JP5128526B2 - Fischer-Tropsch synthesis catalyst and method for producing hydrocarbons - Google Patents
Fischer-Tropsch synthesis catalyst and method for producing hydrocarbons Download PDFInfo
- Publication number
- JP5128526B2 JP5128526B2 JP2009070113A JP2009070113A JP5128526B2 JP 5128526 B2 JP5128526 B2 JP 5128526B2 JP 2009070113 A JP2009070113 A JP 2009070113A JP 2009070113 A JP2009070113 A JP 2009070113A JP 5128526 B2 JP5128526 B2 JP 5128526B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- mass
- fischer
- hours
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims description 164
- 229930195733 hydrocarbon Natural products 0.000 title claims description 55
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 53
- 238000003786 synthesis reaction Methods 0.000 title claims description 43
- 230000015572 biosynthetic process Effects 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 103
- 229910052751 metal Inorganic materials 0.000 claims description 65
- 239000002184 metal Substances 0.000 claims description 65
- 239000007789 gas Substances 0.000 claims description 59
- 239000011656 manganese carbonate Substances 0.000 claims description 56
- 235000006748 manganese carbonate Nutrition 0.000 claims description 56
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 56
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 56
- 229940093474 manganese carbonate Drugs 0.000 claims description 55
- 230000000694 effects Effects 0.000 claims description 36
- 229910052783 alkali metal Inorganic materials 0.000 claims description 31
- 150000001340 alkali metals Chemical class 0.000 claims description 31
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 24
- 229910052707 ruthenium Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 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 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 description 38
- 239000002002 slurry Substances 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 230000009467 reduction Effects 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 230000007423 decrease Effects 0.000 description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 241000894007 species Species 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012916 structural analysis Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 150000003303 ruthenium Chemical class 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 150000001868 cobalt Chemical class 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- -1 naphtha Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010419 fine particle 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
- 150000002739 metals Chemical class 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000005068 transpiration Effects 0.000 description 2
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- DDRQVDNHTVCAGJ-UHFFFAOYSA-K [Cl-].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[Ru+3].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound [Cl-].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[Ru+3].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] DDRQVDNHTVCAGJ-UHFFFAOYSA-K 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-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
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002303 thermal reforming Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、水素と一酸化炭素を主成分とする混合ガス(以下「合成ガス」という)から炭化水素類を製造するための、フィッシャー・トロプシュ合成用触媒、及び該触媒を用いた炭化水素類の製造方法に関する。さらに詳しくは、主として炭酸マンガンからなる担体に、フィッシャー・トロプシュ反応に対する活性を有する金属(以下「FT活性金属」という)を含有させてなる触媒、及び該触媒に合成ガスを接触させ、ナフサ、灯油、軽油、ワックスといった炭化水素類を製造する方法に関する。 The present invention relates to a Fischer-Tropsch synthesis catalyst for producing hydrocarbons from a mixed gas containing hydrogen and carbon monoxide as main components (hereinafter referred to as “synthesis gas”), and hydrocarbons using the catalyst. It relates to the manufacturing method. More specifically, a catalyst mainly comprising manganese carbonate containing a metal having activity against the Fischer-Tropsch reaction (hereinafter referred to as “FT active metal”), and a synthetic gas brought into contact with the catalyst, naphtha, kerosene The present invention relates to a method for producing hydrocarbons such as diesel oil and wax.
合成ガスから炭化水素類を合成する方法として、フィッシャー・トロプシュ反応(Fischer-Tropsch反応)、メタノール合成反応、C2含酸素(エタノール、アセトアルデヒド等)合成反応などが良く知られている。そして、フィッシャー・トロプシュ反応は鉄、コバルト、ニッケルの鉄族元素やルテニウム等の白金族元素を活性金属とする触媒で、メタノール合成反応は銅系触媒で、C2含酸素合成反応はロジウム系触媒で進行することが知られている(例えば、非特許文献1参照)。 As methods for synthesizing hydrocarbons from synthesis gas, Fischer-Tropsch reaction (Fischer-Tropsch reaction), methanol synthesis reaction, C2 oxygen-containing (ethanol, acetaldehyde, etc.) synthesis reaction and the like are well known. The Fischer-Tropsch reaction is a catalyst using iron group elements such as iron, cobalt and nickel and platinum group elements such as ruthenium as active metals, the methanol synthesis reaction is a copper catalyst, and the C2 oxygen-containing synthesis reaction is a rhodium catalyst. It is known to proceed (see, for example, Non-Patent Document 1).
ところで、近年、大気環境保全の観点から、低硫黄分の軽油が望まれており、今後その傾向はますます強くなるものと考えられる。また、原油資源は有限であるとの観点やエネルギーセキュリティーの面から、石油代替燃料の開発が望まれており、今後ますます強く望まれるようになるものと考えられる。これらの要望に応える技術として、エネルギー換算で原油に匹敵する可採埋蔵量があるといわれる天然ガス(主成分メタン)から灯軽油等の液体燃料を合成する技術であるGTL(gas to liquids)がある。 By the way, in recent years, gas oil with low sulfur content has been desired from the viewpoint of the preservation of the air environment, and this trend is expected to become stronger in the future. In addition, from the viewpoint that crude oil resources are limited and from the viewpoint of energy security, the development of alternative fuels for oil is desired, and it is expected that this will become increasingly desirable in the future. As a technology that meets these demands, GTL (gas to liquids), a technology that synthesizes liquid fuels such as kerosene from natural gas (main component methane), which is said to have recoverable reserves equivalent to crude oil in terms of energy, is used. is there.
天然ガスは、硫黄分を含まないか、含んでいても脱硫が容易な硫化水素(H2S)等であるため、得られる灯軽油等の液体燃料には、その中に殆ど硫黄分が無く、またセタン価の高い高性能ディーゼル燃料に利用できるなどの利点があるため、このGTLは近年ますます注目されるようになってきている。 Since natural gas does not contain sulfur or is hydrogen sulfide (H 2 S) or the like that is easy to desulfurize even if it contains, liquid fuel such as kerosene obtained has almost no sulfur in it. In addition, because of the advantage that it can be used for high-performance diesel fuel having a high cetane number, this GTL has been increasingly attracting attention in recent years.
上記GTLの一環として、合成ガスからフィッシャー・トロプシュ反応(以下「FT反応」という)によって炭化水素類を製造する方法(以下「FT法」という)が盛んに研究されている。このFT法において炭化水素類の収率を高めるためには、炭化水素類の製造能力、すなわち活性が高く、ガス成分の生成が少なく、長時間安定した活性を示すといった優れた性能を有する触媒を用いることが有効と考えられる。 As part of the GTL, methods for producing hydrocarbons from synthesis gas by the Fischer-Tropsch reaction (hereinafter referred to as “FT reaction”) (hereinafter referred to as “FT method”) have been actively studied. In order to increase the yield of hydrocarbons in this FT method, a catalyst having excellent performance such as high production capacity of hydrocarbons, that is, high activity, little generation of gas components, and stable activity for a long time. Use is considered effective.
そして、従来から、種々のFT反応用の触媒が提案されており、例えば、コバルトや鉄といったFT活性金属種をアルミナや、シリカ、シリカ−アルミナ、チタニアなどの金属酸化物担体に担持した触媒が提案されている(例えば、特許文献1、特許文献2、特許文献3参照)。また、オレフィン類への高選択性を目的とした触媒として、マンガン酸化物担体にルテニウムを担持させた触媒、このルテニウム担持触媒にさらに第三成分を加えた触媒などのルテニウム系触媒が提案されている(例えば、特許文献4、特許文献5参照)。 Conventionally, various catalysts for FT reaction have been proposed. For example, a catalyst in which an FT active metal species such as cobalt or iron is supported on a metal oxide carrier such as alumina, silica, silica-alumina, titania or the like. It has been proposed (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3). Ruthenium catalysts such as a catalyst in which ruthenium is supported on a manganese oxide support and a catalyst in which a third component is further added to the ruthenium supported catalyst have been proposed as catalysts for high selectivity to olefins. (For example, refer to Patent Document 4 and Patent Document 5).
これらの従来提案されている触媒は、それを用いたFT法において、相応に優れたオレフィン類の選択性や、相応の触媒活性を示すが、更なる触媒活性の向上が望まれる。一般に、触媒の活性が高いほど、触媒重量当たりの目的物の生産性が高く、同じ量の目的物を得るための触媒使用重量は少なくて済み、それに伴い反応器を小型化できるなど、触媒費用や装置費用の軽減が期待できる。また、FT反応用の触媒には、生成物中のメタン等のガス成分の生成が少なく、灯油や軽油といった有用な液状の炭化水素類の得率が高いことが望まれる。 These conventionally proposed catalysts show correspondingly excellent selectivity of olefins and corresponding catalytic activity in the FT method using the catalyst, but further improvement in catalytic activity is desired. In general, the higher the activity of the catalyst, the higher the productivity of the target product per catalyst weight, and the smaller the amount of catalyst used to obtain the same amount of target product, the smaller the reactor cost. And equipment costs can be reduced. Further, it is desired that the catalyst for the FT reaction has a low yield of gas components such as methane in the product and has a high yield of useful liquid hydrocarbons such as kerosene and light oil.
本発明は、上記従来の状況に鑑み、FT法において、CO転化率が高く、ガス成分の生成が少なく、かつ安定してFT合成反応を行うことができ、炭化水素類の生産性を向上させることができるFT合成用触媒、及びその触媒を用いる炭化水素類の製造方法を提供することを目的とする。 In view of the above-described conventional situation, the present invention has a high CO conversion rate, a small amount of gas component generation, and a stable FT synthesis reaction in the FT method, thereby improving the productivity of hydrocarbons. It is an object of the present invention to provide a catalyst for FT synthesis that can be produced, and a method for producing hydrocarbons using the catalyst.
本発明者らは、先に炭酸マンガンを主成分とする担体が従来提案されている金属酸化物系の担体を用いる触媒に比較して、活性が高く、かつ、ガス成分の生成が少ないことを見出している。本発明者らは、上記目的を達成すべくさらに鋭意研究をしたところ、FT活性金属の他にさらにアルカリ金属を、炭酸マンガンを主成分とする担体に含有させた触媒が、従来提案されている金属酸化物系の担体を用いる触媒に比較して、活性が大幅に高く、かつ、ガス成分の生成がより少ないことを見出し、本発明を完成するに至った。 The inventors of the present invention have previously described that a carrier mainly composed of manganese carbonate has a higher activity and less generation of gas components than a catalyst using a metal oxide carrier that has been conventionally proposed. Heading. The inventors of the present invention have made further studies in order to achieve the above object. As a result, a catalyst in which an alkali metal in addition to an FT active metal is further contained in a carrier mainly composed of manganese carbonate has been proposed. The present inventors have found that the activity is significantly higher than that of a catalyst using a metal oxide-based support and the generation of gas components is less, and the present invention has been completed.
本発明の触媒の活性向上やガスの生成の低下の詳細なメカニズムについては解明されておらず、現在、鋭意検討中ではあるが、FT反応に対しては不活性である担体主成分の炭酸マンガンやアルカリ金属が何らかの形でFT活性金属種に作用し、活性を向上させるとともに、ガスの生成を抑制する作用を有するものと推察している。 The detailed mechanism of the improvement in the activity of the catalyst of the present invention and the decrease in the generation of gas has not been elucidated and is currently under intensive study, but is a carrier-based manganese carbonate that is inert to the FT reaction. It is presumed that alkali metals and alkali metals act on the FT active metal species in some form to improve the activity and suppress the generation of gas.
すなわち、本発明は、上記目的を達成するために、下記構成のFT合成用触媒、及びその触媒を用いる炭化水素類の製造方法を提供する。
1.炭酸マンガンを主成分とする担体に、フィッシャー・トロプシュ反応に対する活性を有する金属の少なくとも1種以上とアルカリ金属の少なくとも1種以上とを含有させてなることを特徴とするフィッシャー・トロプシュ合成用触媒。
2.フィッシャー・トロプシュ反応に対する活性を有する金属が、ルテニウム及びコバルトから選ばれた少なくとも1種であることを特徴とする上記1に記載のフィッシャー・トロプシュ合成用触媒。
3.ルテニウムの含有量が、触媒基準、金属換算で0.5〜5質量%であることを特徴とする上記2に記載のフィッシャー・トロプシュ合成用触媒。
4.コバルトの含有量が、触媒基準、金属換算で5〜40質量%であることを特徴とする上記2に記載のフィッシャー・トロプシュ合成用触媒。
5.アルカリ金属の含有量が、触媒基準、金属換算で0.05〜3質量%であることを特徴とする上記1〜4のいずれかに記載のフィッシャー・トロプシュ合成用触媒。
6.アルカリ金属が、ナトリウム及びカリウムから選ばれた少なくとも1種であることを特徴とする上記5に記載のフィッシャー・トロプシュ合成用触媒。
7.上記1〜6のいずれかに記載のフィッシャー・トロプシュ合成用触媒に、水素及び一酸化炭素を主成分とするガスを接触させることを特徴とする炭化水素類の製造方法。
That is, in order to achieve the above object, the present invention provides a catalyst for FT synthesis having the following constitution and a method for producing hydrocarbons using the catalyst.
1. A Fischer-Tropsch synthesis catalyst comprising a carrier comprising manganese carbonate as a main component and containing at least one metal having activity against Fischer-Tropsch reaction and at least one alkali metal.
2. 2. The Fischer-Tropsch synthesis catalyst as described in 1 above, wherein the metal having activity for the Fischer-Tropsch reaction is at least one selected from ruthenium and cobalt.
3. 3. The catalyst for Fischer-Tropsch synthesis as described in 2 above, wherein the ruthenium content is 0.5 to 5% by mass in terms of catalyst and metal.
4). 3. The Fischer-Tropsch synthesis catalyst as described in 2 above, wherein the content of cobalt is 5 to 40% by mass in terms of metal on a catalyst basis.
5. The Fischer-Tropsch synthesis catalyst as described in any one of 1 to 4 above, wherein the alkali metal content is 0.05 to 3% by mass in terms of a catalyst, in terms of metal.
6). 6. The Fischer-Tropsch synthesis catalyst as described in 5 above, wherein the alkali metal is at least one selected from sodium and potassium.
7. A method for producing hydrocarbons, comprising bringing the gas mainly composed of hydrogen and carbon monoxide into contact with the Fischer-Tropsch synthesis catalyst according to any one of 1 to 6 above.
本発明の炭酸マンガンを担体とし、FT活性金属とアルカリ金属を含有する触媒は、従来のアルミナやシリカを担体とする触媒に比較してCO転化率が高く、また、ガス成分であるCH4などの生成割合を低下させることができる。
また、本発明によれば、触媒の活性が高く、炭化水素類の生産性が高い触媒が提供され、触媒コストや反応器のサイズダウン等の効果が見込まれる。
The catalyst containing manganese carbonate of the present invention as a carrier and containing an FT active metal and an alkali metal has a higher CO conversion rate than a conventional catalyst using alumina or silica as a carrier, and is a gas component such as CH 4. The production rate of can be reduced.
Further, according to the present invention, a catalyst having high catalyst activity and high hydrocarbon productivity is provided, and effects such as catalyst cost and reactor size reduction are expected.
以下に本発明を詳細に説明する。
本発明のフィッシャー・トロプシュ合成用触媒(以下「本発明の触媒」とも言う。)は、炭酸マンガンを主成分とする担体(以下「炭酸マンガン担体」とも言う。)に、FT活性金属種およびアルカリ金属を含有させてなるものである。以下、本発明の触媒、及びその調製からそれを用いた炭化水素類の製造方法までを順次詳しく説明する。
The present invention is described in detail below.
The catalyst for Fischer-Tropsch synthesis of the present invention (hereinafter also referred to as “the catalyst of the present invention”) comprises a carrier mainly composed of manganese carbonate (hereinafter also referred to as “manganese carbonate support”), an FT active metal species and an alkali. A metal is contained. Hereinafter, the catalyst of the present invention and the preparation thereof to the production method of hydrocarbons using the same will be described in detail.
<触媒及びその調製>
本発明の触媒における炭酸マンガン担体の主成分である炭酸マンガンとしては、工業的に生産販売されているものを用いることもできるし、また、従来公知の方法で製造することもできる。炭酸マンガンを公知方法で得る場合、可溶性マンガン塩溶液と炭酸アンモニアあるいはアルカリの炭酸塩(たとえば炭酸ナトリウム)を反応させることで得られる。また、二価のマンガンイオンと炭酸イオンあるいは重炭酸イオンとの反応によっても得ることができる。また、炭酸マンガン担体は、炭酸マンガンのみからなるものでも、本発明における所期の炭酸マンガンの効果を阻害しない限りにおいて、炭酸マンガン以外の他の成分を含んでいても良い。この他の成分としては、シリカ、アルミナ、シリカ−アルミナなど、通常担体として用いられる無機酸化物が挙げられる。また、この他の成分の含有量は、本発明における所期の炭酸マンガンの効果を阻害しない限りにおいて適宜設定できるが、一般に、担体基準で5〜50質量%が適当である。
<Catalyst and its preparation>
As manganese carbonate which is the main component of the manganese carbonate support in the catalyst of the present invention, those produced and sold industrially can be used, and can also be produced by a conventionally known method. When manganese carbonate is obtained by a known method, it can be obtained by reacting a soluble manganese salt solution with ammonia carbonate or an alkali carbonate (for example, sodium carbonate). It can also be obtained by reaction of divalent manganese ions with carbonate ions or bicarbonate ions. Further, the manganese carbonate carrier may be composed only of manganese carbonate or may contain other components other than manganese carbonate as long as the effect of the intended manganese carbonate in the present invention is not inhibited. Examples of other components include inorganic oxides that are usually used as carriers, such as silica, alumina, silica-alumina, and the like. The content of the other components can be appropriately set as long as the desired effect of manganese carbonate in the present invention is not impaired, but generally 5 to 50% by mass is appropriate based on the carrier.
本発明の触媒におけるFT活性金属種としては、ニッケル、コバルト、鉄、ルテニウムが挙げられるが、中でも高活性な金属種としてルテニウムやコバルトが好ましく選択される。また、これらの金属種は単独で用いることもできるし、2種以上を複合させて用いることも可能である。 Examples of the FT active metal species in the catalyst of the present invention include nickel, cobalt, iron, and ruthenium. Among them, ruthenium and cobalt are preferably selected as highly active metal species. Moreover, these metal seed | species can also be used independently and can also be used in mixture of 2 or more type.
また、本発明の触媒におけるアルカリ金属種としては、リチウム、ナトリウム、カリウム、ルビジウムなどが挙げられるが、中でもナトリウムやカリウムが好ましく選択される。これらのアルカリ金属種は単独で用いることもできるし、2種以上を複合させて用いることも可能である。 Further, examples of the alkali metal species in the catalyst of the present invention include lithium, sodium, potassium, rubidium and the like, among which sodium and potassium are preferably selected. These alkali metal species can be used alone or in combination of two or more.
本発明の触媒を調製するための、炭酸マンガン担体にFT活性金属種やアルカリ金属種を含有させる方法の一つに、FT活性金属種やアルカリ金属種を炭酸マンガン担体に含浸担持させる方法がある。以下、この含浸担持について、説明する。この含浸担持は、通常の含浸担持方法で行うことができる。 One method for preparing the catalyst of the present invention is to impregnate and support a manganese carbonate carrier with an FT active metal species or alkali metal species. . Hereinafter, the impregnation support will be described. This impregnation support can be performed by a normal impregnation support method.
例えば、炭酸マンガン担体にルテニウム塩やコバルト塩の水溶液を含浸させ、その後、乾燥、焼成することによって行うことができる。このとき、FT活性金属種として2種以上の金属を担持する場合、例えばルテニウム塩とコバルト塩の両方含む水溶液を調製し、ルテニウム塩とコバルト塩を同時に含浸させ、その後、乾燥、焼成することもできるし、各々を別途に順次含浸させ、その後、乾燥、焼成しても良い。炭酸マンガン担体へのFT活性金属種の含浸担持方法は、特に限定されない。
同様に、炭酸マンガン担体にアルカリ金属種を担持する場合は、例えば、ナトリウム塩やカリウム塩の水溶液を含浸させ、その後、乾燥、焼成することによって行われる。
尚、FT活性金属種とアルカリ金属種の担持の順序に関しては特に限定されない。
For example, it can be carried out by impregnating a manganese carbonate carrier with an aqueous solution of ruthenium salt or cobalt salt, and then drying and baking. At this time, when two or more metals are supported as FT active metal species, for example, an aqueous solution containing both a ruthenium salt and a cobalt salt may be prepared, impregnated with a ruthenium salt and a cobalt salt at the same time, and then dried and fired. Alternatively, each may be impregnated separately and then dried and fired. The method for impregnating and supporting the FT active metal species on the manganese carbonate support is not particularly limited.
Similarly, when an alkali metal species is supported on a manganese carbonate support, for example, it is impregnated with an aqueous solution of sodium salt or potassium salt, and then dried and fired.
The order of loading the FT active metal species and the alkali metal species is not particularly limited.
上記含浸担持に用いるルテニウム塩としては、塩化ルテニウム、硝酸ルテニウム、酢酸ルテニウム、塩化六アンモニアルテニウムなどの水溶性ルテニウム塩が挙げられる。また、コバルト塩としては、塩化コバルト、硝酸コバルト、酢酸コバルト、硫酸コバルト、ギ酸コバルトが好ましく用いられる。
また、ナトリウム塩やカリウム塩としては、塩化物、硝酸塩、酢酸塩、炭酸塩などの水溶性の塩が好ましい。
さらに、含浸担持に用いるルテニウム塩、コバルト塩、ナトリウム塩、カリウム塩の溶液の溶媒に、水ではなく、アルコール、エーテル、ケトンなどの有機溶媒を用いることも可能であり、この場合は、これらの塩として各種有機溶媒に可溶な塩を選択する。
Examples of the ruthenium salt used for the impregnation support include water-soluble ruthenium salts such as ruthenium chloride, ruthenium nitrate, ruthenium acetate, and ruthenium hexaammonium chloride. Further, as the cobalt salt, cobalt chloride, cobalt nitrate, cobalt acetate, cobalt sulfate, and cobalt formate are preferably used.
Moreover, as a sodium salt and potassium salt, water-soluble salts, such as a chloride, nitrate, acetate, carbonate, are preferable.
Furthermore, it is also possible to use an organic solvent such as alcohol, ether or ketone instead of water as the solvent of the solution of ruthenium salt, cobalt salt, sodium salt or potassium salt used for impregnation support. A salt that is soluble in various organic solvents is selected as the salt.
本発明の触媒におけるルテニウムの含有量は、触媒基準、金属量換算で好ましくは0.5〜5質量%、より好ましくは0.8〜4.5質量%、特に好ましくは1〜4質量%である。ルテニウムの担持量は活性点数と関連する。ルテニウムの担持量を0.5質量%以上とすることにより、活性点数が保たれ十分な触媒活性を得ることができる。また、ルテニウムの担持量を5質量%以下とすることにより、ルテニウムの分散性の低下や、担体成分と相互作用を持たないルテニウム種が発現するのを抑制できる。 The ruthenium content in the catalyst of the present invention is preferably 0.5 to 5% by mass, more preferably 0.8 to 4.5% by mass, and particularly preferably 1 to 4% by mass in terms of catalyst and metal amount. is there. The amount of ruthenium supported is related to the number of active sites. By setting the supported amount of ruthenium to 0.5% by mass or more, the number of active sites is maintained and sufficient catalytic activity can be obtained. Further, by setting the amount of ruthenium supported to 5% by mass or less, it is possible to suppress a decrease in the dispersibility of ruthenium and the expression of ruthenium species that do not interact with the carrier component.
また、コバルトの含有量は、触媒基準、金属量換算で好ましくは5〜40質量%、より好ましくは5〜35質量%、特に好ましくは5〜30質量%である。コバルトの含有量を5質量%以上とすることにより、活性金属としての顕著な活性向上の効果が認められる。また、40質量%以下とすることにより、触媒調製の際の乾燥工程、焼成処理工程や、FT反応に供した際の反応条件下において、コバルトの凝集を抑制することができ、また、触媒の比表面積や細孔容積の低下を抑制することができ、さらにまた、FT反応における生成物中のガス生成量を抑制することができる。 Further, the content of cobalt is preferably 5 to 40% by mass, more preferably 5 to 35% by mass, and particularly preferably 5 to 30% by mass in terms of catalyst and metal amount. By making the cobalt content 5% by mass or more, a remarkable activity improvement effect as an active metal is recognized. Moreover, by setting it as 40 mass% or less, it can suppress agglomeration of cobalt under the drying process, the calcination process, and the reaction conditions when subjected to the FT reaction in preparing the catalyst. A decrease in specific surface area and pore volume can be suppressed, and furthermore, the amount of gas generated in the product in the FT reaction can be suppressed.
さらに、ナトリウムやカリウムなどのアルカリ金属の含有量は、触媒基準、金属量換算で好ましくは0.05〜3質量%、より好ましくは0.05〜2質量%、特に好ましくは0.1〜1.5質量%である。ナトリウムやカリウムの含有量を0.05質量%以上とすることにより、ガス成分の生成量を抑制する効果が顕著となる。また、3質量%以下とすることにより、FT活性を低下させることなくガス生成量を抑制することが可能となる。 Furthermore, the content of alkali metals such as sodium and potassium is preferably 0.05 to 3% by mass, more preferably 0.05 to 2% by mass, and particularly preferably 0.1 to 1% in terms of catalyst and metal amount. 0.5% by mass. By making the content of sodium or potassium 0.05% by mass or more, the effect of suppressing the generation amount of gas components becomes remarkable. Moreover, by setting it as 3 mass% or less, it becomes possible to suppress a gas production amount, without reducing FT activity.
FT活性金属種やアルカリ金属種を炭酸マンガン担体に含浸した後は、乾燥、焼成を行う。このときの乾燥は、原則、水を蒸散させるために行い、その温度は80〜200℃が好ましく、100〜150℃がより好ましい。乾燥温度を80℃以上とすることで、水の蒸散を十分に促進することが可能であり、200℃以下であれば急激な水の蒸散による活性金属成分の不均一化を抑制することができるため好ましい。 After impregnating the manganese carbonate carrier with the FT active metal species or the alkali metal species, drying and firing are performed. In principle, the drying is performed to evaporate water, and the temperature is preferably 80 to 200 ° C, more preferably 100 to 150 ° C. By setting the drying temperature to 80 ° C. or higher, it is possible to sufficiently promote the transpiration of water, and if it is 200 ° C. or lower, it is possible to suppress the non-uniformity of the active metal component due to the rapid transpiration of water. Therefore, it is preferable.
また、焼成温度は150〜300℃が好ましく、150〜250℃がより好ましい。焼成温度を300℃以内とすることにより、担体成分の炭酸マンガンがマンガン酸化物と炭酸ガスに分解することを抑制することができる。本発明においては、担体成分の炭酸マンガンは、炭酸塩の形態で存在することが必須であり、後記比較例に具体的に示すように、酸化マンガンでは本発明の所期の効果は得られない。また、FT活性金属種やアルカリ金属種の活性化を図るためには相応の温度が必要であるので、焼成温度は上記範囲が好ましい。 The firing temperature is preferably 150 to 300 ° C, more preferably 150 to 250 ° C. By setting the firing temperature within 300 ° C., it is possible to suppress decomposition of manganese carbonate as a carrier component into manganese oxide and carbon dioxide gas. In the present invention, manganese carbonate as a carrier component must be present in the form of a carbonate, and as specifically shown in Comparative Examples described later, manganese oxide does not provide the intended effect of the present invention. . Moreover, in order to activate FT active metal seed | species and alkali metal seed | species, since suitable temperature is required, the calcination temperature is the said range.
また、乾燥や焼成の処理時間は、処理量によって一概には決まらないが、通常1〜10時間である。処理時間を1時間以上とすることにより、水分の蒸散を確実に行い、FT活性金属種やアルカリ金属種の活性化が希薄となることを抑制できる。また、処理時間が10時間を超えても、触媒活性は、10時間以下の場合とほとんど変わらないため、作業性や生産性を考慮すると10時間以下が好ましい。なお、この乾燥や焼成処理は空気中で行うことも、あるいは窒素やヘリウムといった不活性ガス雰囲気でも、水素などの還元ガス雰囲気でもよく、特に限定はされない。 Moreover, although the processing time of drying or baking is not decided unconditionally by a processing amount, it is 1 to 10 hours normally. By setting the treatment time to 1 hour or longer, it is possible to reliably evaporate moisture and to suppress the activation of FT active metal species and alkali metal species from becoming diluted. Further, even if the treatment time exceeds 10 hours, the catalytic activity is almost the same as when the treatment time is 10 hours or less. Therefore, considering workability and productivity, 10 hours or less is preferable. The drying or baking treatment may be performed in the air, or may be an inert gas atmosphere such as nitrogen or helium, or a reducing gas atmosphere such as hydrogen, and is not particularly limited.
上述の焼成工程は、FT活性金属種やアルカリ金属種の活性化を図る目的があるが、焼成処理以外にアルカリ性水溶液処理によって活性化を達成することも可能である。炭酸マンガン担体にFT活性金属種やアルカリ金属種を担持した触媒をアルカリ性水溶液に浸漬して後処理する。アルカリ性水溶液としては、アンモニア水、水酸化ナトリウム水溶液、水酸化カリウム水溶液、炭酸ナトリウム水溶液、炭酸カリウム水溶液などを用いることができ、好ましくはアンモニア水を用いることができる。アルカリ水溶液中のアルカリの濃度は0.05〜1N、好ましくは0.05〜0.5N、より好ましくは0.05〜0.2Nである。0.05N未満では後処理効果が希薄となり、その後の焼成処理を行っても触媒活性の向上があまり見られない。また、1Nを超えると未反応のアルカリ分が多くなり、不経済となるほか、洗浄工程に要する水量や時間が多くなる。後処理の時間はアルカリ分の濃度にも依るが、通常1〜10時間が好ましい。 Although the above-mentioned baking process has the objective of activating FT active metal seed | species and an alkali metal seed | species, activation can also be achieved by alkaline aqueous-solution process besides a baking process. A catalyst in which an FT active metal species or an alkali metal species is supported on a manganese carbonate carrier is immersed in an alkaline aqueous solution for post-treatment. As the alkaline aqueous solution, ammonia water, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution and the like can be used, and preferably ammonia water can be used. The concentration of alkali in the alkaline aqueous solution is 0.05 to 1N, preferably 0.05 to 0.5N, more preferably 0.05 to 0.2N. If it is less than 0.05 N, the post-treatment effect is dilute, and even if the subsequent calcination treatment is performed, the catalytic activity is not significantly improved. Moreover, when it exceeds 1N, unreacted alkali will increase and it will become uneconomical, and the amount of water and time which a washing | cleaning process requires will increase. Although the post-treatment time depends on the alkali concentration, it is usually preferably 1 to 10 hours.
アルカリ性水溶液で後処理した後、水洗し、余剰のアルカリ分を充分に洗浄し上述の乾燥、焼成を行う。なお、このアルカリ性水溶液による処理は、炭酸マンガン担体にFT活性金属種やアルカリ金属種を含浸担持して、乾燥後に行うかあるいは焼成後に行ってもよく、特に限定しない。さらに、後述するスプレードライを行った触媒や成型した触媒について実施することもできる。 After the post-treatment with an alkaline aqueous solution, the substrate is washed with water, the excess alkali is sufficiently washed, and the above-described drying and firing are performed. The treatment with the alkaline aqueous solution may be carried out after drying or firing after impregnating and supporting an FT active metal species or alkali metal species on a manganese carbonate carrier, and is not particularly limited. Furthermore, it can also implement about the catalyst which performed the spray drying mentioned later, and the shape | molded catalyst.
上述の含浸担持法以外の、本発明の炭酸マンガン担体にFT活性金属種やアルカリ金属種を含有させてなる触媒の製造方法としては、炭酸マンガンとFT活性金属種やアルカリ金属種を含む水系のスラリーを調製し、それをスプレードライする方法が挙げられる。このスプレードライ法におけるスラリーの濃度は特に限定はされないが、スラリー濃度が低すぎると炭酸マンガンの沈殿が発生し、触媒成分が不均一となり好ましくなく、また、スラリー濃度が高すぎるとスラリーの送液が困難となるため、適度なスラリー濃度を選択する。さらにこのとき、スラリーの濃度調整や触媒の成形性の向上、球状化を目的にシリカゾルやアルミナ等をバインダー成分として添加することも可能である。このときのバインダーの添加量としては、触媒活性を低下させない程度が好ましく、好ましくは1〜40質量%、より好ましくは3〜30質量%である。バインダー量を1質量%以上とすることで、触媒の成型性や強度面での効果が顕著となる。また、バインダー量を40質量%以下にすることで、炭酸マンガン含有量の低下によるFT活性の低下を抑制することが可能となり好ましい。 Other than the impregnation support method described above, as a method for producing a catalyst in which the manganese carbonate support of the present invention contains an FT active metal species or an alkali metal species, an aqueous system containing manganese carbonate and an FT active metal species or an alkali metal species can be used. The method of preparing a slurry and spray-drying it is mentioned. The concentration of the slurry in this spray drying method is not particularly limited. However, if the slurry concentration is too low, precipitation of manganese carbonate occurs and the catalyst components are not uniform, which is not preferable. If the slurry concentration is too high, the slurry is fed. Therefore, an appropriate slurry concentration is selected. Further, at this time, silica sol, alumina or the like can be added as a binder component for the purpose of adjusting the concentration of the slurry, improving the moldability of the catalyst, and spheroidizing. The amount of the binder added at this time is preferably such that the catalytic activity is not lowered, preferably 1 to 40% by mass, more preferably 3 to 30% by mass. By making the amount of the binder 1% by mass or more, the effect on the moldability and strength of the catalyst becomes remarkable. In addition, it is preferable that the binder amount be 40% by mass or less because a decrease in FT activity due to a decrease in manganese carbonate content can be suppressed.
また、スプレードライ法で触媒を製造する場合、スラリー中に炭酸マンガン、FT活性金属種、アルカリ金属種、バインダー成分を同時に含有させて、スプレーする方法や、炭酸マンガンとバインダーを含むスラリーをスプレーし、その後、上述の含浸担持方法に則って、FT活性金属種やアルカリ金属種を添加する方法がある。また、スプレードライ法における送風温度は上述の含浸担持法における乾燥及び焼成温度内で実施することが好ましい。 In addition, when a catalyst is produced by a spray drying method, manganese slurry, FT active metal species, alkali metal species and a binder component are simultaneously contained in the slurry and sprayed, or a slurry containing manganese carbonate and a binder is sprayed. Thereafter, there is a method of adding an FT active metal species or an alkali metal species in accordance with the above-described impregnation supporting method. Moreover, it is preferable to implement the ventilation temperature in the spray-drying method within the drying and baking temperature in the above-mentioned impregnation supporting method.
上述のスプレードライ法で得られる触媒は一般的に粒子径が約1〜150μmの微粉末状であり、後述する本発明である炭化水素の製造方法における反応器の形式としては流動床、懸濁床、スラリー床に適している。しかし、固定床反応機に用いる場合は、微粉末状では差圧の発生が懸念されるため、触媒の形状としては一般に押し出し成型品、打錠成型品等が好ましく用いられる。これらは、一般的な押し出し製法や打錠製法で成型することが可能であり、炭酸マンガン担体、あるいは炭酸マンガン担体にFT活性金属やアルカリ金属を含有させた触媒を押し出し成型機や打錠成型機を用いて成型することができる。この時、担体や触媒の成型性、結合性、強度を向上させる目的でバインダーを添加することができる。バインダーとしては無機バインダーや有機バインダーが一般的であり、無機バインダーとしてはシリカ、アルミナ、チタニア等が好ましく、有機バインダーとしてはカルボキシメチルセルロースナトリウムやメチルセルロース等が挙げられる。 The catalyst obtained by the above-mentioned spray-drying method is generally in the form of a fine powder having a particle size of about 1 to 150 μm, and the type of reactor in the hydrocarbon production method of the present invention described later is a fluidized bed or suspension. Suitable for floors and slurry beds. However, when used in a fixed bed reactor, since there is concern about the occurrence of differential pressure in the form of fine powder, generally, an extruded molded product, a tableted molded product, etc. are preferably used as the shape of the catalyst. These can be molded by a general extrusion manufacturing method or a tableting manufacturing method, and an extrusion molding machine or a tableting molding machine is manufactured by using a manganese carbonate carrier or a catalyst in which a manganese carbonate carrier contains an FT active metal or an alkali metal. Can be used to mold. At this time, a binder can be added for the purpose of improving the moldability, bondability and strength of the carrier and catalyst. As the binder, an inorganic binder and an organic binder are generally used. As the inorganic binder, silica, alumina, titania and the like are preferable, and as the organic binder, carboxymethyl cellulose sodium, methyl cellulose and the like can be mentioned.
バインダーの添加量としては、触媒活性を低下させない程度が好ましく、好ましくは1〜40質量%、より好ましくは3〜30質量%である。バインダー量を1質量%以上とすることで、触媒の成型性、結合性、押し出し性や強度が良好となる。また、バインダー量を40質量%以下にすることで、炭酸マンガン含有量の低下によるFT活性の低下を抑制することが可能となり好ましい。 The amount of the binder added is preferably such that the catalyst activity is not lowered, preferably 1 to 40% by mass, more preferably 3 to 30% by mass. By setting the binder amount to 1% by mass or more, the moldability, bonding property, extrusion property and strength of the catalyst are improved. In addition, it is preferable that the binder amount be 40% by mass or less because a decrease in FT activity due to a decrease in manganese carbonate content can be suppressed.
なお、炭酸マンガン担体あるいはバインダーを含む炭酸マンガン担体の成型品に対しては、上述の含浸法等でFT活性金属やアルカリ金属を含有させて触媒とする。 In addition, a manganese carbonate carrier or a molded article of a manganese carbonate carrier containing a binder is used as a catalyst by containing an FT active metal or an alkali metal by the above-described impregnation method or the like.
<炭化水素類の製造方法>
本発明の炭化水素類の製造方法は、上記の如くして調製された本発明の触媒をFT反応に供して、すなわち該触媒に水素及び一酸化炭素を主成分とする合成ガスを接触させて行われる。本発明の炭化水素類の製造方法においては、FT反応の反応器の形式に関しては、固定床、流動床、懸濁床、スラリー床などが挙げられ、特に限定はしないが、その一例として、以下に、スラリー床による本発明の炭化水素類の製造方法を説明する。
<Method for producing hydrocarbons>
In the method for producing hydrocarbons of the present invention, the catalyst of the present invention prepared as described above is subjected to the FT reaction, that is, the catalyst is brought into contact with synthesis gas mainly composed of hydrogen and carbon monoxide. Done. In the method for producing hydrocarbons of the present invention, the type of the reactor for the FT reaction includes a fixed bed, a fluidized bed, a suspension bed, a slurry bed, and the like, and is not particularly limited. Next, a method for producing the hydrocarbons of the present invention using a slurry bed will be described.
スラリー床にて本発明の炭化水素類の製造方法を行う場合は、触媒の形状としては、球状が好ましく、また、触媒粒子分布として好ましい範囲は1μm以上150μm以下、さらに好ましくは5μm以上120μm以下、最も好ましくは10μm以上110μm以下である。スラリー床反応形式の場合は、液状の炭化水素中などに触媒を分散させて使用するため、触媒粒子径を1μm以上とすることにより、粒子が細かすぎることによる下流側への触媒粒子の流出を抑制し、反応容器内の触媒濃度の低下を抑制し、下流側機器が触媒微粒子によって障害を受けるなどを抑制することができる。また、触媒粒子径を150μm以内とすることにより、反応容器内全体に触媒粒子が分散せずに、スラリーが不均一となることによる反応活性の低下を抑制することができる。また、触媒形状が凹凸がなく球状であることは、スラリー床の反応形式において、触媒同士の接触や触媒と反応器内壁等との接触による触媒の割れや粉化による微粉の発生が低減されるため好ましい。 When the method for producing the hydrocarbons of the present invention is performed in a slurry bed, the shape of the catalyst is preferably spherical, and the preferred range for the catalyst particle distribution is 1 μm or more and 150 μm or less, more preferably 5 μm or more and 120 μm or less, Most preferably, it is 10 μm or more and 110 μm or less. In the case of the slurry bed reaction mode, the catalyst is dispersed in a liquid hydrocarbon and used. Therefore, by setting the catalyst particle diameter to 1 μm or more, the outflow of the catalyst particles to the downstream side due to the particles being too fine. It is possible to suppress the decrease in the catalyst concentration in the reaction vessel and to suppress the downstream device from being damaged by the catalyst fine particles. In addition, by setting the catalyst particle diameter within 150 μm, the catalyst particles are not dispersed throughout the reaction vessel, and the decrease in reaction activity due to non-uniform slurry can be suppressed. The spherical shape of the catalyst with no irregularities reduces the generation of fine particles due to catalyst cracking or pulverization due to contact between the catalysts or contact between the catalyst and the inner wall of the reactor in the reaction mode of the slurry bed. Therefore, it is preferable.
本発明の炭化水素類の製造方法においては、上記の如くして調製された本発明の触媒は、FT反応に供する前に予め還元処理(活性化処理)される。この還元処理により、触媒がFT反応において所望の触媒活性を示すように活性化される。この還元処理を行わなかった場合には、FT活性金属種が十分に還元されず、FT反応において所望の触媒活性を示さない。 In the method for producing hydrocarbons of the present invention, the catalyst of the present invention prepared as described above is subjected to a reduction treatment (activation treatment) in advance before being subjected to the FT reaction. By this reduction treatment, the catalyst is activated so as to exhibit a desired catalytic activity in the FT reaction. If this reduction treatment is not performed, the FT active metal species are not sufficiently reduced and do not exhibit the desired catalytic activity in the FT reaction.
この還元処理は、触媒を液状炭化水素類に分散させたスラリー状態で還元性ガスと接触させる方法でも、炭化水素類を用いず単に触媒に還元性ガスを通気、接触させる方法でも好ましく行うことができる。前者の方法における触媒を分散させる液状炭化水素類としては、処理条件下において液状のものであれば、オレフィン類、アルカン類、脂環式炭化水素類、芳香族炭化水素類を始めとする種々の炭化水素類を使用できる。また、含酸素、含窒素等のヘテロ元素を含む炭化水素であっても良い。これらの炭化水素類の炭素数は、処理条件下において液状のものであれば特に制限する必要はないが、一般にC6〜C40のものが好ましく、C9〜C40のものがより好ましく、C9〜C35のものが最も好ましい。C6の炭化水素類より重質なものであれば、溶媒の蒸気圧が高くなり過ぎず、処理条件幅が制限されないため好ましい。また、C40の炭化水素類より軽質なものであれば、還元性ガスの溶解度が低下せず、十分な還元処理ができるため好ましい。 This reduction treatment is preferably performed by a method in which the catalyst is brought into contact with the reducing gas in a slurry state dispersed in liquid hydrocarbons, or a method in which the reducing gas is simply vented and brought into contact with the catalyst without using hydrocarbons. it can. As the liquid hydrocarbons in which the catalyst is dispersed in the former method, various liquids such as olefins, alkanes, alicyclic hydrocarbons, and aromatic hydrocarbons can be used as long as they are liquid under the processing conditions. Hydrocarbons can be used. Further, it may be a hydrocarbon containing a hetero element such as oxygen-containing or nitrogen-containing. The number of carbons of these hydrocarbons is not particularly limited as long as they are liquid under the processing conditions, but generally those of C6 to C40 are preferred, those of C9 to C40 are more preferred, and those of C9 to C35 are preferred. Is most preferred. If it is heavier than C6 hydrocarbons, the vapor pressure of the solvent does not become too high, and the range of processing conditions is not limited, which is preferable. Moreover, if it is lighter than C40 hydrocarbons, the solubility of the reducing gas does not decrease, and sufficient reduction treatment can be performed, which is preferable.
また、この還元処理に当たり炭化水素類中に分散させる触媒量は、1〜50質量%の濃度が適当あり、好ましくは2〜40質量%、より好ましくは3〜30質量%の濃度である。触媒量が1質量%以上であれば、触媒の還元効率が低下し過ぎることを防ぐことができる。したがって、触媒の還元効率の低下を防ぐ方法として、還元性ガスの通気量を減少させる方法が挙げられる。これにより、気(還元性ガス)−液(溶媒)−固(触媒)の分散が損なわれることを回避することができる。また、触媒量が50質量%以下であれば、炭化水素類に触媒を分散させたスラリーの粘性が高くなり過ぎず、気泡分散が良好で、触媒の還元が十分なされるため好ましい。 In addition, the amount of catalyst dispersed in the hydrocarbons in the reduction treatment is appropriately 1 to 50% by mass, preferably 2 to 40% by mass, more preferably 3 to 30% by mass. If the amount of catalyst is 1% by mass or more, it is possible to prevent the reduction efficiency of the catalyst from being excessively lowered. Therefore, as a method for preventing a reduction in the reduction efficiency of the catalyst, there is a method for reducing the flow rate of the reducing gas. Thereby, it can be avoided that the dispersion of gas (reducing gas) -liquid (solvent) -solid (catalyst) is impaired. A catalyst amount of 50% by mass or less is preferable because the viscosity of the slurry in which the catalyst is dispersed in hydrocarbons does not become too high, the bubble dispersion is good, and the catalyst is sufficiently reduced.
また、この還元処理の処理温度は、140〜250℃が好ましく、150〜200℃がより好ましく、160〜200℃が最も好適である。140℃以上であれば、FT活性金属種およびアルカリ金属種が十分に還元され、十分な反応活性が得られる。また、250℃以下であれば、担体成分の炭酸マンガンの酸化マンガンへの分解が進行して活性低下を招く危険を回避できる。 Moreover, 140-250 degreeC is preferable, the processing temperature of this reduction process has more preferable 150-200 degreeC, and its 160-200 degreeC is the most suitable. If it is 140 degreeC or more, FT active metal seed | species and alkali metal seed | species will fully be reduce | restored and sufficient reaction activity will be obtained. Moreover, if it is 250 degrees C or less, the danger that the decomposition | disassembly to manganese oxide of the manganese carbonate of a support component will advance and an activity fall will be avoided.
この還元処理には、水素を主成分とする還元性ガスが好ましく用いられる。用いる還元性ガスには、水素以外の成分、例えば水蒸気、窒素、希ガスなどを、還元を妨げない範囲である程度の量を含んでいても良い。 For this reduction treatment, a reducing gas mainly containing hydrogen is preferably used. The reducing gas to be used may contain a certain amount of components other than hydrogen, for example, water vapor, nitrogen, rare gas, etc. within a range that does not hinder the reduction.
また、この還元処理は、上記処理温度と共に、水素分圧及び処理時間にも影響されるが、水素分圧は、0.1〜10MPaが好ましく、0.5〜6MPaがより好ましく、1〜5MPaが最も好ましい。還元処理時間は、触媒量、水素通気量等によっても異なるが、一般に、0.1〜72時間が好ましく、1〜48時間がより好ましく、4〜48時間が最も好ましい。処理時間が0.1時間以上であれば、触媒の活性化が不十分となることを回避できる。また、72時間以下であれば、触媒性能の向上に十分である。 Moreover, although this reduction process is influenced also by hydrogen partial pressure and process time with the said process temperature, 0.1-10 MPa is preferable, as for hydrogen partial pressure, 0.5-6 MPa is more preferable, and 1-5 MPa. Is most preferred. The reduction treatment time varies depending on the amount of catalyst, the amount of hydrogen flow, etc., 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 0.1 hour or longer, it is possible to avoid insufficient activation of the catalyst. Moreover, if it is 72 hours or less, it is enough for the improvement of catalyst performance.
本発明の炭化水素類の製造方法においては、上記の如く還元処理した本発明の触媒がFT反応、すなわち炭化水素類の合成反応に供せられる。
本発明の炭化水素類の製造方法におけるFT反応は、触媒を液状炭化水素類中に分散せしめた分散状態となし、この分散状態の触媒に水素と一酸化炭素からなる合成ガスを接触させる。この際、触媒を分散させる炭化水素類としては、上記の予め行う還元処理で用いられる炭化水素類と同様のものを用いることができる。すなわち、反応条件下において液状のものであれば、オレフィン類、アルカン類、脂環式炭化水素類、芳香族炭化水素類を始めとする種々の炭化水素類を使用でき、含酸素、含窒素等のヘテロ元素を含む炭化水素であっても良く、その炭素数は特に制限する必要はないが、一般にC6〜C40のものが好ましく、C9〜C40のものがより好ましく、C9〜C35のものが最も好ましい。C6の炭化水素類より重質なものであれば、溶媒の蒸気圧が高くなり過ぎず、反応条件幅が制限されないため好ましい。また、C40の炭化水素類より軽質なものであれば、原料の合成ガスの溶解度が低下せず、反応活性の低下を回避することができる。上記の予め行う還元処理において、触媒を液状炭化水素類に分散させて行う方法が採用されている場合は、該還元処理で用いられた液状炭化水素類をそのままこのFT反応において用いることができる。
In the method for producing hydrocarbons of the present invention, the catalyst of the present invention reduced as described above is used for the FT reaction, that is, the hydrocarbon synthesis reaction.
The FT reaction in the method for producing hydrocarbons of the present invention is in a dispersed state in which a catalyst is dispersed in liquid hydrocarbons, and a synthesis gas comprising hydrogen and carbon monoxide is brought into contact with the dispersed catalyst. At this time, as the hydrocarbons in which the catalyst is dispersed, the same hydrocarbons used in the reduction treatment performed in advance can be used. That is, various hydrocarbons including olefins, alkanes, alicyclic hydrocarbons, aromatic hydrocarbons can be used as long as they are liquid under the reaction conditions, including oxygen, nitrogen, etc. The number of carbons does not need to be particularly limited, but is generally preferably C6 to C40, more preferably C9 to C40, and most preferably C9 to C35. preferable. If it is heavier than C6 hydrocarbons, the vapor pressure of the solvent does not become too high, and the reaction condition width is not limited, which is preferable. Moreover, if it is lighter than C40 hydrocarbons, the solubility of the raw material synthesis gas will not decrease, and a decrease in reaction activity can be avoided. In the reduction treatment performed in advance, in the case where a method in which the catalyst is dispersed in liquid hydrocarbons is employed, the liquid hydrocarbons used in the reduction treatment can be used as they are in this FT reaction.
FT反応に当たって炭化水素類中に分散させる触媒量は、好ましくは1〜50質量%の濃度であり、より好ましくは2〜40質量%、最も好ましくは3〜30質量%の濃度である。触媒量が1質量%以上であれば、触媒の活性が不足することを回避できる。なお、活性が不足するとその活性の不足を補うために、合成ガスの通気量を減少させ、その合成ガスの通気量の低下により気(合成ガス)−液(溶媒)−固(触媒)の分散が損なわれる。また、触媒量が50質量%以下であれば、炭化水素類に触媒を分散させたスラリーの粘性が高くなりすぎ、気泡分散が悪くなり、反応活性が十分得られなくなることを回避することができる。 The amount of the catalyst dispersed in the hydrocarbons in the FT reaction is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and most preferably 3 to 30% by mass. If the amount of catalyst is 1% by mass or more, it is possible to avoid a lack of catalyst activity. In addition, if the activity is insufficient, in order to make up for the lack of activity, the aeration amount of the synthesis gas is decreased, and the gas (synthesis gas) -liquid (solvent) -solid (catalyst) dispersion is caused by the decrease in the aeration amount of the synthesis gas. Is damaged. Further, if the amount of catalyst is 50% by mass or less, it is possible to avoid that the viscosity of the slurry in which the catalyst is dispersed in hydrocarbons becomes too high, resulting in poor bubble dispersion and insufficient reaction activity. .
FT反応に用いる合成ガスは、水素及び一酸化炭素を主成分としていれば良く、FT反応を妨げない他の成分が混入されていても差し支えない。また、FT反応の速度(k)は、水素分圧に約一次で依存するので、水素及び一酸化炭素の分圧比(H2/COモル比)が0.6以上であることが望まれる。この反応は、体積減少を伴う反応であるため、水素及び一酸化炭素の分圧の合計値が高いほど好ましい。水素及び一酸化炭素の分圧比は、その上限は特に制限されないが、現実的なこの分圧比の範囲としては0.6〜2.7が好ましく、より好ましくは0.8〜2.5、特に好ましくは1〜2.3である。この分圧比が0.6以上であれば、生成する炭化水素類の収量が低下することを防ぐことができ、また、この分圧比が2.7以下であれば、生成する炭化水素類においてガス成分や軽質分が増える傾向を抑止することができる。 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. Further, since the rate (k) of the FT reaction depends on the first order of the hydrogen partial pressure, it is desirable that the partial pressure ratio of hydrogen and carbon monoxide (H 2 / CO molar ratio) is 0.6 or more. Since this reaction is a reaction accompanied by volume reduction, it is preferable that the total value of the partial pressures of hydrogen and carbon monoxide is higher. The upper limit of the partial pressure ratio of hydrogen and carbon monoxide is not particularly limited, but the practical range of the partial pressure ratio is preferably 0.6 to 2.7, more preferably 0.8 to 2.5, and particularly Preferably it is 1-2. If this partial pressure ratio is 0.6 or more, it is possible to prevent the yield of produced hydrocarbons from decreasing, and if this partial pressure ratio is 2.7 or less, gas is produced in the produced hydrocarbons. The tendency to increase the components and light components can be suppressed.
上記合成ガス中に混入していても差し支えないFT反応を妨げない他の成分としては、二酸化炭素が挙げられる。本発明の炭化水素類の製造方法では、天然ガスや石油製品などの改質反応により得られる二酸化炭素の混入している合成ガスも何ら問題なく用いることができる。また、二酸化炭素以外のFT反応を妨げない他の成分が混入されていても差し支えなく、例えば、天然ガスや石油製品等の水蒸気改質反応あるいは自己熱改質反応から得られるようなメタンや水蒸気や部分酸化された窒素等が含有された合成ガスでも良い。また、この二酸化炭素は、二酸化炭素の含有されてない合成ガスに積極的に添加することもできる。本発明の炭化水素類の製造方法の実施に当たって、天然ガスや石油製品を自己熱改質法あるいは水蒸気改質法等で改質して得られた二酸化炭素を含有する合成ガスを、その中の二酸化炭素を除去するための脱炭酸処理をすることなくそのままFT反応に供すれば、脱炭酸処理に要する設備建設コスト及び運転コストを削減することができ、FT反応で得られる炭化水素類の製造コストを低減することができる。 Another component that does not interfere with the FT reaction that may be mixed in the synthesis gas includes carbon dioxide. In the method for producing hydrocarbons of the present invention, synthesis gas mixed with carbon dioxide obtained by a reforming reaction of natural gas or petroleum products can be used without any problem. Also, other components that do not interfere with the FT reaction other than carbon dioxide may be mixed. For example, methane or steam obtained from steam reforming reaction or autothermal reforming reaction of natural gas, petroleum products, etc. Or a synthesis gas containing partially oxidized nitrogen or the like may be used. The carbon dioxide can also be positively added to synthesis gas that does not contain carbon dioxide. In carrying out the method for producing hydrocarbons of the present invention, a synthesis gas containing carbon dioxide obtained by reforming natural gas or petroleum products by a self-thermal reforming method or a steam reforming method is contained therein. If the FT reaction is used as it is without decarboxylation to remove carbon dioxide, the equipment construction cost and operation cost required for the decarboxylation treatment can be reduced, and the hydrocarbons obtained by the FT reaction can be produced. Cost can be reduced.
本発明の炭化水素類の製造方法において、FT反応に供する合成ガス(混合ガス)の全圧(全成分の分圧の合計値)は、0.5〜10MPaが好ましく、0.7〜7MPaがさらに好ましく、0.8〜5MPaがなおさらに好ましい。この全圧が0.5MPa以上であれば、連鎖成長が十分となり、ガソリン分、灯軽油分、ワックス分などの収率が低下することを防ぐことができる。平衡上は、水素及び一酸化炭素の分圧が高いほど有利になるが、上記全圧が10MPa以下であれば、プラント建設コスト等が高まったり、圧縮に必要な圧縮機などの大型化により運転コストが上昇するなどの産業上の観点からの不利益を相応に抑止することができる。 In the method for producing hydrocarbons of the present invention, the total pressure of the synthesis gas (mixed gas) subjected to the FT reaction (total value of partial pressures of all components) is preferably 0.5 to 10 MPa, and 0.7 to 7 MPa. More preferably, 0.8-5 MPa is still more preferable. If this total pressure is 0.5 MPa or more, chain growth is sufficient, and it is possible to prevent the yield of gasoline, kerosene, wax, and the like from decreasing. In terms of equilibrium, the higher the partial pressure of hydrogen and carbon monoxide, the more advantageous. However, if the total pressure is 10 MPa or less, the plant construction cost increases and the operation is increased by increasing the size of the compressor required for compression. The disadvantages from the industrial point of view, such as rising costs, can be suppressed accordingly.
このFT反応においては、一般に、合成ガスのH2/COモル比が同一であれば、反応温度が低いほど連鎖成長確率やC5+選択性(FT反応性生物中の炭素数5以上の生成物の割合)が高くなるが、CO転化率は低くなる。逆に、反応温度が高くなれば、連鎖成長確率、C5+選択性は低くなるが、CO転化率は高くなる。また、H2/CO比が高くなれば、CO転化率が高くなり、連鎖成長確率、C5+選択性は低下し、H2/CO比が低くなれば、その逆となる。これらのファクターが反応に及ぼす効果は、用いる触媒の種類等によってその大小が異なるが、本発明の触媒を用いる方法においては、反応温度は、200〜350℃が適当であり、210〜310℃が好ましく、220〜290℃がさらに好ましい。なお、CO転化率は下記式で定義されるものである。
〔CO転化率〕
CO転化率=[(単位時間当たりの原料ガス中のCOモル数)−(単位時間当たりの出口ガス中のCOモル数)]/単位時間当たりの原料ガス中のCOモル数×100
Generally, in this FT reaction, if the H 2 / CO molar ratio of the synthesis gas is the same, the lower the reaction temperature, the higher the chain growth probability and the C5 + selectivity (for products having 5 or more carbon atoms in the FT-reactive organism). Ratio) increases, but CO conversion decreases. Conversely, if the reaction temperature is increased, the chain growth probability and C5 + selectivity are lowered, but the CO conversion is increased. In addition, the higher the H 2 / CO ratio, the higher the CO conversion rate, the lower the chain growth probability and C5 + selectivity, and vice versa when the H 2 / CO ratio is low. The effect of these factors on the reaction varies depending on the type of catalyst used, but in the method using the catalyst of the present invention, the reaction temperature is suitably 200 to 350 ° C, and 210 to 310 ° C. Preferably, 220 to 290 ° C is more preferable. The CO conversion rate is defined by the following formula.
[CO conversion rate]
CO conversion rate = [(number of moles of CO in raw material gas per unit time) − (number of moles of CO in outlet gas per unit time)] / number of moles of CO in raw material gas per unit time × 100
以下、実施例及び比較例によりさらに具体的に本発明を説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.
以下の実施例において、CO分析は、Active Carbon(60/80mesh)を分離カラムに用いた熱伝導度型ガスクロマトグラフ(TCD−GC)で行った。なお、原料ガスには、Arを内部標準として25vol%添加した合成ガス(H2とCOの混合ガス)を用いた。COのピーク位置、ピーク面積をArと比較することで定性及び定量分析した。触媒の化学成分の同定はICP(CQM-10000P、島津製作所製)により求めた。 In the following Examples, CO analysis was performed by a thermal conductivity gas chromatograph (TCD-GC) using Active Carbon (60/80 mesh) as a separation column. Incidentally, the raw material gas used was 25 vol% added syngas as an internal standard (mixed gas of H 2 and CO) to Ar. Qualitative and quantitative analysis was performed by comparing the peak position and peak area of CO with Ar. The chemical component of the catalyst was identified by ICP (CQM-10000P, manufactured by Shimadzu Corporation).
また、CH4選択率は下記式により算出した。
CH4選択率(%)=(単位時間当たりの出口ガス中のCH4モル数)/{(単位時間当たりの原料ガス中のCOモル数)−(単位時間当たりの出口ガス中のCOモル数)}×100
Further, CH 4 selectivity was calculated by the following equation.
CH 4 selectivity (%) = (CH 4 moles in outlet gas per unit time) / {(number of CO moles in raw material gas per unit time) − (number of CO moles in outlet gas per unit time) )} × 100
実施例1
炭酸マンガンとして和光純薬工業製の炭酸マンガン(II)n水和物を使用した。N2吸着法で測定した比表面積は46.4m2/g、細孔容積は0.15ml/g、細孔径は4.2nmであった。予め150℃で5時間乾燥した後、炭酸マンガン4.9gを秤量し、それに、水3.0gに塩化ルテニウム(小島化学製Ru Assay 40.79質量%)0.18gを溶解した水溶液を含浸させ、1時間放置した後、空気中、80℃で3時間乾燥した。
Example 1
Manganese (II) carbonate n hydrate manufactured by Wako Pure Chemical Industries was used as manganese carbonate. The specific surface area measured by the N 2 adsorption method was 46.4 m 2 / g, the pore volume was 0.15 ml / g, and the pore diameter was 4.2 nm. After drying at 150 ° C. for 5 hours in advance, 4.9 g of manganese carbonate was weighed, and then impregnated with an aqueous solution in which 0.18 g of ruthenium chloride (Ru Assay 40.79% by mass manufactured by Kojima Chemical) was dissolved in 3.0 g of water. After being left for 1 hour, it was dried in air at 80 ° C. for 3 hours.
乾燥品全量を0.05Nのアンモニア水100mlに浸漬し、マグネチックスターラーで約1時間アルカリ水溶液処理した後ろ過し、300mlの水で洗浄ろ過した。これを80℃で3時間乾燥後、150℃で3時間焼成した。次に、得られた焼成品3.0gを秤量し、これに、0.007gの炭酸ナトリウム(和光純薬製)を1.5gの水に溶解した炭酸ナトリウム水溶液を含浸させ、1時間放置した後、空気中、80℃で3時間乾燥後、150℃で3時間焼成して触媒Aを得た。
触媒AについてX線回折にて構造分析を行った結果、マンガンは炭酸マンガンを維持していた。また、ICPにて触媒Aの化学組成分析を行った結果、ルテニウムは金属換算で1.5質量%、ナトリウムは金属換算で0.1質量%であった。
The total amount of the dried product was immersed in 100 ml of 0.05N aqueous ammonia, treated with an aqueous alkaline solution with a magnetic stirrer for about 1 hour, filtered, washed with 300 ml of water and filtered. This was dried at 80 ° C. for 3 hours and then calcined at 150 ° C. for 3 hours. Next, 3.0 g of the obtained baked product was weighed and impregnated with an aqueous sodium carbonate solution obtained by dissolving 0.007 g of sodium carbonate (manufactured by Wako Pure Chemical Industries) in 1.5 g of water, and left for 1 hour. Thereafter, the catalyst A was obtained by drying in air at 80 ° C. for 3 hours and calcining at 150 ° C. for 3 hours.
As a result of structural analysis of the catalyst A by X-ray diffraction, manganese maintained manganese carbonate. Further, as a result of chemical composition analysis of the catalyst A by ICP, ruthenium was 1.5% by mass in terms of metal and sodium was 0.1% by mass in terms of metal.
触媒A、2.4gを分散媒のノルマルヘキサデカン40ml(スラリー濃度7.2重量%)と共に内容積100mlの反応器に充填し、水素分圧0.9MPa・G、温度170℃、流量100(STP)ml/min(STP:standard temperature and pressure)で水素を触媒Aに接触させて3時間還元した。還元後、H2/CO比約2の合成ガス(Ar約25vol.%含む)に切り換え、温度260℃、圧力0.9MPa・GにしてFT反応を行った。
W/F(weight/flow)[g・hr/mol]は約11g・hr/molであった。FT反応開始20時間後のCO転化率は約52.7%、CH4選択率は約8.1%、100時間後のCO転化率は約51.8%であった。
Catalyst A (2.4 g) was charged into a reactor having an internal volume of 100 ml together with 40 ml of normal hexadecane (slurry concentration: 7.2 wt%) as a dispersion medium, a hydrogen partial pressure of 0.9 MPa · G, a temperature of 170 ° C., and a flow rate of 100 (STP). ) Hydrogen was brought into contact with catalyst A at ml / min (STP: standard temperature and pressure) and reduced for 3 hours. After the reduction, the FT reaction was carried out at a temperature of 260 ° C. and a pressure of 0.9 MPa · G by switching to a synthesis gas having an H 2 / CO ratio of about 2 (including about 25 vol.% Ar).
W / F (weight / flow) [g · hr / mol] was about 11 g · hr / mol. The CO conversion after 20 hours from the start of the FT reaction was about 52.7%, the CH 4 selectivity was about 8.1%, and the CO conversion after 100 hours was about 51.8%.
実施例2
ルテニウムの含有量が金属換算で3.0質量%、ナトリウム含有量が金属換算で1.0質量%となるように炭酸マンガン、塩化ルテニウムおよび炭酸ナトリウムの量を調節した以外は実施例1と同様にして触媒Bを得た。
この触媒BについてX線回折にて構造分析を行った結果、マンガンは炭酸マンガンを維持していた。ICPにて触媒Bの化学組成分析を行った結果、ルテニウムは金属換算で3.0質量%、ナトリウムは金属換算で1.0質量%であった。この触媒Bを実施例1と同様の方法でFT反応に供した。FT反応開始20時間後のCO転化率は約72.4%、CH4選択率は7.8%、100時間後のCO転化率は約72.1%であった。
Example 2
Example 1 except that the amounts of manganese carbonate, ruthenium chloride and sodium carbonate were adjusted so that the ruthenium content was 3.0% by mass in terms of metal and the sodium content was 1.0% by mass in terms of metal. Thus, catalyst B was obtained.
As a result of structural analysis of the catalyst B by X-ray diffraction, manganese maintained manganese carbonate. As a result of analyzing the chemical composition of the catalyst B by ICP, ruthenium was 3.0% by mass in terms of metal, and sodium was 1.0% by mass in terms of metal. This catalyst B was subjected to the FT reaction in the same manner as in Example 1. The CO conversion rate 20 hours after the start of the FT reaction was about 72.4%, the CH 4 selectivity was 7.8%, and the CO conversion rate after 100 hours was about 72.1%.
実施例3
触媒化成工業製のシリカゾル(SI-550)270gに実施例1で用いた塩化ルテニウム11.0gを溶解し、次いで炭酸マンガン乾燥品210g、炭酸ナトリウム2.0gを添加し、混合した。これに、メチルセルロース(和光純薬製MC4000)を30.0gを添加し、乳鉢で十分に混練した。次に、硝酸コバルト(和光純薬製)49.5gを水40.0gに溶解した水溶液を徐々に加えてさらに良く混練した。この混練品を押出し成型機(押し出し穴径1.5mm)を用いて押し出し、成型品を80℃で3時間乾燥後、200℃で3時間空気中焼成し、触媒Cを得た。
この触媒CについてX線回折にて構造分析を行った結果、マンガンは炭酸マンガンを維持していた。ICPにて触媒Cの化学組成分析を行った結果、ルテニウムは金属換算で1.5質量%、コバルトは金属換算で10.0%、ナトリウムは金属換算で0.3質量%であった。この触媒Cを粉砕し、実施例1と同様の方法でFT反応に供した。FT反応開始20時間後のCO転化率は約77.7%、CH4選択率は14.2%、100時間後のCO転化率は約77.1%であった。
Example 3
11.0 g of ruthenium chloride used in Example 1 was dissolved in 270 g of silica sol (SI-550) manufactured by Catalyst Chemical Industry, and then 210 g of dried manganese carbonate and 2.0 g of sodium carbonate were added and mixed. To this, 30.0 g of methylcellulose (MC4000 manufactured by Wako Pure Chemical Industries, Ltd.) was added and sufficiently kneaded in a mortar. Next, an aqueous solution in which 49.5 g of cobalt nitrate (manufactured by Wako Pure Chemical Industries) was dissolved in 40.0 g of water was gradually added and further kneaded. This kneaded product was extruded using an extrusion molding machine (extrusion hole diameter: 1.5 mm), and the molded product was dried at 80 ° C. for 3 hours and then calcined in air at 200 ° C. for 3 hours to obtain Catalyst C.
As a result of structural analysis of the catalyst C by X-ray diffraction, manganese maintained manganese carbonate. As a result of chemical composition analysis of catalyst C by ICP, ruthenium was 1.5% by mass in terms of metal, cobalt was 10.0% in terms of metal, and sodium was 0.3% by mass in terms of metal. The catalyst C was pulverized and subjected to the FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 77.7%, the CH 4 selectivity was 14.2%, and the CO conversion after 100 hours was about 77.1%.
実施例4
炭酸マンガン3.50gを秤量し、それに、水5.0gに硝酸コバルト7.5gを溶解した水溶液を含浸させ、1時間放置した後、空気中、80℃で3時間乾燥し200℃で3時間焼成した。次に、得られた焼成品3.0gを秤量し、これに、0.04gの炭酸カリウム(和光純薬製)を1.5gの水に溶解した炭酸カリウム水溶液を含浸させ、1時間放置した後、空気中、80℃で3時間乾燥後、200℃で3時間焼成して触媒Dを得た。
この触媒DについてX線回折にて構造分析を行った結果、マンガンは炭酸マンガンを維持していた。また、ICPにて触媒Dの化学組成分析を行った結果、コバルトは金属換算で30.1質量%、カリウムは金属換算で0.8質量%であった。この触媒Dを粉砕し、実施例1と同様の方法でFT反応に供した。FT反応開始20時間後のCO転化率は約69.1%、CH4選択率は12.6%、100時間後のCO転化率は約67.9%であった。
Example 4
Weigh 3.50 g of manganese carbonate, impregnate it with an aqueous solution of 7.5 g of cobalt nitrate dissolved in 5.0 g of water, leave it for 1 hour, and then dry in air at 80 ° C. for 3 hours and at 200 ° C. for 3 hours. Baked. Next, 3.0 g of the obtained fired product was weighed and impregnated with an aqueous potassium carbonate solution prepared by dissolving 0.04 g of potassium carbonate (manufactured by Wako Pure Chemical Industries) in 1.5 g of water, and left for 1 hour. Thereafter, the catalyst D was obtained by drying in air at 80 ° C. for 3 hours and calcining at 200 ° C. for 3 hours.
As a result of structural analysis of the catalyst D by X-ray diffraction, manganese maintained manganese carbonate. Moreover, as a result of conducting the chemical composition analysis of the catalyst D in ICP, cobalt was 30.1 mass% in metal conversion, and potassium was 0.8 mass% in metal conversion. The catalyst D was pulverized and subjected to the FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 69.1%, the CH 4 selectivity was 12.6%, and the CO conversion after 100 hours was about 67.9%.
比較例1
炭酸マンガン4.9gを秤量し、水3.0gに塩化ルテニウム0.37gを溶解した水溶液を含浸し、1時間放置した後、空気中、80℃で3時間乾燥し、その後150℃で3時間焼成し触媒Eを得た。この触媒EについてX線回折にて構造分析を行った結果、マンガンは炭酸マンガンを維持していた。
また、ICPにて触媒Eの化学組成分析を行った結果、ルテニウムは金属換算で2.9質量%であった。この触媒Eを実施例1と同様の方法でFT反応に供した。FT反応開始20時間後のCO転化率は約70.9%、CH4選択率は11.5%、100時間後のCO転化率は約70.3%であった。
Comparative Example 1
Weighing 4.9 g of manganese carbonate, impregnating an aqueous solution of 0.37 g of ruthenium chloride in 3.0 g of water, allowing it to stand for 1 hour, drying in air at 80 ° C. for 3 hours, and then at 150 ° C. for 3 hours The catalyst E was obtained by calcination. As a result of structural analysis of this catalyst E by X-ray diffraction, manganese maintained manganese carbonate.
Moreover, as a result of conducting the chemical composition analysis of the catalyst E in ICP, ruthenium was 2.9 mass% in metal conversion. This catalyst E was subjected to FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 70.9%, the CH 4 selectivity was 11.5%, and the CO conversion after 100 hours was about 70.3%.
比較例2
炭酸マンガン4.4gを秤量し、それに、水3.0gに塩化ルテニウム0.18gおよび硝酸コバルト2.5gを溶解した水溶液を含浸させ、1時間放置した後、空気中、80℃で3時間乾燥し、その後200℃で3時間焼成し触媒Fを得た。この触媒FについてX線回折にて構造分析を行った結果、マンガンは炭酸マンガンを維持していた。
また、ICPにて触媒Fの化学組成分析を行った結果、ルテニウムは金属換算で1.5質量%、コバルトは金属換算で10.1質量%であった。この触媒Fを実施例1と同様の方法でFT反応に供した。FT反応開始20時間後のCO転化率は約76.7%、CH4選択率は約35.4%、100時間後のCO転化率は約76.2%であった。
Comparative Example 2
Weigh 4.4 g of manganese carbonate, impregnate it with an aqueous solution of 0.18 g of ruthenium chloride and 2.5 g of cobalt nitrate in 3.0 g of water, leave it for 1 hour, and then dry in air at 80 ° C. for 3 hours. And then calcined at 200 ° C. for 3 hours to obtain Catalyst F. As a result of structural analysis of the catalyst F by X-ray diffraction, manganese maintained manganese carbonate.
Moreover, as a result of conducting the chemical composition analysis of the catalyst F in ICP, ruthenium was 1.5 mass% in metal conversion, and cobalt was 10.1 mass% in metal conversion. This catalyst F was subjected to FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 76.7%, the CH 4 selectivity was about 35.4%, and the CO conversion after 100 hours was about 76.2%.
比較例3
実施例4において、カリウム金属の担持を実施せずにコバルト金属の含浸担持までを行い触媒Gを得た。この触媒GについてX線回折にて構造分析を行った結果、マンガンは炭酸マンガンを維持していた。
また、ICPにて触媒Gの化学組成分析を行った結果、コバルトは金属換算で30.2質量%であった。この触媒Gを実施例1と同様の方法でFT反応に供した。FT反応開始20時間後のCO転化率は約68.2%、CH4選択率は約20.8%、100時間後のCO転化率は約67.1%であった。
Comparative Example 3
In Example 4, catalyst G was obtained by carrying out impregnation with cobalt metal without carrying potassium metal. As a result of structural analysis of the catalyst G by X-ray diffraction, manganese maintained manganese carbonate.
Moreover, as a result of conducting the chemical composition analysis of the catalyst G in ICP, cobalt was 30.2 mass% in metal conversion. This catalyst G was subjected to the FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 68.2%, the CH 4 selectivity was about 20.8%, and the CO conversion after 100 hours was about 67.1%.
比較例4
炭酸マンガンに代えて酸化アルミニウム粉末(Pural SB, Condea製)を予め充分乾燥した後、4.9gを秤量し、それに、水4.4gに塩化ルテニウム0.18gを溶解した水溶液を含浸させ、1時間放置した後、空気中、80℃で3時間乾燥し、その後200℃で3時間焼成し触媒Hを得た。
ICPにて触媒Hの化学組成分析を行った結果、ルテニウムは金属換算で1.5質量%であった。この触媒Hを実施例1と同様の方法でFT反応に供した。FT反応開始20時間後のCO転化率は約30.2%、CH4選択率は約21.0%、100時間後のCO転化率は約18.9%であった。
Comparative Example 4
In place of manganese carbonate, aluminum oxide powder (Pural SB, manufactured by Condea) was sufficiently dried in advance, and 4.9 g was weighed, and then impregnated with an aqueous solution in which 0.18 g of ruthenium chloride was dissolved in 4.4 g of water. After standing for a period of time, it was dried in air at 80 ° C. for 3 hours, and then calcined at 200 ° C. for 3 hours to obtain Catalyst H.
As a result of analyzing the chemical composition of the catalyst H by ICP, ruthenium was 1.5% by mass in terms of metal. This catalyst H was subjected to FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 30.2%, the CH 4 selectivity was about 21.0%, and the CO conversion after 100 hours was about 18.9%.
比較例5
炭酸マンガンに代えて和光純薬工業製の酸化マンガン(II)(MnO)4.9gを秤量し、それに、水3.0gに塩化ルテニウム0.18gを溶解した水溶液を含浸させ、1時間放置した後、空気中、80℃で3時間乾燥し、その後150℃で3時間焼成した。次に、得られた焼成品3.0gを秤量し、これに、0.007gの炭酸ナトリウム(和光純薬製)を1.5gの水に溶解した炭酸ナトリウム水溶液を含浸させ、1時間放置した後、空気中、80℃で3時間乾燥後、150℃で3時間焼成して触媒Iを得た。
ICPにて触媒Iの化学組成分析を行った結果、ルテニウムは金属換算で1.5質量%、ナトリウムは金属換算で0.1質量%であった。この触媒Iを実施例1と同様の方法でFT反応に供した。FT反応開始20時間後のCO転化率は約11.9%、CH4選択率は6.5%、100時間後のCO転化率は約9.6%であった。
Comparative Example 5
Instead of manganese carbonate, 4.9 g of manganese oxide (II) (MnO) manufactured by Wako Pure Chemical Industries, Ltd. was weighed, impregnated with an aqueous solution of 0.18 g of ruthenium chloride in 3.0 g of water, and allowed to stand for 1 hour. Thereafter, it was dried in air at 80 ° C. for 3 hours and then calcined at 150 ° C. for 3 hours. Next, 3.0 g of the obtained baked product was weighed and impregnated with an aqueous sodium carbonate solution obtained by dissolving 0.007 g of sodium carbonate (manufactured by Wako Pure Chemical Industries) in 1.5 g of water, and left for 1 hour. Thereafter, the catalyst I was obtained by drying in air at 80 ° C. for 3 hours and calcining at 150 ° C. for 3 hours.
As a result of analyzing the chemical composition of the catalyst I by ICP, ruthenium was 1.5% by mass in terms of metal and sodium was 0.1% by mass in terms of metal. This catalyst I was subjected to the FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 11.9%, the CH 4 selectivity was 6.5%, and the CO conversion after 100 hours was about 9.6%.
上記実施例1〜4及び比較例1〜5の実験結果を表1及び表2に示す。表1及び表2から、本発明の炭酸マンガン担体を用い、アルカリ金属を含有する触媒は、従来のアルミナやシリカを担体とする触媒やアルカリ金属を含有しない触媒に比較してCO転化率が高く、また、ガス成分であるCH4の生成割合が低いことが明らかである。 The experimental results of Examples 1 to 4 and Comparative Examples 1 to 5 are shown in Tables 1 and 2. From Tables 1 and 2, the catalyst containing the manganese carbonate support of the present invention and containing an alkali metal has a higher CO conversion rate than the conventional catalyst using alumina or silica as a support or a catalyst containing no alkali metal. Also, it is clear that the production ratio of CH 4 which is a gas component is low.
さらに、本発明の触媒の性能は長時間安定的に発揮されることが分かる。また、本発明のこのような効果は、酸化マンガンの担体を用いたのでは認められず、炭酸マンガンの担体を用いることで発現していることが分かる。 Furthermore, it turns out that the performance of the catalyst of this invention is exhibited stably for a long time. Further, it can be seen that such an effect of the present invention is not observed when a manganese oxide carrier is used, but is manifested by using a manganese carbonate carrier.
Claims (7)
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009070113A JP5128526B2 (en) | 2009-03-23 | 2009-03-23 | Fischer-Tropsch synthesis catalyst and method for producing hydrocarbons |
PCT/JP2009/059076 WO2009157260A1 (en) | 2008-06-24 | 2009-05-15 | Catalyst for fischer-tropsch synthesis, and process for production of hydrocarbon |
MYPI2010006116A MY153782A (en) | 2008-06-24 | 2009-05-15 | Catalyst for fischer-tropsch synthesis and method for producing hydrocarbons |
US13/000,915 US8598063B2 (en) | 2008-06-24 | 2009-05-15 | Catalyst for Fischer-Tropsch synthesis and method for producing hydrocarbons |
EP09769970.6A EP2301663B1 (en) | 2008-06-24 | 2009-05-15 | Catalyst for fischer-tropsch synthesis and method for producing hydrocarbons |
AU2009263607A AU2009263607B8 (en) | 2008-06-24 | 2009-05-15 | Catalyst for Fischer-Tropsch synthesis and method for producing hydrocarbons |
ES09769970T ES2882830T3 (en) | 2008-06-24 | 2009-05-15 | Catalyst for Fischer-Tropsch synthesis and method for producing hydrocarbons |
CN2009801241661A CN102076413B (en) | 2008-06-24 | 2009-05-15 | Catalyst for fischer-tropsch synthesis, and process for production of hydrocarbon |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009070113A JP5128526B2 (en) | 2009-03-23 | 2009-03-23 | Fischer-Tropsch synthesis catalyst and method for producing hydrocarbons |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2010221108A JP2010221108A (en) | 2010-10-07 |
JP5128526B2 true JP5128526B2 (en) | 2013-01-23 |
Family
ID=43038879
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2009070113A Active JP5128526B2 (en) | 2008-06-24 | 2009-03-23 | Fischer-Tropsch synthesis catalyst and method for producing hydrocarbons |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5128526B2 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012152666A (en) * | 2011-01-24 | 2012-08-16 | Cosmo Oil Co Ltd | Production method for catalyst for fischer-tropsch synthesis |
EP2669010A1 (en) * | 2011-01-24 | 2013-12-04 | Cosmo Oil Co., Ltd. | Catalyst for fischer-tropsch synthesis, and production method therefor, as well as hydrocarbon production method using fischer-tropsch synthesis catalyst |
JP5683012B2 (en) * | 2011-06-17 | 2015-03-11 | コスモ石油株式会社 | Gasoline composition and method for producing gasoline composition |
JP5683011B2 (en) * | 2011-06-17 | 2015-03-11 | コスモ石油株式会社 | Gasoline composition and method for producing gasoline composition |
JP5683015B2 (en) * | 2011-06-17 | 2015-03-11 | コスモ石油株式会社 | Gasoline composition and method for producing gasoline composition |
JP5683013B2 (en) * | 2011-06-17 | 2015-03-11 | コスモ石油株式会社 | Gasoline composition and method for producing gasoline composition |
JP5683016B2 (en) * | 2011-06-17 | 2015-03-11 | コスモ石油株式会社 | Gasoline composition and method for producing gasoline composition |
JP5683014B2 (en) * | 2011-06-17 | 2015-03-11 | コスモ石油株式会社 | Gasoline composition and method for producing gasoline composition |
WO2014024774A1 (en) * | 2012-08-10 | 2014-02-13 | 住友化学株式会社 | Method for producing olefin having 2-4 carbon atoms and method for producing propylene |
AU2015366160B2 (en) | 2014-12-19 | 2020-04-16 | Bp P.L.C. | Process for preparation of a supported cobalt-containing Fischer-Tropsch synthesis catalyst |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60146835A (en) * | 1983-12-29 | 1985-08-02 | Res Assoc Petroleum Alternat Dev<Rapad> | Preparation of olefin |
JPH062232B2 (en) * | 1985-02-25 | 1994-01-12 | エクソン リサ−チ アンド エンヂニアリング コムパニ− | Cobalt-promoted Fisher-Tropsch catalyst |
US4801573A (en) * | 1987-10-23 | 1989-01-31 | 501 Den Norske Stats Oljeslenskap A.S. | Catalyst for production of hydrocarbons |
JP4205301B2 (en) * | 2000-11-24 | 2009-01-07 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Process for producing hydrocarbons by Fischer-Tropsch process |
EP1515912B1 (en) * | 2002-06-25 | 2007-08-22 | Albemarle Netherlands B.V. | Use of cationic layered materials, compositions comprising these materials, and the preparation of cationic layered materials |
JP4006328B2 (en) * | 2002-12-16 | 2007-11-14 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Production method of hydrocarbons by Fischer-Tropsch process |
-
2009
- 2009-03-23 JP JP2009070113A patent/JP5128526B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2010221108A (en) | 2010-10-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5128526B2 (en) | Fischer-Tropsch synthesis catalyst and method for producing hydrocarbons | |
US8987163B2 (en) | Production of lower olefins from synthesis gas | |
JP5129037B2 (en) | Fischer-Tropsch synthesis catalyst and method for producing hydrocarbons | |
WO2005079979A1 (en) | Catalyst for producing hydrocarbons, method for preparing the same, and method for producing hydrocarbons using the same | |
US11912943B2 (en) | Fischer-Tropsch process, supported Fischer-Tropsch synthesis catalyst and uses thereof | |
WO2009157260A1 (en) | Catalyst for fischer-tropsch synthesis, and process for production of hydrocarbon | |
JP2011045874A (en) | Catalyst for ft synthesis and method of manufacturing the same, and method of manufacturing hydrocarbon using the catalyst | |
JP4773116B2 (en) | Method for producing catalyst for producing hydrocarbons from synthesis gas, and method for producing hydrocarbons from synthesis gas using the catalyst | |
EP3628400A1 (en) | Fischer-tropsch process, supported fischer-tropsch synthesis catalyst and uses thereof | |
WO2012102256A1 (en) | Catalyst for fischer-tropsch synthesis, and production method therefor, as well as hydrocarbon production method using fischer-tropsch synthesis catalyst | |
JP5553880B2 (en) | Method for producing catalyst for Fischer-Tropsch synthesis | |
WO2020064929A1 (en) | Fischer-tropsch process | |
JP4421913B2 (en) | Method for producing catalyst for producing hydrocarbons and method for producing hydrocarbons using the catalyst | |
JP4267482B2 (en) | Hydrocarbon production catalyst and method for producing hydrocarbons using the catalyst | |
JP2024502262A (en) | Methane production method | |
JP2012152665A (en) | Catalyst for fischer-tropsch synthesis and production method therefor | |
JP2012152666A (en) | Production method for catalyst for fischer-tropsch synthesis |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110328 |
|
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: 20121002 |
|
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: 20121031 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 5128526 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151109 Year of fee payment: 3 |
|
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 |
|
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 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |