is less than 60 m 2 Zg, the dispersibility of metal perruthenium may decrease, which is not preferable.
- the upper limit of the specific surface area in general, when handling a solid catalyst, the larger the specific surface area, the higher the frequency of gas-liquid-solid contact.
- the practical upper limit of the specific surface area of the carrier composed of the aluminum oxide and the manganese oxide used in the present invention is about 350 to 380 m 2 / g, the metal It is thought that the maximum of the catalyst supporting ruthenium is about 350 m 2 / g.
- the specific surface area of the catalyst was determined by the BET method (Braunauer-Emett-Tailor method) using high-purity nitrogen as a probe.
- the bulk density of the catalyst used in the present invention is 0.8 to 1.8 gZml, preferably 0.9 to 1.5 gZm1, and more preferably 0.9 to 1.3. g / m 1.
- the metal It is considered that the minimum value of the catalyst loaded with is about 0.8 g / ml.
- the bulk density exceeds 1.8 g / m1
- the catalyst used in the present invention preferably has a catalyst particle size distribution range of 5 to 200, more preferably 5 to 180 ⁇ , and 10 to 150 ⁇ m Is even more preferred.
- the catalyst since the catalyst is used in a dispersed state by being dispersed in liquid hydrocarbons, it is desirable to consider its particle size distribution. Fine particles, such as those smaller than 5 im, pass through the filter etc. and overflow to the downstream side, causing problems such as a decrease in the catalyst concentration in the reaction vessel, and the downstream equipment being hindered by catalyst particles. Is more likely to occur.
- particles as large as more than 200 m are difficult to disperse uniformly in liquid hydrocarbons over the entire reaction vessel, or the slurry in which the catalyst is dispersed becomes uneven. Thus, the possibility that the reaction activity decreases is increased.
- the dispersion may be biased when dispersed in liquid hydrocarbons.
- the average particle diameter of the catalyst used in the present invention is preferably from 20 to 100 ⁇ , more preferably from 25 to 100 ⁇ m, even more preferably from 25 to 80 im. If the average particle size is outside the upper and lower limits of the above range of 20 to 100 m, the catalyst particles may be unevenly dispersed in the liquid hydrocarbons, and the reaction activity may be reduced. is there.
- the catalyst used in the present invention can be prepared according to a generally known method for preparing a supported catalyst.
- the metal or ruthenium is supported on the carrier made of the aluminum oxide or the manganese oxide, first, the metal is supported, moisture is removed, and then firing is performed. Next, ruthenium is supported, and after removing water, it is sufficiently dried.
- the metal or ruthenium supported on the carrier may be, for example, a metal compound or a ruthenium compound. Immersed in a solution of a catalyst species compound such as described above to allow the catalyst species compound to be adsorbed on the carrier, adhere by ion exchange, or be deposited by adding a precipitant such as alkali.
- the solution may be evaporated to dryness, or the solution of the catalyst seed compound may be dropped on the carrier, for example, to bring the carrier into contact with the solution of the catalyst seed compound.
- the amounts of these catalyst species compounds to be contained in the carrier are adjusted so that the supported amounts of metal and ruthenium in the obtained target catalyst are the above-mentioned predetermined amounts.
- the metal compound supported on the carrier include sodium, potassium, lithium, beryllium, barium, magnesium, cellium, calcium, yttrium, and the like, carbonates, nitrates, and ammonium salts. Compounds such as potassium and calcium are preferably used. These metal compounds can be used alone or in combination of two or more.
- ruthenium compound various ruthenium compounds conventionally used for preparing a ruthenium-supported catalyst can be appropriately selected and used.
- Preferred examples thereof include water-soluble ruthenium salts such as ruthenium chloride, ruthenium nitrate, ruthenium acetate, and ruthenium hexaammonium, and ruthenium compounds soluble in organic solvents such as ruthenium carbonyl, ruthenium acetyl acetate, and the like.
- the support containing the metal and ruthenium as described above is dried. In general, this drying can be performed by maintaining the composition at room temperature to 300 ° C. for 10 to 48 hours.
- the dried catalyst-type-containing carrier is appropriately pulverized and classified as necessary, to obtain a powder having a desired catalyst particle size distribution and, if necessary, a desired average particle size, and thus used in the present invention.
- a catalyst having predetermined physical properties can be obtained.
- the catalyst prepared as described above is subjected to a reduction treatment (activation treatment) before being subjected to the FT reaction.
- the catalyst is activated so as to exhibit a desired catalytic activity in the FT reaction. If this reduction treatment is not performed, the metal and ruthenium supported on the carrier will not be sufficiently reduced, and will not exhibit the desired catalytic activity in the FT reaction.
- the reduction treatment is preferably performed by a method in which the catalyst is contacted with a reducing gas in a slurry state in which the catalyst is dispersed in liquid hydrocarbons, or a method in which the reducing gas is simply passed through the catalyst without using hydrocarbons.
- a method in which the catalyst is dispersed in the former method various kinds of liquid hydrocarbons such as olefins, alkanes, alicyclic hydrocarbons, and aromatic hydrocarbons can be used as long as they are liquid under the treatment conditions. Hydrocarbons can be used. Further, it may be a hydrocarbon containing a hetero element such as oxygen-containing or nitrogen-containing.
- the carbon number of these hydrocarbons is not particularly limited as long as it is liquid under the treatment conditions, but is generally c 6 to c 4 . Rather the preferred ones, are more preferably a c 9 to c 40, it is the most preferred of c 9 ⁇ c 3 5. intended for lighter than hydrocarbons c 6 increases the vapor pressure of the solvent, so that the processing condition width is limited. In addition, C 4. If it is heavier than the above hydrocarbons, there is a concern that the solubility of the reducing gas will decrease, and sufficient reduction treatment will not be possible.
- the amount of the catalyst dispersed in the hydrocarbons is suitably from 1 to 50% by mass, preferably from 3 to 40% by mass, and more preferably from 5 to 35% by mass.
- the amount of the catalyst is less than 1% by mass, the reduction efficiency of the catalyst decreases.
- As a method of preventing the reduction efficiency of the reduction of the catalyst there is a method of reducing the amount of gas passing through the reducing gas. This is not preferable because the dispersion of the catalyst is impaired.
- the temperature of the reduction treatment is preferably from 140 to 310 ° C, more preferably from 150 to 250 ° C, and most preferably from 160 to 220 ° C.
- ruthenium is not sufficiently reduced, and sufficient reaction activity cannot be obtained.
- phase transitions such as manganese oxide on the carrier, changes in oxidation state, etc. proceed to form a complex with ruthenium, which causes sintering of the catalyst. (Sintering), and the possibility of causing a decrease in activity is increased.
- a reducing gas mainly composed of hydrogen is used.
- the reducing gas used may contain a certain amount of components other than hydrogen, for example, water vapor, nitrogen, a rare gas, etc. within a range that does not hinder the reduction.
- This reduction treatment is affected by the hydrogen partial pressure and the processing time together with the above-mentioned processing temperature, but the hydrogen partial pressure is preferably 0.1 to 1 OMPa, more preferably 0.5 to 6 MPa, 1-5 MPa is most preferred.
- the reduction treatment time varies depending on the amount of catalyst, the amount of hydrogen introduced, and the like, but is generally preferably 0.1 to 72 hours, more preferably 1 to 48 hours, and most preferably 4 to 48 hours. If the treatment time is less than 0.1 hour, the activation of the catalyst becomes insufficient. Further, even if the reduction treatment is carried out for a long time exceeding 72 hours, there is no adverse effect on the catalyst, but there is no improvement in the catalyst performance, but undesired problems such as an increase in treatment cost are caused.
- the catalyst after the above-mentioned reduction treatment preferably has a certain range of ruthenium dispersibility. That is, in general, the dispersibility of the ruthenium is the percentage of the number of moles of adsorbed carbon monoxide (CO) of the catalyst after the reduction treatment to the number of moles of ruthenium in the catalyst, and is defined by the following equation. You. Number of moles of CO adsorbed on catalyst
- the number of Ru moles in the catalyst indicates the proportion of ruthenium species active in hydrogenation of CO out of the ruthenium in the catalyst, and the ruthenium dispersibility is high for the same amount of ruthenium carried.
- the catalyst used for the FT reaction needs both the hydrogenation activity of CO and the activity of chain growth, and even if the hydrogenation activity of CO is increased, the activity of the chain growth is low.
- the catalyst used in the present invention preferably has a ruthenium dispersibility of 16 to 50% after the reduction treatment.
- the catalyst reduced as described above is subjected to the FT reaction, that is, the synthesis reaction of hydrocarbons.
- the catalyst is formed in a dispersed state in which the catalyst is dispersed in liquid hydrocarbons, and a synthesis gas is brought into contact with the catalyst in the dispersed state.
- the hydrocarbons in which the catalyst is dispersed the same hydrocarbons as those used in the above-described reduction treatment can be used.
- heteroelements such as various hydrocarbons including olefins, alkanes, alicyclic hydrocarbons, aromatic hydrocarbons, oxygen-containing, nitrogen-containing, etc. Can be used, and the number of carbon atoms is not particularly limited, but is generally C 6 to C 4 . Preferably, it is C 9 -C 4 . More preferably a, the most favorable preferable ones C 9 ⁇ C 3 5. If the hydrocarbons are lighter than C 6 hydrocarbons, the vapor pressure of the solvent will increase, and the range of reaction conditions will be limited. In addition, C 4.
- the solubility of the synthesis gas as the raw material decreases and the reaction activity decreases.
- the liquid hydrocarbons used in the reduction treatment may be directly used in the FT reaction. it can.
- the amount of the catalyst dispersed in the hydrocarbons is 1 to 50% by mass, preferably 3 to 40% by mass, more preferably 5 to 35% by mass. 1 mass of catalyst. If it is less than / 0 , the activity decreases.
- a method of preventing the activity from decreasing there is a method of reducing the amount of the synthesis gas to be passed.
- the amount of the synthesis gas is reduced, the dispersion of the gas (synthesis gas), one liquid (solvent) and one solid (catalyst) is impaired. Therefore, it is not preferable.
- the amount of the catalyst is more than 50% by mass, the viscosity of the slurry in which the catalyst is dispersed in the hydrocarbons becomes too high, the bubble dispersion becomes poor, and sufficient reaction activity cannot be obtained. Not preferred.
- the synthesis gas used for the FT reaction only needs to contain hydrogen and carbon monoxide as main components, and other components that do not interfere with the FT reaction may be mixed. Since the rate (k) of the FT reaction is approximately linearly dependent on the hydrogen partial pressure, hydrogen and carbon monoxide Is desired to have a partial pressure ratio (H 2 / CO molar ratio) of 0.6 or more. Since this reaction is a reaction involving a decrease in volume, the higher the total value of the partial pressures of hydrogen and carbon monoxide, the better.
- the upper limit of the partial pressure ratio of hydrogen and carbon monoxide is not particularly limited, a practical range of the partial pressure ratio is 0.6 to 2.7, and preferably 0.8 to 2.7. It is 2.5, more preferably 1-2.
- the total value of the partial pressures of hydrogen and carbon monoxide is preferably from 1 to 10 MPa, more preferably from 1 to 6 MPa, and from 1.5 to 4.5 MPa. MPa is most preferred. If it is less than IMPa, the rate of the FT reaction becomes insufficient, and the yield of gasoline, kerosene oil, wax, etc. tends to decrease, which is not preferable.
- the upper limit of the partial pressure is regulated.
- the substantial absence of carbon dioxide means that carbon dioxide does not exist or is less than 0.5% with respect to the total pressure of hydrogen and carbon monoxide in the mixed gas.
- carbon dioxide as the coexisting carbon dioxide, for example, those obtained from the reforming reaction of petroleum products or natural gas can be used without any problem, and other components that do not hinder the FT reaction It may be mixed, for example, it may contain steam or partially oxidized nitrogen or the like, such as one from a steam reforming reaction of petroleum products.
- This carbon dioxide can be positively added to the synthesis gas containing no carbon dioxide, or can be obtained by reforming natural gas by an autothermal reforming method or a steam reforming method. It is also possible to use the carbon dioxide in the carbon dioxide-containing synthesis gas, that is, to directly use the carbon dioxide-containing synthesis gas for the FT reaction without decarbonation treatment. You.
- the facility construction and operation costs required for the decarbonation treatment can be reduced, and the production cost of hydrocarbons obtained by the FT reaction can be reduced.
- the amount of coexisting carbon dioxide is 0.5 to 50%, preferably 0.5 to 30%, more preferably 0.5 to 30%, based on the total pressure of hydrogen and carbon monoxide in the mixed gas used for the FT reaction. Or 1 to 10%. If the partial pressure of carbon dioxide in the synthesis gas (mixed gas) to be subjected to the FT reaction is lower than the above range, the effect of promoting the FT reaction by carbon dioxide cannot be obtained, and the range exceeds the above range.
- the partial pressures of hydrogen and carbon monoxide in the synthesis gas (mixed gas) to be subjected to the FT reaction decrease, and the yield of hydrocarbons decreases, which is economically disadvantageous.
- it may be allowed to coexist in the reaction system from the beginning of the FT reaction.However, in order to more effectively exert the effect of promoting the FT reaction of carbon dioxide and improve the conversion rate of carbon monoxide. For this purpose, it is preferable to introduce and coexist in the reaction system within 10 to 100 hours after the start of the FT reaction.
- the total pressure of the synthesis gas (mixed gas) to be subjected to the FT reaction is preferably 1 to: L OMPa, and 1. 5 to 6 MPa is more preferable, and 1.8 to 4.5 MPa is still more preferable. If it is less than IMPa, chain growth is insufficient, and the yields of gasoline, kerosene and gas oil, wax and the like tend to decrease, which is not preferable. In terms of equilibrium, the higher the partial pressure of hydrogen and carbon monoxide, the more advantageous. However, the higher the partial pressure, the higher the cost of plant construction, etc., and the larger the compressor required for compression, the lower the operating cost.
- the upper limit of the partial pressure is regulated from an industrial viewpoint such as a rise.
- the mixed gas containing hydrogen and carbon monoxide for example, in the absence of carbon dioxide or in the coexistence of carbon dioxide, produces water, nitrogen, noble gas, etc. within a range that does not interfere with the FT reaction. It may contain a certain amount.
- this FT reaction generally, if the H 2 / CO molar ratio of the synthesis gas is the same, the lower the reaction temperature, the higher the chain growth and the higher the olefin selectivity, but the lower the CO conversion. Conversely, as the reaction temperature increases, the chain growth and the selectivity for olefins decrease, but the CO conversion increases.
- the reaction temperature in the substantial absence of carbon dioxide, is preferably 170 to 300 ° C, and 190 to 300 ° C. -290 ° C is more preferred, and 200-290 ° C is even more preferred.
- the reaction temperature is preferably from 200 to 350 ° C, more preferably from 210 to 310 ° C, even more preferably from 220 to 290 ° C.
- CO conversion rate The CO conversion, chain growth probability ( ⁇ ), and C 5 + productivity are defined by the following equations. CO conversion rate
- CO conversion rate -X100 Number of moles of co in raw material gas per unit time Chain growth probability (c:
- the C 5 + productivity refers to the amount of C 5 + produced per unit weight of the catalyst, and is defined by the following equation.
- the CP (CQM-10000P, manufactured by Shimadzu Corporation) was used to determine the particle size distribution using a laser light scattering particle size analyzer (Mastersizer MSX-46, manufactured by Malvern), and the manganese oxide structure was analyzed by X-ray diffraction (RI NT 2500 , Manufactured by Rigaku Denki Kogyo).
- a fully automatic catalytic gas adsorption measuring device (R-6015, manufactured by Okura Riken) equipped with a TCD gas chromatograph was used.
- the procedure for measuring the number of adsorbed CO moles is as follows: a catalyst is placed in a test tube, helium gas is used as a carrier gas, and hydrogen gas is used as a reducing gas. The test was then performed by switching to helium gas and cooling to 50 ° C, and then measuring the number of adsorbed CO moles by flowing a constant amount of CO gas into the test tube.
- Water Pure water (hereinafter abbreviated as “water”) was added dropwise to the alumina powder which had been sufficiently dried in advance to determine the saturated water absorption.
- the saturated water absorption at this time was 0.9 m 1 / g.
- 30 g of aluminum oxide is impregnated with an aqueous solution of 168 g of manganese nitrate hexahydrate dissolved in 27 m1 of water, allowed to stand for about 4 hours, dried in air at a temperature of 110 ° C, and then dried in a Matsufur furnace. It was baked at 600 ° C for 3 hours in air.
- Catalyst A had an average particle size of 95 ⁇ , a bulk density of 1.6 gZm 1, and a specific surface area of 100 m 2 Zg.
- X-ray diffraction result of structural analysis by, manganese oxide is Mn 2 0 3, and an average number of charges Mn 3+.
- AO.3 g of the catalyst was charged into a reactor having an internal volume of 100 ml together with 3 Oml (n-C 16 H 34 , hereinafter referred to as a solvent) of a dispersion medium, normal hexadecane (slurry, 1 g / 10 Om 1) Hydrogen was brought into contact with catalyst A at a hydrogen partial pressure of 10 MPa a ⁇ G, a temperature of 140 ° C. and a flow rate of 100 ml / min (STP: standard temperature and pressure), and reduced for 1 hour. After reduction, the atmosphere was replaced with helium gas, the temperature was set to 100 ° C, and the pressure was set to normal pressure. Thereafter, argon 10 V o 1%, carbon monoxide 56.
- 3 Oml n-C 16 H 34 , hereinafter referred to as a solvent
- STP standard temperature and pressure
- the reactor was charged with 10.5 g of catalyst C, and hydrogen partial pressure IMP aG, temperature 220 ° C, Hydrogen was brought into contact with catalyst C at a flow rate of 10 Oml Zmin (STP) and reduced for 48 hours.
- the atmosphere was replaced with helium gas, the temperature was set to 100 ° C, the pressure was set to normal pressure, and then 3 Oml of the solvent (slurry concentration: 35 g / 10 Om1) was pumped. After that, switch to argon 10 Vo 1%, carbon monoxide 27.3 Vo 1%, and the remaining hydrogen syngas (H 2 ZCO ratio 2.3), temperature 280 ° C, 112 2 + ⁇ 0 pressure
- the FT reaction was performed under the conditions of 1.8 MPa and G.
- the gas flow rate of the synthesis gas at which the conversion was 60% was W / F 2.2 g ⁇ hr / mo 1.
- the chain propagation probability is 0. 89
- C 5 + selectivity was 82%
- Orefin / paraffin ratio in C 3 is 3.8
- C 5 + productivity 930 g / kg / hr.
- the reactor was charged with 12 g of catalyst D, and hydrogen was reduced for 24 hours by bringing hydrogen into contact with catalyst D at a hydrogen partial pressure of 0.5 MPa ⁇ G, a temperature of 250 ° C, and a flow rate of 100 ml / min (STP).
- the atmosphere was replaced with helium gas, the temperature was adjusted to 100 ° C., and the pressure was adjusted.
- 30 ml of a solvent slurry concentration: 40 gZl Om 1
- the FT reaction was performed under the conditions of 5MPa.G.
- the gas flow rate of the synthesis gas at which the conversion was 60% was WZF 2.0 g ⁇ hr Zmo1.
- the chain growth probability (a) is 0. 8 8
- C 5 + selectivity was 8 3%
- C a A ssay 1 7 mass 0/0 calcium nitrate tetrahydrate
- 2.2 g of ruthenium chloride particle distribution 5 to 200 ⁇ m, average particle size 95 ⁇ m, bulk density 1.6 g / m 1 and specific surface area 10
- Has the physical properties of 0m 2 / g, 1 11 1 wt% in terms of 0.1% by mass ⁇ & terms, M 1 1 2 0 3 60 wt%, the remainder aluminum oxide (aluminum oxide: manganese oxide 10 ° parts by mass: 154 parts by mass).
- catalyst F 0.3 g was charged into a reactor together with 3 Oml of solvent (slurry concentration: 3 g / 10 Oml), and hydrogen partial pressure was 1 OMPaG, temperature was 10 ° C, and flow rate was 100 ml / min (STP). Hydrogen was brought into contact with catalyst F and reduced for 1 hour. After reduction, the atmosphere was replaced with helium gas, the temperature was set to 100 ° C, and the pressure was set to normal pressure. The Ru dispersibility of Catalyst F after reduction was 38%. Thereafter, argon 10 V o 1%, carbon monoxide 56.
- the FT reaction was performed in the same manner as above, except that carbon dioxide was not introduced.
- the chain growth probability ( ⁇ ) was 0.92
- the C 5 + selectivity was 92%
- the olefin / paraffin ratio in C 3 was 4, and the C 5 + productivity was 420 g / kg / hr. .
- the nitrate manganese 1 14. 8 g alkaline alumina powder 30 g, then sodium carbonate (N a As say 43. 2 Mass 0/0) 0. 7 g, then impregnated with ruthenium chloride 3 ⁇ . 6 g, particle distribution 1 0 to 180 mu m, an average particle diameter of 80 mu m, bulk density 1. 45 g / m 1 Oyopi ratio surface area 14 Om 2 / ⁇ of It has physical properties, 2% by mass in terms of Ru, 0.5% by mass in terms of Na, 50% by mass of Mn 2 O 3 0 /.
- the atmosphere was replaced with helium gas, the temperature was set to 100 ° C., the pressure was set to normal pressure, and then 3 Oml of the solvent (slurry concentration: 5 gZl0 Oml) was pumped into the reactor.
- the Ru dispersibility of the reduced Catalyst H was 33%.
- alumina powder was impregnated with 49.5 g of manganese nitrate, 1 g of sodium carbonate, and then 3.9 g of ruthenium chloride, and the particle distribution was obtained.
- 20 ⁇ : 1 50 ⁇ ⁇ , average particle size 60 mu m, bulk density: 1. have the physical properties of the 2 5 gm 1 and a specific surface area 1 6 5m 2 / g, R u converted 3 mass 0/0, Na converted 0 . 9 mass%, Mn 2 O 3 3 3 0 wt%, the remainder aluminum oxide to obtain a catalyst I comprising a (Al Miniumu oxide: manganese oxide 1 00 parts by 45 weight parts).
- aluminum oxide: manganese oxide 100 parts by mass: 46 parts by mass
- the reactor was charged with 10.5 g of the catalyst K, and hydrogen was reduced for 48 hours by bringing the hydrogen into contact with the catalyst K at a hydrogen partial pressure of IMPa ⁇ G, a temperature of 220 ° C, and a flow rate of 100 m1 / min (STP).
- the atmosphere was replaced with helium gas, the temperature was set to 100 ° C., the pressure was set to normal pressure, and 3 Oml of the solvent (slurry concentration: 35 gZl0 Om 1) was pumped.
- the Ru dispersibility of the reduced catalyst was 29%. Thereafter, argon 10 V o 1%, carbon monoxide 2 7.
- the FT reaction was performed in the same manner as above, except that carbon dioxide was not introduced.
- the chain growth probability (h) is 0.89
- the C 5 + selectivity is 82%
- the olefin Z paraffin ratio in C 3 is 3.8
- the C 5 + productivity is 9 30 gZk gZh r.
- a reactor was charged with 12 g of catalyst L, and hydrogen was brought into contact with catalyst L at a partial pressure of hydrogen of 0.5 MPa a G at a temperature of 250 ° C and a flow rate of 10 Om l Zmin (STP). It was reduced for 24 hours. After reduction, the atmosphere was replaced with helium gas, the temperature was adjusted to 100 ° C. and the pressure, and then 3 Oml of the solvent (slurry concentration: 40 g / 10 Om1) was pumped. The Ru dispersibility of the reduced Catalyst L was 22%.
- the chain growth probability ( ⁇ ) is 0.87, C 5 + selectivity is 79%, ratio of olefin / paraffin in C 3 is 3.8, and C 5 + productivity was 1100 g / kg / hr.
- the FT reaction was performed in the same manner as above, except that carbon dioxide was not introduced. That As a result, the chain growth probability ( ⁇ ) was 0.88, the C 5 + selectivity was 80%, the ratio of olefin / paraffin in C 3 was 3.9, and the C 5 + productivity was 1000 g / kg gZhr. there were.
- alumina powder was impregnated with 85.7 g of manganese nitrate, 102.7 g of calcium nitrate, and then 85.7 g of ruthenium chloride. , particle distribution. 5 to 70 mu m, an average particle diameter of 25 m, Ru converted 30% of the bulk density 1. 8 gZm 1 and a specific surface area of 6 Om 2 Zg, C a conversion of 10 mass 0 /.
- the nitrate manganese 37. 5 g Al force Li alumina powder 10 g, then the sodium carbonate 0. 7 g, then impregnated with chloride Ruteniu arm 39. 3 g , Particle distribution 10 ⁇ 150 / ⁇ 111, average particle size 80 ⁇ m, bulk density 1.4 g / m 1 and specific surface area 1 11 Conversion 40 wt%, 0.1 calculated as Na 9 mass 0/0,: ⁇ 11 2 0 3 30 wt%, the remainder aluminum Sani ⁇ ( ⁇ Ruminiumu oxide: manganese oxide 100 parts by weight: 103 (Parts by mass) was obtained.
- Example 2 According to the same preparation method as in Example 1, 0.9 g of sodium carbonate and then 3.6 g of ruthenium chloride are impregnated into 40 g of alkaline alumina powder to obtain a particle distribution of 10 to 150 m and an average particle diameter of 80 m. Catalyst with bulk density 0.75 g / m 1 and specific surface area 360 m 2 / g, 3 mass% in terms of Ru, 0.9 mass% in terms of Na, with aluminum oxide remaining (no manganese oxide) Got S.
- the FT reaction was performed in the same manner as above, except that carbon dioxide was not introduced.
- the chain growth probability ( ⁇ ;) is 0.8
- C 5 + selectivity is 73%
- the ratio of olefin / paraffin in C 3 is 0.5
- C 5 + production to raw is 210 g. / kg / hr.
- a catalyst was prepared in the same manner as in Example 1, except that 145 g of manganese nitrate was calcined, and 0.9 g of sodium carbonate and then 1 g of ruthenium chloride were impregnated therein.
- ⁇ L 50 Atm, average particle diameter 80 m, bulk density 2.4 g Zm 1 and specific surface area 40 m 2 Zg, 3% by mass in terms of Ru, 0.9% by mass in terms of Na, remaining Mn 2 0 3 to obtain a catalyst T consisting of (without aluminum acid I dry matter).
- 9 g of catalyst T was charged into a reactor together with 30 Oml of a solvent (slurry concentration: 30 g / 10 Om1), and the catalyst was reduced with hydrogen in the same manner as in Comparative Example 6.
- the reactor was charged with 9 g of Catalyst U together with 30 ml of solvent (30 g of slurry / 10 Om 1), and the catalyst was reduced with hydrogen in the same manner as in Comparative Example 6. Then, the FT reaction was started by contacting a synthesis gas of carbon monoxide and hydrogen, and then the FT reaction was performed by introducing carbon dioxide. The Ru dispersibility of Catalyst U after reduction was 35%. The gas flow rate of the synthesis gas at which the conversion was 60% was WZF 5.8 g ⁇ hr / mo1.
- the chain growth probability ( ⁇ ) is 0.81, C 5 + selectivity is 72%, the ratio of olefins in C 3 is less than 1, and C 5 + productivity is 350 g / kg. / hr.
- the FT reaction was performed in the same manner as above, except that carbon dioxide was not introduced. As a result, the chain growth probability ( ⁇ ) was 0.85, the C 5 + selectivity was 79%, the ratio of olefins in C 3 was less than 1, and the C 5 + productivity was 380 g / kg. / hr.
- the FT reaction was performed in the same manner as in Example 4 except that the partial pressure of carbon dioxide introduced after 20 hours from the start of the FT reaction was changed to 1.2 MPa. Chain growth probability in 48 hours after the start of the reaction (ratio) is 0. 8 8, C 5 + selectivity was 81% Orefin / paraffin ratio in C 3 is 3.5, and C 5 + productivity was 330 g / kg / hr.
- Example 1 Example 2
- Example 3 Example 3
- Example 4 Example 5 Catalyst> A B c D E
- Example 6 Example 7
- Example 8 Example 9 ⁇ Free E F G H
- Example 1 0
- Example 1 1
- Example 1 2
- a high chain growth probability (alpha, excellent Orefin selectivity Contact Yopi C 5 + productivity, and a high catalytic activity, without causing the like Hitosupo' bets generation
- the F ⁇ reaction can be performed stably and smoothly, and the decarboxylation step for removing carbon dioxide in the synthesis gas can be simplified or omitted, and liquid hydrocarbons can be produced efficiently.
- the method of the present invention is a method that can greatly contribute to increasing the production of kerosene gas oil fractions, including hydrocracking of the generated wax and dimerization and trimerization of the generated olefins.
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Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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NZ528955A NZ528955A (en) | 2001-06-18 | 2002-06-17 | Method for producing hydrocarbons by Fischer-Tropsch process |
US10/476,131 US6924316B2 (en) | 2001-06-18 | 2002-06-17 | Method for producing hydrocarbons by Fischer-Tropsch process |
AU2002313208A AU2002313208B2 (en) | 2001-06-18 | 2002-06-17 | Method for producing hydrocarbons by fischer-tropsch process |
EP02738738A EP1408099A4 (en) | 2001-06-18 | 2002-06-17 | TECHNIQUE FOR PRODUCING HYDROCARBON ACCORDING TO THE FISCHER-TROPSCH PROCESS |
NO20035616A NO337629B1 (no) | 2001-06-18 | 2003-12-16 | Fremgangsmåte for fremstilling av flytende hydrokarbonfraksjoner ved hjelp av Fischer-Tropsch prosess |
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JP2001183341A JP4660021B2 (ja) | 2001-06-18 | 2001-06-18 | フィッシャートロプシュ法による炭化水素類の製造方法 |
JP2001-183341 | 2001-06-18 | ||
JP2001300819A JP4660039B2 (ja) | 2001-09-28 | 2001-09-28 | 二酸化炭素の共存下のフィッシャートロプシュ法による炭化水素類の製造方法 |
JP2001-300819 | 2001-09-28 |
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WO2002102932A1 true WO2002102932A1 (en) | 2002-12-27 |
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PCT/JP2002/006015 WO2002102932A1 (en) | 2001-06-18 | 2002-06-17 | Method for producing hydrocarbons by fischer-tropsch process |
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US (1) | US6924316B2 (ja) |
EP (1) | EP1408099A4 (ja) |
AU (1) | AU2002313208B2 (ja) |
MY (1) | MY139370A (ja) |
NO (1) | NO337629B1 (ja) |
NZ (1) | NZ528955A (ja) |
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EP1719555A4 (en) * | 2004-02-24 | 2012-04-11 | Japan Oil Gas & Metals Jogmec | CATALYST FOR PRODUCTION OF HYDROCARBONS, PREPARATION METHOD THEREFOR, AND HYDROCARBON PRODUCTION PROCESS USING SAME |
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DE102005038488A1 (de) * | 2005-08-13 | 2007-02-22 | Bayerische Motoren Werke Ag | Verstärkungsblech für eine B-Säule einer Fahrzeugkarosserie |
KR101320388B1 (ko) * | 2006-02-18 | 2013-10-22 | 삼성에스디아이 주식회사 | 탄화수소 개질 촉매, 그 제조방법 및 이를 포함하는연료처리장치 |
US20070254968A1 (en) * | 2006-04-27 | 2007-11-01 | Syntroleum Corporation | Method of delivery, replacement, and removal of fischer-tropsch catalyst |
JP2009016782A (ja) * | 2007-06-04 | 2009-01-22 | Tokyo Electron Ltd | 成膜方法及び成膜装置 |
US8394861B2 (en) | 2007-06-27 | 2013-03-12 | Hrd Corporation | Gasification of carbonaceous materials and gas to liquid processes |
US8026403B2 (en) * | 2007-06-27 | 2011-09-27 | H R D Corporation | System and process for production of liquid product from light gas |
AU2009263607B8 (en) * | 2008-06-24 | 2014-01-23 | Cosmo Oil Co., Ltd. | Catalyst for Fischer-Tropsch synthesis and method for producing hydrocarbons |
JP5398082B2 (ja) | 2008-12-22 | 2014-01-29 | 旭化成ケミカルズ株式会社 | シクロオレフィン製造用ルテニウム触媒の調製方法、シクロオレフィンの製造方法、及び製造装置 |
JP5301330B2 (ja) | 2009-03-27 | 2013-09-25 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 液体炭化水素の合成方法及び液体炭化水素の合成システム |
JP5730495B2 (ja) * | 2010-03-30 | 2015-06-10 | 独立行政法人石油天然ガス・金属鉱物資源機構 | フィッシャー・トロプシュ合成反応用活性化触媒の製造方法、触媒スラリーの製造方法、並びに触媒スラリーのフィッシャー・トロプッシュ合成反応器への供給方法 |
US8912367B2 (en) | 2012-06-21 | 2014-12-16 | H R D Corporation | Method and system for liquid phase reactions using high shear |
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JPH11179204A (ja) * | 1997-12-19 | 1999-07-06 | Cosmo Sogo Kenkyusho Kk | 一酸化炭素及び二酸化炭素を含有するガスのメタン化触媒及びその製造方法 |
US6121333A (en) * | 1998-06-25 | 2000-09-19 | Agip Petroli S.P.A. | Process for the preparation of hydrocarbons from synthesis gas |
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US4728672A (en) * | 1984-10-08 | 1988-03-01 | Research Association For Petroleum Alternatives Development | Process for producing hydrocarbons |
JPS61280638A (ja) * | 1985-06-06 | 1986-12-11 | Toshiba Corp | 半導体装置の製造方法 |
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2002
- 2002-06-17 US US10/476,131 patent/US6924316B2/en not_active Expired - Fee Related
- 2002-06-17 WO PCT/JP2002/006015 patent/WO2002102932A1/ja active IP Right Grant
- 2002-06-17 EP EP02738738A patent/EP1408099A4/en not_active Withdrawn
- 2002-06-17 NZ NZ528955A patent/NZ528955A/en not_active IP Right Cessation
- 2002-06-17 AU AU2002313208A patent/AU2002313208B2/en not_active Ceased
- 2002-06-18 MY MYPI20022257A patent/MY139370A/en unknown
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EP0253924A1 (en) * | 1981-10-13 | 1988-01-27 | Shell Internationale Researchmaatschappij B.V. | Synthesis gas conversion using ROR-activated catalyst |
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EP1719555A4 (en) * | 2004-02-24 | 2012-04-11 | Japan Oil Gas & Metals Jogmec | CATALYST FOR PRODUCTION OF HYDROCARBONS, PREPARATION METHOD THEREFOR, AND HYDROCARBON PRODUCTION PROCESS USING SAME |
EP2559482A1 (en) * | 2004-02-24 | 2013-02-20 | Japan Oil, Gas and Metals National Corporation | Catalyst and process for producing hydrocarbons |
Also Published As
Publication number | Publication date |
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AU2002313208B2 (en) | 2007-07-26 |
MY139370A (en) | 2009-09-30 |
EP1408099A4 (en) | 2004-10-06 |
NO20035616L (no) | 2004-02-18 |
NO20035616D0 (no) | 2003-12-16 |
US6924316B2 (en) | 2005-08-02 |
NO337629B1 (no) | 2016-05-18 |
EP1408099A1 (en) | 2004-04-14 |
NZ528955A (en) | 2005-02-25 |
US20040157938A1 (en) | 2004-08-12 |
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