JP2011127014A - Method for producing hydrocarbon - Google Patents
Method for producing hydrocarbon Download PDFInfo
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- JP2011127014A JP2011127014A JP2009287597A JP2009287597A JP2011127014A JP 2011127014 A JP2011127014 A JP 2011127014A JP 2009287597 A JP2009287597 A JP 2009287597A JP 2009287597 A JP2009287597 A JP 2009287597A JP 2011127014 A JP2011127014 A JP 2011127014A
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- Prior art keywords
- reaction
- catalyst
- hydrocarbons
- zeolite
- synthesis
- Prior art date
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- Granted
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 85
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 239000004215 Carbon black (E152) Substances 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 175
- 238000006243 chemical reaction Methods 0.000 claims abstract description 129
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 104
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 102
- 239000007789 gas Substances 0.000 claims abstract description 67
- 239000010457 zeolite Substances 0.000 claims abstract description 67
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 64
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 63
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 63
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 63
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 63
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 63
- 239000002184 metal Substances 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011973 solid acid Substances 0.000 claims abstract description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 11
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 49
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 17
- 229910052707 ruthenium Inorganic materials 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
- 230000008569 process Effects 0.000 claims description 4
- 239000003502 gasoline Substances 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 18
- 150000001336 alkenes Chemical class 0.000 abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001491 aromatic compounds Chemical class 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 29
- 239000007864 aqueous solution Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 16
- 230000009467 reduction Effects 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000002028 Biomass Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000002309 gasification Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000003350 kerosene Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- 150000003303 ruthenium Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000001868 cobalt Chemical class 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 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
- 238000002441 X-ray diffraction Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000004993 emission spectroscopy Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 238000012916 structural analysis Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- -1 various alcohols Chemical class 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002131 composite material Substances 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
- 238000005516 engineering process Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 230000005068 transpiration Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 241001474374 Blennius Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 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
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 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
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000001125 extrusion Methods 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
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000011160 research 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
- 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
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002303 thermal reforming Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
Abstract
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、フィッシャー・トロプシュ（ＦＴ）反応により炭化水素類を製造する方法に関する。さらに詳しくは、炭酸マンガン及びＦＴ活性金属を含むＦＴ合成触媒と、固体酸を示すゼオライトとを用いることを特徴とする炭化水素類の製造方法に関する。 The present invention relates to a method for producing hydrocarbons by a Fischer-Tropsch (FT) reaction from a mixed gas containing hydrogen and carbon monoxide as main components (hereinafter referred to as “synthesis gas”). More specifically, the present invention relates to a method for producing hydrocarbons characterized by using an FT synthesis catalyst containing manganese carbonate and an FT active metal and a zeolite showing a solid acid.
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（Ｆｉｓｃｈｅｒ−Ｔｒｏｐｓｃｈ）反応（以下「ＦＴ反応」という。）やメタノール合成反応などが良く知られている。ＦＴ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ある。一方、メタノール合成反応は銅系触媒で進行し、Ｃ２含酸素（エタノール、アセトアルデヒド等）合成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 a method for synthesizing hydrocarbons from synthesis gas, a Fischer-Tropsch reaction (hereinafter referred to as “FT reaction”), a methanol synthesis reaction, and the like are well known. The FT reaction is a catalyst that uses an iron group element of iron, cobalt, nickel, or a platinum group element such as ruthenium as an active metal. On the other hand, it is known that methanol synthesis reaction proceeds with a copper-based catalyst, and C2 oxygen-containing (ethanol, acetaldehyde, etc.) synthesis proceeds with a rhodium-based catalyst (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。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。 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 to meet these demands, GTL (gas to liquids) is a technology that synthesizes liquid fuel 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 there. 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、ＦＴ反応によって、合成ガスから炭化水素類を製造する方法が盛んに研究されている。このＦＴ反応によって得られる炭化水素類は、メタンからワックスに至るまでの幅広い炭化水素と各種アルコールなどの微量の含酸素化合物であり、ある特定の留分を選択的に生成することはできない。そこで、例えば、ＦＴ反応によって効率的に灯軽油留分を得るために、ＦＴ反応によって生成する直留の灯軽油留分に加えて、それよりも重質なワックス留分を水素化分解して灯軽油留分を生成し、灯軽油留分の収率を増やすことが一般的に行われている。 As part of the GTL, methods for producing hydrocarbons from synthesis gas by the FT reaction have been actively studied. The hydrocarbons obtained by this FT reaction are a wide range of hydrocarbons ranging from methane to wax and trace amounts of oxygen-containing compounds such as various alcohols, and cannot selectively produce a specific fraction. Therefore, for example, in order to efficiently obtain a kerosene fraction by the FT reaction, in addition to the straight kerosene fraction produced by the FT reaction, a heavier wax fraction is hydrocracked. It is common practice to produce a kerosene fraction and increase the yield of the kerosene fraction.
一方、ＦＴ反応によって、ガソリン留分も得ることができる。しかしながら、ＦＴ反応によって生成される炭化水素は、直鎖のパラフィンやオレフィンが主成分であるため、ＦＴ反応によって得られるガソリン留分は、オクタン価が非常に低く実用性がない。通常、炭化水素のオクタン価は、芳香族炭化水素が最も高く、次いで、ナフテン系炭化水素、オレフィン系炭化水素、パラフィン系炭化水素の順に低くなる。また、同族の炭化水素では、炭素数の少ない、いわゆる低沸点のものほどオクタン価が高く、同じ炭素数でも分岐の多いものほど高い。 On the other hand, a gasoline fraction can also be obtained by FT reaction. However, since the hydrocarbons produced by the FT reaction are mainly composed of linear paraffins and olefins, the gasoline fraction obtained by the FT reaction has a very low octane number and is not practical. Normally, the octane number of hydrocarbons is the highest for aromatic hydrocarbons, and then decreases in the order of naphthenic hydrocarbons, olefinic hydrocarbons, and paraffinic hydrocarbons. In the case of the same family hydrocarbons, the lower the number of carbon atoms, the lower the boiling point, the higher the octane number, and the higher the number of carbon atoms with the same number of branches.
従来から、ＦＴ合成によって生成する炭化水素を、ゼオライトなどの固体酸触媒によって分解、異性化することによりガソリン留分を製造する方法が提案されている。例えば、ルテニウムやコバルトといったＦＴ活性金属種（ＦＴ反応に活性を示す金属種）を含むＦＴ合成触媒とＺＳＭ−５やβゼオライトとが共存する触媒を用いて、１段階の反応により合成ガスからガソリン留分を製造する方法（１段法）が提案されている（例えば、特許文献１及び２参照。）。また、ＦＴ合成触媒による反応と固体酸触媒による反応との２段階の反応により、それぞれを最適な温度で反応させてガソリン留分を製造する方法（２段法）も提案されている（例えば、特許文献３参照。）。 Conventionally, a method for producing a gasoline fraction by decomposing and isomerizing a hydrocarbon produced by FT synthesis with a solid acid catalyst such as zeolite has been proposed. For example, using a FT synthesis catalyst containing FT active metal species such as ruthenium and cobalt (metal species showing activity in FT reaction) and a catalyst in which ZSM-5 and β zeolite coexist, the synthesis gas is converted into gasoline by a one-step reaction. A method for producing a fraction (one-stage method) has been proposed (see, for example, Patent Documents 1 and 2). In addition, a method (two-stage method) for producing a gasoline fraction by reacting at an optimum temperature by a two-stage reaction of a reaction with an FT synthesis catalyst and a reaction with a solid acid catalyst has also been proposed (for example, (See Patent Document 3).
従来法のうちの１段法では、ＦＴ合成触媒と固体酸触媒の最適反応温度域が異なるため、両反応を共に効率よく行うことができない、という問題がある。例えば、ＦＴ合成触媒に最適な比較的低温で反応を行った場合、ＣＨ４などの低級炭化水素の生成は抑えられ炭素数５以上の高級炭化水素が効率よく生成するが、低温のため固体酸触媒の活性が低く、生成した炭化水素の分解や異性化反応が低下し、ガソリン収率が低下するとともに、芳香族炭化水素や分岐状の炭化水素といった高オクタン価な炭化水素の生成も低下する。逆に、固体酸触媒に最適な温度で反応を行った場合、ＦＴ反応で、ＣＨ４などの低級炭化水素やＣＯ２といったガス成分の生成が促進され、ガソリン収率が低下するといった問題が生じる。 The conventional one-stage method has a problem that both reactions cannot be performed efficiently because the optimum reaction temperature ranges of the FT synthesis catalyst and the solid acid catalyst are different. For example, when the reaction is carried out at a relatively low temperature that is optimal for an FT synthesis catalyst, the production of lower hydrocarbons such as CH 4 is suppressed and higher hydrocarbons having 5 or more carbon atoms are efficiently produced. The activity of the catalyst is low, the decomposition and isomerization reaction of the produced hydrocarbons are lowered, the gasoline yield is lowered, and the production of high octane hydrocarbons such as aromatic hydrocarbons and branched hydrocarbons is also lowered. Conversely, when the reaction is carried out at an optimum temperature for the solid acid catalyst, the FT reaction promotes the generation of gas components such as lower hydrocarbons such as CH 4 and CO 2, resulting in a decrease in gasoline yield. .
一方で２段法では、それぞれの触媒の最適温度で反応を進行させることが可能であり、効率よくガソリン留分を製造することが可能である。しかしながら、プロセスのコストが向上するといった問題や、２段目の反応前に水素を投入して水素化分解を進行させるために、生成物中のイソパラフィンは生成されるがオレフィン分が減少し、オクタン価の低下に繋がるといった問題がある。 On the other hand, in the two-stage method, the reaction can proceed at the optimum temperature of each catalyst, and a gasoline fraction can be efficiently produced. However, since the cost of the process is increased and hydrogenolysis is carried out by introducing hydrogen before the second stage reaction, isoparaffin in the product is produced, but the olefin content is reduced, and the octane number is reduced. There is a problem that leads to a decrease in
本発明では、ＣＯ転化率が高く、ガス成分の生成が少なく、かつ芳香族やナフテン、オレフィン、分岐状のパラフィン炭化水素といった高オクタン価成分の選択性に富むガソリン留分を、合成ガスから効率よく得るための方法を提供することを目的とする。 In the present invention, a gasoline fraction having a high CO conversion rate, a low generation of gas components, and a high selectivity of high octane components such as aromatics, naphthenes, olefins, and branched paraffin hydrocarbons can be efficiently produced from synthesis gas. The object is to provide a method for obtaining.
本発明者らは、上記目的を達成すべく研究を進めたところ、炭酸マンガン及びＦＴ反応に活性な金属種を含有するＦＴ合成触媒と、固体酸を示すゼオライトとを用いることによって、従来報告されている合成ガスからガソリン留分を製造する方法に比較して活性が高く、ガス成分の生成が少なく、かつ芳香族やナフテン、オレフィン、分岐状のパラフィンに富み高オクタン価なガソリン留分を製造可能なことを見出し、本発明を完成するに至った。 The inventors of the present invention have made researches to achieve the above object, and have been reported in the past by using an FT synthesis catalyst containing manganese carbonate and a metal species active in the FT reaction, and a zeolite showing a solid acid. Compared with the method of producing gasoline fractions from synthetic gas, high activity, less generation of gas components, rich in aromatics, naphthenes, olefins and branched paraffins can be produced. As a result, the present invention has been completed.
すなわち、本発明は、
（１） フィッシャー・トロプシュ反応に活性を示す１種以上の金属及び炭酸マンガンを含有するフィッシャー・トロプシュ合成触媒を用いて、水素及び一酸化炭素を主成分とするガスから炭化水素類を合成するＦＴ反応と、前記ＦＴ反応により得られた炭化水素類を、固体酸を示すゼオライトに接触させる変換反応と、を有することを特徴とする炭化水素類の製造方法、
（２） 前記ＦＴ反応及び前記変換反応を、同一反応器内で同時に行うことを特徴とする前記（１）記載の炭化水素類の製造方法、
（３） 前記ＦＴ反応及び前記変換反応を、前記フィッシャー・トロプシュ合成触媒と、固体酸を示すゼオライトとを含有する触媒組成物を用いて行うことを特徴とする前記（２）記載の炭化水素類の製造方法、
（４） 前記ＦＴ反応及び前記変換反応を、２３０〜３５０℃で行うことを特徴とする前記（１）〜（３）のいずれかに記載の炭化水素類の製造方法、
（５） 前記金属が、ルテニウム及びコバルトからなる群より選択される１種以上であることを特徴とする前記（１）〜（４）のいずれかに記載の炭化水素類の製造方法、
（６） 前記ゼオライトがＺＳＭ−５であることを特徴とする前記（１）〜（５）のいずれかに記載の炭化水素類の製造方法、
を提供するものである。
That is, the present invention
(1) FT for synthesizing hydrocarbons from gas mainly composed of hydrogen and carbon monoxide using a Fischer-Tropsch synthesis catalyst containing one or more metals active in Fischer-Tropsch reaction and manganese carbonate A method for producing hydrocarbons, characterized by comprising: a reaction and a conversion reaction in which the hydrocarbons obtained by the FT reaction are brought into contact with zeolite showing a solid acid,
(2) The method for producing hydrocarbons according to (1), wherein the FT reaction and the conversion reaction are simultaneously performed in the same reactor,
(3) The hydrocarbon according to (2), wherein the FT reaction and the conversion reaction are performed using a catalyst composition containing the Fischer-Tropsch synthesis catalyst and a zeolite showing a solid acid. Manufacturing method,
(4) The method for producing hydrocarbons according to any one of (1) to (3), wherein the FT reaction and the conversion reaction are performed at 230 to 350 ° C.
(5) The method for producing hydrocarbons according to any one of (1) to (4), wherein the metal is one or more selected from the group consisting of ruthenium and cobalt.
(6) The method for producing hydrocarbons according to any one of (1) to (5), wherein the zeolite is ZSM-5,
Is to provide.
本発明の炭化水素類の製造方法では、原料合成ガスのＣＯ転化率が高く、また、ガス成分の生成が少なく、かつ芳香族やナフテン、オレフィン、分岐状のパラフィン炭化水素といった高オクタン価成分の選択性に富むガソリン留分を、合成ガスから効率的に得ることができる。 In the method for producing hydrocarbons of the present invention, the CO conversion rate of the raw syngas is high, the production of gas components is small, and selection of high octane components such as aromatic, naphthene, olefin, and branched paraffin hydrocarbons is possible. A rich gasoline fraction can be efficiently obtained from synthesis gas.
本発明の炭化水素類の製造方法は、ＦＴ反応に活性を示す１種以上の金属及び炭酸マンガンを含有するＦＴ合成触媒を用いて、水素及び一酸化炭素を主成分とするガスから炭化水素類を合成するＦＴ反応と、前記ＦＴ反応により得られた炭化水素類を、固体酸を示すゼオライトに接触させる変換反応と、を有することを特徴とする。 The method for producing hydrocarbons of the present invention uses hydrocarbons from gas mainly composed of hydrogen and carbon monoxide using an FT synthesis catalyst containing one or more metals active in the FT reaction and manganese carbonate. And a conversion reaction in which the hydrocarbons obtained by the FT reaction are brought into contact with zeolite showing a solid acid.
本発明の炭化水素類の製造方法により、従来公知の方法に比べて非常に効率よく高オクタン価なガソリン留分を製造し得ることに関する詳細については、未だ解明されておらず、現在、鋭意検討中ではあるが、以下のように推察される。本発明の炭化水素類の製造方法では、合成ガスからＦＴ合成触媒により合成された炭化水素類が、固体酸を示すゼオライトに接触することにより、適度に分解又は異性化される。一般的に、ゼオライトによる炭化水素類の分解又は異性化反応等を効率よく行うためには、２３０℃以上でゼオライトを反応させることが好ましい。本発明においては、ＦＴ合成触媒として炭酸マンガンを含有するＦＴ合成触媒を用いることにより、高い反応温度においても、炭素数１〜４の低級炭化水素やＣＯ２といったガス成分の生成が抑制され、効率的に炭化水素を生成することができるとともに、高温度で固体酸触媒（ゼオライト）が有効に作用し、高オクタン価なガソリン留分製造が可能になると推察している。 The details regarding the ability to produce a high-octane gasoline fraction very efficiently compared to known methods by the method for producing hydrocarbons of the present invention have not yet been elucidated, and are currently under intensive investigation. However, it is guessed as follows. In the method for producing hydrocarbons of the present invention, hydrocarbons synthesized from synthesis gas by an FT synthesis catalyst are appropriately decomposed or isomerized by contacting with a zeolite showing a solid acid. In general, in order to efficiently perform the decomposition or isomerization reaction of hydrocarbons with zeolite, it is preferable to react the zeolite at 230 ° C. or higher. In the present invention, the use of an FT synthesis catalyst containing manganese carbonate as the FT synthesis catalyst suppresses the generation of gas components such as lower hydrocarbons having 1 to 4 carbon atoms and CO 2 even at a high reaction temperature. It is speculated that hydrocarbons can be produced, and that a solid acid catalyst (zeolite) acts effectively at high temperatures, making it possible to produce a high-octane gasoline fraction.
以下に、本発明において用いられるＦＴ合成触媒の調製から、当該ＦＴ合成触媒を用いた本発明の炭化水素類の製造方法までを順次説明する。 Hereinafter, the preparation from the preparation of the FT synthesis catalyst used in the present invention to the process for producing the hydrocarbons of the present invention using the FT synthesis catalyst will be sequentially described.
＜ＦＴ合成触媒＞
本発明において用いられるＦＴ合成触媒は、１種以上のＦＴ活性金属種と炭酸マンガンとを含有する。
本発明に用いられるＦＴ合成触媒中に含有される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。中でも、より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可能であり、２種以上を複合させて用いることも可能である。
<FT synthesis catalyst>
The FT synthesis catalyst used in the present invention contains one or more FT active metal species and manganese carbonate.
Examples of the FT active metal species contained in the FT synthesis catalyst used in the present invention include nickel, cobalt, iron, and ruthenium. Among these, ruthenium and cobalt are preferably selected as higher active metal species. Moreover, these metal seed | species can also be used independently and can also be used combining 2 or more types.
本発明に用いられるＦＴ合成触媒を構成する炭酸マンガンとしては、市販の試薬を用いてもよく、また、従来公知の方法で製造されたものを用いてもよい。従来公知の炭酸マンガンの製法としては、可溶性マンガン塩溶液とアンモニアあるいはアルカリの炭酸塩溶液とを反応させる方法が挙げられる。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、炭酸マンガンを得ることができる。 As manganese carbonate constituting the FT synthesis catalyst used in the present invention, commercially available reagents may be used, and those produced by a conventionally known method may be used. A conventionally known method for producing manganese carbonate includes a method of reacting a soluble manganese salt solution with ammonia or an alkali carbonate solution. Manganese carbonate can also be obtained by reaction of divalent manganese ions with carbonate ions or bicarbonate ions.
炭酸マンガンとＦＴ活性金属種とを含有させる方法の一つに、ＦＴ活性金属種を炭酸マンガンに含浸担持させる方法がある。炭酸マンガンへのＦＴ活性金属種の担持は通常の含浸担持で行われる。例えば、ルテニウム塩やコバルト塩の水溶液に炭酸マンガンを浸漬させることにより、ルテニウム塩やコバルト塩を炭酸マンガンに含浸させた後、乾燥、焼成を行う。ＦＴ活性金属種として２種以上の金属を炭酸マンガンに担持させる場合、ルテニウム塩とコバルト塩を両方含む水溶液を調製し、当該水溶液を炭酸マンガンに含浸させた後に乾燥、焼成をする方式でもよく、ルテニウム塩水溶液とコバルト塩水溶液を、それぞれ別個に炭酸マンガンに含浸させた後に乾燥、焼成をする段階方式でも良く、特に規定はしない。 One method of incorporating manganese carbonate and FT active metal species is to impregnate and support manganese carbonate with FT active metal species. The loading of the FT active metal species on the manganese carbonate is carried out by ordinary impregnation loading. For example, manganese carbonate is immersed in an aqueous solution of ruthenium salt or cobalt salt to impregnate the manganese carbonate with ruthenium salt or cobalt salt, and then dried and fired. When two or more metals are supported on manganese carbonate as the FT active metal species, an aqueous solution containing both a ruthenium salt and a cobalt salt is prepared, and the aqueous solution is impregnated with manganese carbonate, followed by drying and firing. There may be a stage system in which a ruthenium salt aqueous solution and a cobalt salt aqueous solution are impregnated separately in manganese carbonate and then dried and fired, and there is no particular limitation.
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。なお、含浸担持に用いるルテニウム塩やコバルト塩の溶液を、水溶液にかえて、アルコール、エーテル、ケトンなどの有機溶媒の溶液とすることも可能である。この場合は、各種有機溶媒に可溶な塩を選択する。 Examples of the ruthenium salt 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. Note that the solution of ruthenium salt or cobalt salt used for impregnation support can be replaced with an aqueous solution to form a solution of an organic solvent such as alcohol, ether, or ketone. In this case, a salt that is soluble in various organic solvents is selected.
ＦＴ合成触媒中のルテニウムの含有量は、触媒基準に対し、金属量換算で０．１〜５ｍａｓｓ％、好ましくは０．３〜４．５ｍａｓｓ％、より好ましくは０．５〜４ｍａｓｓ％である。ルテニウムの含有量は活性点数と関連する。ルテニウムの含有量が０．１ｍａｓｓ％未満の場合には、活性点数が不足となり十分な触媒活性が得られなくなるおそれがある。一方で、ルテニウムの含有量が５ｍａｓｓ％を超過した場合には、炭酸マンガン等の担体上にルテニウムが十分担持されなくなり、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の発現が起こりやすくなる。よって、必要以上のルテニウムの担持は、単に触媒コストを増加させるため好ましくない。 The ruthenium content in the FT synthesis catalyst is 0.1 to 5 mass%, preferably 0.3 to 4.5 mass%, more preferably 0.5 to 4 mass%, in terms of metal amount, relative to the catalyst standard. The ruthenium content is related to the number of active sites. If the ruthenium content is less than 0.1 mass%, the number of active sites may be insufficient, and sufficient catalytic activity may not be obtained. On the other hand, when the content of ruthenium exceeds 5 mass%, ruthenium is not sufficiently supported on a carrier such as manganese carbonate, resulting in a decrease in dispersibility and expression of a ruthenium species that does not interact with the carrier component. It tends to happen. Therefore, excessive loading of ruthenium is not preferable because it simply increases the catalyst cost.
ＦＴ合成触媒中のコバルトの含有量は、触媒基準に対し、金属量換算で５〜４０ｍａｓｓ％、好ましくは５〜３５ｍａｓｓ％、より好ましくは５〜３０ｍａｓｓ％である。コバルトの含有量が５ｍａｓｓ％未満の場合には、活性金属であるコバルトが少なすぎ、顕著な活性向上の効果が認められなくなるおそれがある。一方で、コバルトの含有量が４０ｍａｓｓ％を超過した場合には、この後の乾燥、焼成処理やＦＴ反応の条件下において、コバルトの凝集が進行しやすく、活性点の低下に繋がるおそれがある。さらに、コバルトの含有量が過剰となると、触媒の比表面積や細孔容積の低下を招く可能性があるとともに、生成物中のガス成分の生成量が増加しやすくなるため好ましくない。 The content of cobalt in the FT synthesis catalyst is 5 to 40 mass%, preferably 5 to 35 mass%, more preferably 5 to 30 mass% in terms of metal amount with respect to the catalyst standard. When the content of cobalt is less than 5 mass%, there is too little cobalt as an active metal, and there is a possibility that a remarkable activity improvement effect may not be recognized. On the other hand, when the cobalt content exceeds 40 mass%, the aggregation of cobalt tends to proceed under the conditions of the subsequent drying, firing treatment and FT reaction, which may lead to a decrease in active sites. Furthermore, if the cobalt content is excessive, the specific surface area and pore volume of the catalyst may be reduced, and the amount of gas components generated in the product tends to increase, which is not preferable.
本発明に用いられるＦＴ合成触媒には、炭酸マンガン及びＦＴ活性金属種によるＦＴ反応を阻害しない程度において、その他の成分を含有させることもできる。その他の成分としては、例えば、シリカ、アルミナ、シリカーアルミナなど、通常担体として用いられる無機酸化物が挙げられる。これらの担体（無機酸化物）成分のＦＴ合成触媒における含有量は、炭酸マンガンやＦＴ活性金属種の効果を阻害しない限りにおいて適宜設定することができるが、一般に、担体（これらの担体成分含有量と炭酸マンガン含有量との総和）基準で５〜５０ｍａｓｓ％が適当である。 The FT synthesis catalyst used in the present invention may contain other components as long as the FT reaction by manganese carbonate and FT active metal species is not inhibited. Examples of other components include inorganic oxides usually used as carriers, such as silica, alumina, silica-alumina, and the like. The content of these carrier (inorganic oxide) components in the FT synthesis catalyst can be appropriately set as long as the effects of manganese carbonate and FT active metal species are not impaired. Generally, the carrier (content of these carrier components) 5-50 mass% is appropriate on the basis of the sum of the content of manganese and the content of manganese carbonate.
さらに、本発明に用いられるＦＴ合成触媒には、炭酸マンガン及びＦＴ活性金属種に加えて、アルカリ金属種を含有させることもできる。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可能であり、２種以上を複合させて用いることも可能である。 Furthermore, the FT synthesis catalyst used in the present invention can contain an alkali metal species in addition to manganese carbonate and FT active metal species. Examples of the alkali metal species 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.
ＦＴ合成触媒に、炭酸マンガン及びＦＴ活性金属種に加えてアルカリ金属種を含有させる方法は、特に限定しない。例えば、ＦＴ活性金属種と同様にして、炭酸マンガンにアルカリ金属種を含浸担持させることができる。具体的には、例えば、ナトリウム塩やカリウム塩の水溶液を炭酸マンガンに含浸させた後、乾燥、焼成を行う。なお、ＦＴ活性金属種とアルカリ金属種を炭酸マンガンに担持させる順序は、特に限定されず、両者を含む水溶液に炭酸マンガンを浸漬させて同時に担持させることもできる。また、炭酸マンガンに含浸担持させる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。 A method for adding an alkali metal species to the FT synthesis catalyst in addition to the manganese carbonate and the FT active metal species is not particularly limited. For example, in the same manner as the FT active metal species, manganese carbonate can be impregnated with an alkali metal species. Specifically, for example, an aqueous solution of sodium salt or potassium salt is impregnated with manganese carbonate, and then dried and fired. The order in which the FT active metal species and the alkali metal species are supported on the manganese carbonate is not particularly limited, and the manganese carbonate may be immersed in an aqueous solution containing both and supported simultaneously. The sodium salt or potassium salt impregnated and supported on manganese carbonate is preferably a water-soluble salt such as chloride, nitrate, acetate or carbonate.
ＦＴ合成触媒中のナトリウムやカリウムなどのアルカリ金属の含有量は、触媒基準に対し、金属量換算で好ましくは０．０５〜３ｍａｓｓ％、より好ましくは０．０５〜２ｍａｓｓ％、さらに好ましくは０．１〜１．５ｍａｓｓ％である。ナトリウムやカリウムの含有量を０．０５ｍａｓｓ％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、３ｍａｓｓ％以下とすることにより、ＦＴ活性を低下させることなく、ガス成分の生成量を抑制することが可能となる。 The content of alkali metals such as sodium and potassium in the FT synthesis catalyst is preferably 0.05 to 3 mass%, more preferably 0.05 to 2 mass%, and still more preferably 0. 1 to 1.5 mass%. By setting the content of sodium or potassium to 0.05 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 the production | generation amount of a gas component, without reducing FT activity.
ルテニウムやコバルトといったＦＴ活性金属種を炭酸マンガンに含浸させた後、乾燥、焼成を行う。このときの乾燥は、原則、ＦＴ活性金属種を炭酸マンガンに含浸担持させるときに用いた水等の溶媒を蒸散させるために行い、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℃以上とすることにより、水等の蒸散を充分に促進することができる。一方、乾燥温度を２００℃以下とすることにより、水等の急激な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。 After impregnating manganese carbonate with an FT active metal species such as ruthenium or cobalt, drying and firing are performed. The drying at this time is performed in order to evaporate a solvent such as water used when impregnating and supporting the FT active metal species in manganese carbonate, 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, transpiration of water or the like can be sufficiently promoted. On the other hand, by setting the drying temperature to 200 ° C. or less, it is possible to suppress non-uniformity of the active metal component due to rapid evaporation of water or the like.
また、焼成温度は１５０〜３５０℃が好ましく、１５０〜３００℃がより好ましく、１５０〜２５０℃がさらに好ましい。焼成温度が３５０℃を大きく超えると、触媒成分中の炭酸マンガンが、マンガン酸化物と炭酸ガスへ分解するため好ましくない。本発明に係るＦＴ合成触媒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、酸化マンガンでは本発明の効果は得られない。一方で、焼成温度が低すぎると、ＦＴ活性金属種の活性化が図られないため好ましくない。 Moreover, 150-350 degreeC is preferable, as for baking temperature, 150-300 degreeC is more preferable, and 150-250 degreeC is further more preferable. If the calcination temperature greatly exceeds 350 ° C., manganese carbonate in the catalyst component decomposes into manganese oxide and carbon dioxide gas, which is not preferable. Manganese carbonate, which is an FT synthesis catalyst component according to the present invention, must be present in the form of a carbonate, and the effects of the present invention cannot be obtained with manganese oxide. On the other hand, if the firing temperature is too low, activation of the FT active metal species cannot be achieved, which is not preferable.
乾燥や焼成の時間については、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。処理時間が１時間未満では水分の蒸散が不十分となる可能性や、ＦＴ活性金属種の活性化が希薄となり好ましくない。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、特に規定はしない。 The time for drying and firing is not generally determined depending on the amount of treatment, but is usually 1 to 10 hours. If the treatment time is less than 1 hour, the transpiration of moisture may be insufficient, and the activation of the FT active metal species is diluted, which is not preferable. Further, even if the treatment time exceeds 10 hours, the catalytic activity is almost the same as the case of 10 hours or less. Therefore, in consideration of 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 defined.
上述の含浸担持法以外に、炭酸マンガン及びＦＴ活性金属種を含有するＦＴ合成触媒の製造方法としては、炭酸マンガン及びＦＴ活性金属種を含む水系のスラリーを調製し、これをスプレードライする方法が挙げられる。このときのスラリーの濃度は特に規定しないが、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い。逆に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、スラリーの濃度調製や触媒の成形性の向上、球状化を目的に、シリカゾル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、一般には５〜２０ｍａｓｓ％の範囲で選択される。 In addition to the impregnation support method described above, as a method for producing an FT synthesis catalyst containing manganese carbonate and FT active metal species, an aqueous slurry containing manganese carbonate and FT active metal species is prepared and spray-dried. Can be mentioned. The concentration of the slurry at this time is not particularly specified, but if the slurry concentration is too low, manganese carbonate precipitates and the catalyst components become non-uniform, which is not preferable. On the other hand, if the slurry concentration is too high, it becomes difficult to feed the slurry, so an appropriate slurry concentration is selected. Further, at this time, silica sol 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 catalyst activity is not lowered, and is generally selected in the range of 5 to 20 mass%.
スプレードライ法でＦＴ合成触媒を得る場合、炭酸マンガン、ＦＴ活性金属種、及びバインダー成分を同時に含有させたスラリーをスプレーする方法や、炭酸マンガン及び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、得られたスプレードライ品にＦＴ活性金属種を添加する方法がある。なお、スプレードライ法における送風温度は、上記の乾燥及び焼成温度内で実施することが好ましい。 When obtaining an FT synthesis catalyst by spray drying, a method of spraying a slurry containing manganese carbonate, an FT active metal species, and a binder component at the same time, or a slurry containing manganese carbonate and a binder is sprayed, and then the impregnation described above. In accordance with the loading method, there is a method of adding FT active metal species to the obtained spray-dried product. In addition, it is preferable to implement the ventilation temperature in spray-drying method within said drying and baking temperature.
さらに他の本発明に用いられるＦＴ合成触媒の調製法としては、炭酸マンガンをＦＴ活性金属種の水溶液に浸漬させて、活性金属を炭酸マンガン上に吸着させる方法や、イオン交換により活性金属を炭酸マンガンに付着させる方法、炭酸マンガンをＦＴ活性金属種の水溶液に浸漬させる際に、アルカリなどの沈殿剤を加えることにより、活性金属を炭酸マンガンに沈着させる方法等が挙げられる。 As another method for preparing the FT synthesis catalyst used in the present invention, manganese carbonate is immersed in an aqueous solution of FT active metal species, and the active metal is adsorbed on manganese carbonate, or the active metal is carbonated by ion exchange. Examples thereof include a method of adhering to manganese and a method of depositing an active metal on manganese carbonate by adding a precipitant such as an alkali when immersing manganese carbonate in an aqueous solution of FT active metal species.
上述の焼成処理は、ＦＴ活性金属種の活性化を図る目的があるが、焼成処理以外に、若しくは焼成処理に加えて、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。具体的には、炭酸マンガンにＦＴ活性金属種を担持させたＦＴ合成触媒を、アルカリ性水溶液に浸漬させる後処理を行う。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。アルカリ性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。アルカリの濃度が０．０５Ｎ未満である場合には、アルカリ性水溶液処理効果が希薄となり、その後に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おそれがある。逆に１Ｎを超える場合には、未反応のアルカリ分が多くなり、不経済であることに加えて、洗浄処理に要する水量や時間が多くなる。なお、アルカリ性水溶液処理の時間は、アルカリ分の濃度にも依るが、通常１〜１０時間が好ましい。 The above baking treatment has the purpose of activating the FT active metal species, but the activation can also be achieved by an alkaline aqueous solution treatment in addition to or in addition to the baking treatment. Specifically, a post-treatment is performed in which an FT synthesis catalyst in which FT active metal species is supported on manganese carbonate is immersed in an alkaline aqueous solution. 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 alkali concentration in the alkaline aqueous solution is 0.05 to 1N, preferably 0.05 to 0.5N, more preferably 0.05 to 0.2N. When the alkali concentration is less than 0.05 N, the alkaline aqueous solution treatment effect becomes dilute, and there is a possibility that the catalytic activity is not significantly improved even if the calcination treatment is performed thereafter. On the other hand, when it exceeds 1 N, the amount of unreacted alkali increases, which is uneconomical and increases the amount of water and time required for the cleaning treatment. In addition, although the time of alkaline aqueous solution processing is based also on the density | concentration of an alkali component, 1 to 10 hours are preferable normally.
アルカリ性水溶液で処理した後、水洗し、余剰のアルカリ分を充分に洗浄した後に、上述の乾燥、焼成処理を行う。なお、このアルカリ性水溶液処理は、炭酸マンガンにＦＴ活性金属種を含浸担持させた後、乾燥後に行ってもよく、焼成後に行ってもよく、特に限定しない。さらに、スプレードライを行って得られた触媒や、成型した触媒に対して実施することもできる。 After the treatment with an alkaline aqueous solution, the product is washed with water and the excess alkali content is sufficiently washed, and then the above-described drying and baking treatments are performed. The alkaline aqueous solution treatment is not particularly limited, and may be performed after drying or after firing after impregnating and supporting FT active metal species in manganese carbonate. Furthermore, it can also implement with respect to the catalyst obtained by performing spray drying, and the shape | molded catalyst.
＜ゼオライト＞
本発明に用いられるゼオライトとしては、固体酸を示すゼオライトであれば、特に限定されるものではなく、公知のゼオライトの中から適宜選択して用いることができる。固体酸とは、固体の表面がブレンステッド酸性やルイス酸性を示すものであり、均一系や不均一系の酸触媒反応に活性を有するものである。ＦＴ反応により合成された炭化水素類は、ゼオライトの固体表面の酸に接触することにより、水素化分解又は異性化される。
<Zeolite>
The zeolite used in the present invention is not particularly limited as long as it is a zeolite showing a solid acid, and can be appropriately selected from known zeolites. The solid acid is one in which the surface of the solid exhibits Bronsted acidity or Lewis acidity, and is active in homogeneous or heterogeneous acid-catalyzed reactions. Hydrocarbons synthesized by the FT reaction are hydrocracked or isomerized by contacting the acid on the solid surface of the zeolite.
好ましいゼオライトとしては、ＺＳＭ−５、βゼオライト、Ｙ型ゼオライト、ＵＳＹゼオライト、モルデナイトなどが挙げられるが、特にＺＳＭ−５が好ましい。ゼオライトは、市販品を用いてもよく、公知の方法で水熱合成したものを用いることもできる。これらのゼオライトは、通常、イオン交換可能な陽イオンとしてアルカリ金属を含有するが、本発明に用いるゼオライトは、陽イオンの５０％以上をプロトン、アルカリ土類金属イオン、遷移金属イオン、又は希土類金属イオンで置換されたものであって、固体酸性を有するものが好ましく、特にＨ（プロトン）−ＺＳＭ−５が好適に用いられる。 Preferred zeolites include ZSM-5, β zeolite, Y-type zeolite, USY zeolite, mordenite and the like, with ZSM-5 being particularly preferred. As the zeolite, a commercially available product may be used, or a product hydrothermally synthesized by a known method may be used. These zeolites usually contain an alkali metal as an ion-exchangeable cation, but the zeolite used in the present invention contains 50% or more of the cation as a proton, an alkaline earth metal ion, a transition metal ion, or a rare earth metal. Those substituted with ions and having solid acidity are preferred, and H (proton) -ZSM-5 is particularly preferably used.
＜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ＦＴ合成触媒を用いて、合成ガスから炭化水素類を合成するＦＴ反応と、ＦＴ反応により得られた炭化水素類を、固体酸を示すゼオライトに接触させる変換反応とを有する。炭化水素類をゼオライトに接触させると、分解反応や異性化反応等の様々な反応により、炭化水素類が変換される。その結果、ガソリン留分が増大すると推察される。
<Method for producing hydrocarbons>
The method for producing hydrocarbons of the present invention comprises the FT reaction for synthesizing hydrocarbons from synthesis gas using the FT synthesis catalyst prepared as described above, and the hydrocarbons obtained by the FT reaction, A conversion reaction in contact with a zeolite that exhibits a solid acid. When hydrocarbons are brought into contact with zeolite, hydrocarbons are converted by various reactions such as decomposition reaction and isomerization reaction. As a result, it is assumed that the gasoline fraction increases.
ＦＴ反応は、触媒として前述の特定のＦＴ合成触媒を用いる以外は、当該技術分野で公知の方法又はそれを適宜改変することにより、行うことができる。具体的には、例えば、合成ガスを前述の特定のＦＴ合成触媒に接触させることにより、ＦＴ反応を行うことができる。同様に、変換反応も、触媒として前述の特定のゼオライトを用い、このゼオライトをＦＴ反応により得られた炭化水素類に接触させることができる方法であれば、特に限定されるものではなく、当該技術分野で公知の方法又はそれを適宜改変することにより、行うことができる。 The FT reaction can be carried out by a method known in the art or by appropriately modifying it, except that the above-mentioned specific FT synthesis catalyst is used as a catalyst. Specifically, for example, the FT reaction can be performed by bringing the synthesis gas into contact with the specific FT synthesis catalyst described above. Similarly, the conversion reaction is not particularly limited as long as the above-described specific zeolite is used as a catalyst and the zeolite can be brought into contact with hydrocarbons obtained by the FT reaction. It can be carried out by a method known in the field or by appropriately modifying it.
本発明の炭化水素類の製造方法は、ＦＴ反応工程と変換反応工程を別個に行う２段法であってもよい。ＦＴ反応工程と変換反応工程を別個に行うことにより、各反応工程を、それぞれ最適な反応条件下で行うことができる。一般的に、ゼオライトによる炭化水素類の変換反応は、温度が高いほど効率よく行われる。このため、例えば、ＦＴ反応工程を行った後、合成された炭化水素類に対して、ＦＴ反応工程よりも高温で変換反応工程を行うこともできる。また、変換反応工程開始時に、反応器内に、さらに水素を添加してもよい。 The hydrocarbon production method of the present invention may be a two-stage method in which the FT reaction step and the conversion reaction step are performed separately. By separately performing the FT reaction step and the conversion reaction step, each reaction step can be performed under optimum reaction conditions. Generally, the conversion reaction of hydrocarbons by zeolite is performed more efficiently as the temperature is higher. For this reason, for example, after the FT reaction step, the conversion reaction step can be performed on the synthesized hydrocarbons at a higher temperature than the FT reaction step. Further, hydrogen may be further added to the reactor at the start of the conversion reaction step.
ＦＴ反応工程と変換反応工程を別個に行う場合、予めＦＴ合成触媒が投入されている反応器に合成ガスを通気してＦＴ反応を行った後、合成された炭化水素類を、予めゼオライトが投入されている別の反応器に導入して変換反応を行うことができる。その他、ＦＴ反応後に、当該ＦＴ反応を行った反応器に、ゼオライトを投入して変換反応を行ってもよい。 When the FT reaction step and the conversion reaction step are performed separately, the synthesis gas is passed through the reactor in which the FT synthesis catalyst has been charged in advance to perform the FT reaction, and then the synthesized hydrocarbons are charged in advance with the zeolite. The reaction can be carried out by introducing it into another reactor. In addition, after the FT reaction, the conversion reaction may be performed by introducing zeolite into a reactor in which the FT reaction has been performed.
本発明の炭化水素類の製造方法は、ＦＴ反応と変換反応を、同一反応器内で同時に行う１段法であってもよい。ＦＴ反応と変換反応を一の工程で行うことにより、作業工程が簡略化され、経済的である。特に本発明において用いるＦＴ合成触媒は、２３０〜３５０℃という高温条件においても、ＣＯ転化率及びＣ５＋選択性（炭素数５以上の炭化水素類の合成の選択性）が高い、という優れた触媒である。このため、本発明の炭化水素類の製造方法では、ＦＴ反応をゼオライトによる変換反応と同じ反応条件で行った場合でも、ガス成分等の生成を抑制しつつ、効率よく炭化水素類を合成することができる。 The method for producing hydrocarbons of the present invention may be a one-stage method in which the FT reaction and the conversion reaction are simultaneously performed in the same reactor. By performing the FT reaction and the conversion reaction in one step, the work process is simplified and economical. In particular, the FT synthesis catalyst used in the present invention is an excellent catalyst having high CO conversion and C5 + selectivity (selectivity for synthesis of hydrocarbons having 5 or more carbon atoms) even at a high temperature of 230 to 350 ° C. is there. For this reason, in the method for producing hydrocarbons of the present invention, even when the FT reaction is performed under the same reaction conditions as the conversion reaction with zeolite, the hydrocarbons are efficiently synthesized while suppressing the generation of gas components and the like. Can do.
ＦＴ反応と変換反応を同一反応器内で同時に行う場合、反応器内に、ＦＴ合成触媒とゼオライトを、それぞれ別個に投入してもよく、ＦＴ合成触媒とゼオライトの両方を含む触媒組成物を予め調製し、この触媒組成物を反応器内に投入してもよい。ＦＴ合成触媒とゼオライトの両方を含む触媒組成物（以下、単に「触媒組成物」と略記する場合がある。）の調製法等については後述する。 When the FT reaction and the conversion reaction are simultaneously performed in the same reactor, the FT synthesis catalyst and the zeolite may be separately introduced into the reactor, and the catalyst composition containing both the FT synthesis catalyst and the zeolite is previously prepared. The catalyst composition may be prepared and charged into the reactor. A method for preparing a catalyst composition containing both the FT synthesis catalyst and the zeolite (hereinafter sometimes simply referred to as “catalyst composition”) will be described later.
各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。ＦＴ反応と変換反応を別の反応器で行う場合には、両反応の反応器の形式は、同種であってもよく、異種であってもよい。 The reactor type of each reaction includes a fixed bed, a fluidized bed, a suspension bed, a slurry bed and the like, and is not particularly limited. When the FT reaction and the conversion reaction are performed in separate reactors, the types of the reactors for both reactions may be the same or different.
固定床にて触媒の活性評価を行う場合は、粉体触媒ではリアクター内での差圧の発生が懸念されるため、触媒の形状としては押出し品やビード品等の成型品であることが好ましい。本発明において用いられるＦＴ合成触媒、ゼオライト、及び触媒組成物の大きさとしては、反応器の規模にもよるが、触媒形状として粒子径が０．５ｍｍ〜５ｍｍであることが好ましく、１．０ｍｍ〜３ｍｍであることがより好ましい。粒子径が０．５ｍｍ以上の場合には、リアクター内の差圧の上昇を十分に抑制することができる。一方、粒子径を３ｍｍ以下とすることにより、触媒の有効係数を向上させ、効率よく反応を進行させることが可能となる。 When evaluating the activity of the catalyst in a fixed bed, since the powder catalyst is concerned about the occurrence of differential pressure in the reactor, the shape of the catalyst is preferably a molded product such as an extruded product or a bead product. . The size of the FT synthesis catalyst, zeolite, and catalyst composition used in the present invention is preferably 0.5 mm to 5 mm as a catalyst shape, although it depends on the scale of the reactor. More preferably, it is ˜3 mm. When the particle diameter is 0.5 mm or more, an increase in the differential pressure in the reactor can be sufficiently suppressed. On the other hand, when the particle diameter is 3 mm or less, the effectiveness factor of the catalyst can be improved, and the reaction can proceed efficiently.
本発明に用いる触媒組成物は、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、所望の触媒活性を示さない。還元処理温度は、１４０〜３５０℃が好ましく、１５０〜３００℃がより好ましい。１４０℃未満では、ＦＴ活性金属種が十分に還元されず、十分な反応活性が得られない。また、３５０℃を大幅に超える高温では、触媒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可能性が高くなる。 The catalyst composition used in the present invention is subjected to a reduction treatment (activation treatment) in advance before being subjected to the reaction. By this reduction treatment, the catalyst is activated so as to exhibit a desired catalytic activity in the 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. The reduction treatment temperature is preferably 140 to 350 ° C, more preferably 150 to 300 ° C. If it is less than 140 degreeC, FT active metal seed | species will not fully be reduced, and sufficient reaction activity will not be obtained. Further, at a high temperature significantly exceeding 350 ° C., there is a high possibility that decomposition of the catalyst component, manganese carbonate, into manganese oxide proceeds, leading to a decrease in activity.
この還元処理には、水素を主成分とする還元性ガスを好ましく用いることができる。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。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。還元処理における水素分圧は、０．１〜１０ＭＰａが好ましく、０．５〜６ＭＰａがより好ましく、０．９〜３ＭＰａ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、３〜４８時間が最も好ましい。処理時間が０．１時間未満では、触媒の活性化が不十分となるおそれがある。一方、７２時間を超える長時間還元処理をしたとしても、触媒に与える悪影響は無いが、触媒性能の向上も見られないため、処理コストが嵩むなどの好ましくない問題を生じる。 For this reduction treatment, a reducing gas mainly containing hydrogen can be 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. This reduction treatment is affected by the hydrogen partial pressure and the treatment time as well as the treatment temperature. The hydrogen partial pressure in the reduction treatment is preferably 0.1 to 10 MPa, more preferably 0.5 to 6 MPa, and most preferably 0.9 to 3 MPa. 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 3 to 48 hours. If the treatment time is less than 0.1 hour, the activation of the catalyst may be insufficient. On the other hand, even if the reduction treatment is performed for a long time exceeding 72 hours, there is no adverse effect on the catalyst, but no improvement in the catalyst performance is observed.
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触媒組成物に合成ガスを通気させて行うことができる。 In the method for producing hydrocarbons of the present invention, synthesis gas can be passed through the catalyst composition reduced as described above.
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、反応を妨げない範囲において、他の成分が混入されていても差し支えない。例えば、一例として、本発明に係る触媒組成物を用いた炭化水素類の製造方法においては、バイオマスをガス化した合成ガスを用いることができる。この際のバイオマスの種類としては、食糧、建材、パルプなどの農林水産資源バイオマスや、農業、林産、畜産廃棄物などの廃棄物バイオマス、サトウキビ、パームヤシ、海藻などのプランテーションバイオマスなどが挙げられる。中でも、食糧と競合しない未利用の廃棄物バイオマスを用いることが好ましい。バイオマスのガス化方法については特に制限はされない。例えば、バイオマスのガス化方法としては、直接ガス化、間接ガス化、常圧ガス化、加圧ガスなど各種あり、また、ガス化炉形式としては固定床、流動床、噴流床など多岐にわたる。触媒組成物を用いた炭化水素類の製造方法においては、これらのいずれの方法を用いてガス化したバイオマスを用いてもよい。 The synthesis gas used may be mainly composed of hydrogen and carbon monoxide, and other components may be mixed as long as the reaction is not hindered. For example, as an example, in the method for producing hydrocarbons using the catalyst composition according to the present invention, a synthesis gas obtained by gasifying biomass can be used. The types of biomass in this case include agricultural, forestry and fishery resource biomass such as food, building materials and pulp, waste biomass such as agriculture, forestry and livestock waste, and plantation biomass such as sugar cane, palm palm and seaweed. Among them, it is preferable to use unused waste biomass that does not compete with food. There is no particular limitation on the biomass gasification method. For example, biomass gasification methods include various types such as direct gasification, indirect gasification, atmospheric pressure gasification, and pressurized gas. Gasification furnace types include a fixed bed, a fluidized bed, and a spouted bed. In the method for producing hydrocarbons using the catalyst composition, biomass gasified using any of these methods may be used.
反応の速度（ｋ）は、水素分圧に約一次で依存するため、水素及び一酸化炭素の分圧比（Ｈ２／ＣＯモル比）は、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、前述したバイオマスのガス化では、原料種やガス化方法の違いにより変動するが、本発明ではその上限は特に制限されない。 Since the reaction rate (k) depends on the hydrogen partial pressure in the first order, the partial pressure ratio of hydrogen and carbon monoxide (H 2 / CO molar ratio) is desirably 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 partial pressure ratio of hydrogen and carbon monoxide varies in the biomass gasification described above depending on the raw material species and the gasification method, but the upper limit is not particularly limited in the present invention.
現実的なこの水素及び一酸化炭素の分圧比の範囲としては、０．６〜２．７が適当であり、好ましくは０．８〜２．５、より好ましくは１〜２．３である。この分圧比が０．６未満では、生成する炭化水素類の収量が低下する傾向が見られ、また、この分圧比が２．７を超えると、生成する炭化水素類において、ガス成分が増える傾向が見られる。 As a practical range of the hydrogen / carbon monoxide partial pressure ratio, 0.6 to 2.7 is appropriate, preferably 0.8 to 2.5, and more preferably 1 to 2.3. When the partial pressure ratio is less than 0.6, the yield of the generated hydrocarbons tends to be reduced, and when the partial pressure ratio exceeds 2.7, the generated hydrocarbons tend to increase in gas components. Is seen.
さらに、本発明に係る触媒組成物を用いた炭化水素類の製造方法においては、合成ガス中に二酸化炭素が共存しても問題はない。合成ガス中に共存させる二酸化炭素としては、例えば石油製品の改質反応や天然ガス等から得られるものでも問題なく用いることができる。また、ＦＴ反応を妨げない他の成分が混入されている二酸化炭素も、合成ガス中に共存させることができる。例えば、石油製品等の水蒸気改質反応から出るもののように水蒸気や部分酸化された窒素等が含有された二酸化炭素でも良い。 Furthermore, in the method for producing hydrocarbons using the catalyst composition according to the present invention, there is no problem even if carbon dioxide coexists in the synthesis gas. As carbon dioxide to be coexisted in the synthesis gas, for example, those obtained from a reforming reaction of petroleum products or natural gas can be used without any problem. Carbon dioxide mixed with other components that do not interfere with the FT reaction can also coexist in the synthesis gas. For example, carbon dioxide containing water vapor, partially oxidized nitrogen, or the like, such as that from a steam reforming reaction of petroleum products or the like, may be used.
このような二酸化炭素を、二酸化炭素が含有されてない合成ガスに積極的に添加したガスを、触媒組成物に通気させてもよい。また、天然ガス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、脱炭酸処理することなくそのまま、触媒組成物に通気させて反応に供することもできる。二酸化炭素を含有する合成ガスをそのまま反応に供することにより、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、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。 A gas in which such carbon dioxide is positively added to synthesis gas not containing carbon dioxide may be passed through the catalyst composition. In addition, synthesis gas containing carbon dioxide obtained by reforming natural gas by the self-thermal reforming method or steam reforming method is passed through the catalyst composition as it is without decarboxylation. It can also be used. By subjecting the synthesis gas containing carbon dioxide to the reaction as it is, it is possible to reduce the equipment construction cost and operation cost required for the decarboxylation treatment, and it is possible to reduce the production cost of the resulting hydrocarbons.
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、０．３〜１０ＭＰａが好ましく、０．５〜７ＭＰａがより好ましく、０．８〜５ＭＰａがさらに好ましい。低圧では、連鎖成長が不十分となり、ガソリン分、灯軽油分、ワックス分などの収率が低下する傾向が見られるため好ましくない。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、該分圧が高まるほどプラント建設コスト等が高額となりやすく、また、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傾向にある。したがって、産業上の観点から該分圧の上限は規制される。 The total pressure (total value of partial pressures of all components) of the synthesis gas (mixed gas) subjected to the reaction is preferably 0.3 to 10 MPa, more preferably 0.5 to 7 MPa, and further preferably 0.8 to 5 MPa. Low pressure is not preferable because chain growth becomes insufficient and the yield of gasoline, kerosene, wax, etc. tends to decrease. In terms of equilibrium, the higher the partial pressure of hydrogen and carbon monoxide, the more advantageous. However, the higher the partial pressure, the more expensive the plant construction costs, and the larger the compressors required for compression, the higher the operating costs. Tend to rise. Therefore, the upper limit of the partial pressure is restricted from an industrial viewpoint.
ＦＴ反応における合成ガスと触媒との接触時間（以下Ｗ／Ｆと記す：ｗｅｉｇｈｔ／ｆｌｏｗ［ｇ・ｈ／ｍｏｌ］）は、好ましくは１〜１００、より好ましくは１．５〜９０、さらに好ましくは２〜８０である。Ｗ／Ｆの値は、処理量や用いる触媒の性能によって異なるが、一般に、Ｗ／Ｆが１以上であれば、十分なＣＯ転化率が得られ、液体生成物の収率が向上する。また、Ｗ／Ｆが１００以下であれば、用いる触媒量の増加による不必要な反応器の大型化を抑制することができる。 The contact time between the synthesis gas and the catalyst in the FT reaction (hereinafter referred to as W / F: weight / flow [g · h / mol]) is preferably 1 to 100, more preferably 1.5 to 90, and even more preferably. 2-80. Although the value of W / F varies depending on the throughput and the performance of the catalyst used, generally, when W / F is 1 or more, a sufficient CO conversion is obtained and the yield of the liquid product is improved. Moreover, if W / F is 100 or less, an unnecessary increase in the size of the reactor due to an increase in the amount of catalyst used can be suppressed.
ＦＴ合成触媒上では、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、連鎖成長確率及び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、連鎖成長確率及び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ＦＴ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。本発明の炭化水素類の製造方法を、ＦＴ反応と変換反応を同一反応器内で同時に行う１段法により行う場合には、反応温度は２３０〜３５０℃を採用し、２４０〜３１０℃が好ましく、２５０〜３００℃がさらに好ましい。反応温度が２３０℃以上であれば、ＦＴ合成触媒及びゼオライトの双方が有効に作用し、炭化水素類の生成及びその分解反応や異性化反応等によって高オクタン価なガソリン留分の製造が可能になる。また、反応温度を３５０℃以下とすることで、ＦＴ合成触媒上での好ましくないガス成分の生成を抑制すること、及びゼオライト上での過分解によるガス成分の生成を抑えることが可能となる。
なお、ＣＯ転化率、及び各種生成物の選択率は下記式で定義されるものである。
On FT synthesis catalyst, generally, if the H 2 / CO mole ratio of the syngas is the same, the lower the reaction temperature chain growth probability and C5 + but selectivity is high, CO conversion is low. Conversely, if the reaction temperature increases, the chain growth probability and C5 + selectivity decrease, but the CO conversion increases. Also, 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 FT reaction varies depending on the type of catalyst used. When the hydrocarbon production method of the present invention is performed by a one-stage method in which the FT reaction and the conversion reaction are simultaneously performed in the same reactor, the reaction temperature is 230 to 350 ° C, preferably 240 to 310 ° C. 250 to 300 ° C. is more preferable. If the reaction temperature is 230 ° C. or higher, both the FT synthesis catalyst and the zeolite work effectively, and it becomes possible to produce a high-octane gasoline fraction by the generation of hydrocarbons and their decomposition and isomerization reactions. . In addition, by setting the reaction temperature to 350 ° C. or lower, it is possible to suppress generation of undesirable gas components on the FT synthesis catalyst and to suppress generation of gas components due to overdecomposition on zeolite.
In addition, CO conversion rate and the selectivity of various products are defined by the following formula.
〔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
[CO conversion rate]
CO conversion rate = [(number of CO moles in raw material gas per unit time) − (number of CO moles in outlet gas per unit time)] / (number of CO moles in raw material gas per unit time) × 100
＜ＦＴ合成触媒及びゼオライトを含有する触媒組成物＞
本発明に用いられる触媒組成物は、ＦＴ合成触媒とゼオライトとを含有していればよく、従来公知のいずれの方法を用いて調製してもよい。例えば、ＦＴ合成触媒とゼオライトをそれぞれ別個に調製した後に、両者を物理的に混合することによって、ＦＴ合成触媒とゼオライトを両方含有する触媒組成物を調製することができる。また、炭酸マンガンとゼオライトの複合成型体に、ＦＴ活性金属を上述の方法で含浸担持させることによっても、本発明に用いられる触媒組成物を調製することができる。
<Catalyst composition containing FT synthesis catalyst and zeolite>
The catalyst composition used in the present invention only needs to contain an FT synthesis catalyst and zeolite, and may be prepared using any conventionally known method. For example, a catalyst composition containing both the FT synthesis catalyst and the zeolite can be prepared by preparing the FT synthesis catalyst and the zeolite separately and then physically mixing them. The catalyst composition used in the present invention can also be prepared by impregnating and supporting an FT active metal by the above-described method on a composite molded body of manganese carbonate and zeolite.
別個に調製したＦＴ合成触媒及びゼオライトを混合する方法としては、例えば、ＦＴ合成触媒及びゼオライトを物理的に混合して均一な混合物としてもよく、ＦＴ合成触媒とゼオライトとを一の容器に積層して充填した積層体としてもよい。積層体とする場合には、両者が少なくとも１層ずつ形成されたものであればよく、一の容器にＦＴ合成触媒とゼオライトを交互に充填し、ＦＴ合成触媒からなる層とゼオライトからなる層を交互に積層させた積層体であってもよい。 As a method of mixing the separately prepared FT synthesis catalyst and zeolite, for example, the FT synthesis catalyst and zeolite may be physically mixed to form a uniform mixture. The FT synthesis catalyst and zeolite are laminated in one container. It is good also as the laminated body filled up. In the case of a laminated body, it is sufficient that both of them are formed at least one layer. One container is filled with FT synthesis catalyst and zeolite alternately, and a layer made of FT synthesis catalyst and a layer made of zeolite are formed. It may be a laminated body laminated alternately.
また、触媒組成物を実装置に用いる場合、成型が必要となるが、成型に関しても従来公知の方法を用いることができる。例えば、ＦＴ合成触媒及びゼオライトの混合物を、公知の成型方法に供することにより、本発明に用いられる触媒組成物を成型することができる。その他、炭酸マンガンとゼオライトの複合成型体に、ＦＴ活性金属を上述の方法で含浸担持させて得られた触媒組成物を、公知の成型方法に供することにより、本発明に用いられる触媒組成物を成型することができる。このような公知の成型方法としては、例えば、打錠成型、押し出し成型、ビード化などが挙げられる。なお、これらの成型方法は、常法により行うことができる。 Moreover, when using a catalyst composition for an actual apparatus, shaping | molding is required, However A conventionally well-known method can be used also about shaping | molding. For example, the catalyst composition used in the present invention can be molded by subjecting a mixture of FT synthesis catalyst and zeolite to a known molding method. In addition, a catalyst composition obtained by impregnating and supporting an FT active metal on a composite molded body of manganese carbonate and zeolite by the above-described method is subjected to a known molding method, whereby the catalyst composition used in the present invention is obtained. Can be molded. Examples of such known molding methods include tableting molding, extrusion molding, and beading. In addition, these molding methods can be performed by a conventional method.
成型する際に、触媒組成物に対して、成型性向上のために、シリカやアルミナなどをバインダー成分として混合することや、押出し性向上のために、セルロース系成型助剤やエポキシ系成型助剤、ＰＶＡなどの成型助剤を触媒活性に影響を及ぼさない範囲で添加することも可能である。 When molding, the catalyst composition is mixed with silica or alumina as a binder component in order to improve moldability, or in order to improve extrudability, cellulosic molding aid or epoxy molding aid. It is also possible to add a molding aid such as PVA as long as it does not affect the catalytic activity.
本発明に用いられる触媒組成物においては、触媒組成物中のＦＴ合成触媒の含有割合が１０〜９０重量％、好ましくは２０〜８０重量％、より好ましくは３０〜６０重量％である。ＦＴ合成触媒を１０重量％以上含有させた場合には、ＦＴ反応による炭化水素の生成が十分進行するため好ましい。また、ＦＴ合成触媒の含有量が９０重量％以下の場合には、触媒組成物中に十分量のゼオライトを含有させることができる。 In the catalyst composition used for this invention, the content rate of the FT synthesis catalyst in a catalyst composition is 10 to 90 weight%, Preferably it is 20 to 80 weight%, More preferably, it is 30 to 60 weight%. When the FT synthesis catalyst is contained in an amount of 10% by weight or more, it is preferable because the generation of hydrocarbons by the FT reaction proceeds sufficiently. When the content of the FT synthesis catalyst is 90% by weight or less, a sufficient amount of zeolite can be contained in the catalyst composition.
また、本発明に用いられる触媒組成物としては、触媒組成物中のゼオライトの含有量が１０重量％以上であることが好ましい。ゼオライトを１０重量％以上含有させた場合には、生成した炭化水素類がゼオライト上で効率よく分解されガソリン留分へと変換されるため好ましい。 Moreover, as a catalyst composition used for this invention, it is preferable that content of the zeolite in a catalyst composition is 10 weight% or more. When the zeolite is contained in an amount of 10% by weight or more, it is preferable because the generated hydrocarbons are efficiently decomposed on the zeolite and converted into a gasoline fraction.
次に実施例を示して本発明をさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited to a following example.
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）を用いて行った。原料ガスには、内部標準としてＡｒを２５ｖｏｌ％添加した合成ガス（Ｈ２とＣＯの混合ガス）を用いた。定性及び定量分析は、ＣＯのピーク位置及びピーク面積をＡｒと比較することにより行った。また、生成物の組成分析は、キャピラリーカラム（ＴＣ−１）を用い、水素炎イオン検出器ガスクロマトグラフ（ＦＩＤ−ＧＣ）を用いて行った。触媒の化学成分の同定は、ＩＣＰ発光分光分析法（ＣＱＭ−１００００Ｐ、島津製作所製）により求めた。 In the following examples, CO analysis was performed using a thermal conductivity gas chromatograph (TCD-GC) using Active Carbon (60/80 mesh) as a separation column. As the source gas, a synthesis gas (mixed gas of H 2 and CO) added with 25 vol% Ar as an internal standard was used. Qualitative and quantitative analysis was performed by comparing the peak position and peak area of CO with Ar. The composition analysis of the product was performed using a capillary column (TC-1) and a flame ion detector gas chromatograph (FID-GC). The chemical component of the catalyst was identified by ICP emission spectroscopy (CQM-10000P, manufactured by Shimadzu Corporation).
［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。予め１５０℃で５時間乾燥させた炭酸マンガン８．００ｇを秤量し、バインダー成分として用いる触媒化成工業製のシリカゾルＳＩ−５５０（ＳｉＯ２含有量２０．６％）９．７１ｇ中に分散させ、その後、空気中１２０℃で３時間乾燥後、空気中２００℃で焼成した。この焼成品４．８５ｇに、塩化ルテニウム（小島化学製、Ｒｕ Ａｓｓａｙ ４０．７９ｍａｓｓ％）０．３６８ｇを溶解した水溶液を含浸させて１時間放置した。その後、空気中、８０℃で３時間乾燥し、さらに１５０℃で３時間焼成し、ＦＴ合成触媒である触媒ａを得た。Ｘ線回折法にて構造分析を行った結果、触媒ａ中のマンガンは炭酸マンガンの状態を維持していた。また、ＩＣＰ発光分光分析法にて触媒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２．９ｍａｓｓ％であった。
[Example 1]
Manganese carbonate (II) n hydrate manufactured by Wako Pure Chemical Industries was used as manganese carbonate. 8.00 g of manganese carbonate previously dried at 150 ° C. for 5 hours is weighed and dispersed in 9.71 g of silica sol SI-550 (SiO 2 content 20.6%) manufactured by Catalyst Kasei Kogyo Co., Ltd. used as a binder component. After drying in air at 120 ° C. for 3 hours, it was fired in air at 200 ° C. 4.85 g of this baked product was impregnated with an aqueous solution in which 0.368 g of ruthenium chloride (manufactured by Kojima Chemical Co., Ltd., Ru Assay 40.79 mass%) was dissolved, and left for 1 hour. Then, it was dried in air at 80 ° C. for 3 hours and further calcined at 150 ° C. for 3 hours to obtain a catalyst a which is an FT synthesis catalyst. As a result of structural analysis by the X-ray diffraction method, manganese in the catalyst a maintained the state of manganese carbonate. Moreover, as a result of conducting the chemical composition analysis of the catalyst a by ICP emission spectroscopy, ruthenium was 2.9 mass% in terms of metal.
触媒ａを４ｇとＨ−ＺＳＭ−５（ズードケミー製ＭＦＩ−９０）４ｇとを乳鉢で十分混合し、ＦＴ合成触媒とゼオライトの両方を含む触媒組成物である触媒Ａを得た。
触媒Ａの活性を確認するため、触媒Ａ６ｇを１００ｍｅｓｈの炭化ケイ素３４．６ｇで希釈し、内径１０ｍｍの反応管に充填し、水素分圧０．９ＭＰａ・Ｇ、温度１７０℃、流量１００（ＳＴＰ）ｍｌ／ｍｉｎ（ＳＴＰ：ｓｔａｎｄａｒｄ ｔｅｍｐｅｒａｔｕｒｅ ａｎｄ ｐｒｅｓｓｕｒｅ）で水素を通気させて３時間還元した。還元後、Ｈ２／ＣＯ比約２の合成ガス（Ａｒを約２５ｖｏｌ％含む）に切り換え、温度２６０℃、全圧０．９ＭＰａ・Ｇに設定して反応を行った。
触媒Ａに対する合成ガス（Ｈ２＋ＣＯ）の接触時間（Ｗ／Ｆ：ｗｅｉｇｈｔ／ｆｌｏｗ［ｇ・ｈ／ｍｏｌ］）は約１３．４ｇ・ｈ／ｍｏｌであった。なお、混合したＨ−ＺＳＭ−５はＦＴ反応に対して全く活性を示さないことから、Ｗ／Ｆは、触媒Ａ中のＦＴ合成触媒である触媒ａに対する合成ガスの接触時間で表している。反応結果及びこの時得られた生成物の組成分析結果を表１及び図１に、さらに生成物の炭化水素タイプ別分析結果を表２に、それぞれ示す。なお、図１中、「●」が実施例１の結果を示す。
4 g of catalyst a and 4 g of H-ZSM-5 (MFI-90 manufactured by Zude Chemie) were sufficiently mixed in a mortar to obtain catalyst A which is a catalyst composition containing both an FT synthesis catalyst and zeolite.
In order to confirm the activity of catalyst A, 6 g of catalyst A was diluted with 34.6 g of 100 mesh silicon carbide, filled in a reaction tube having an inner diameter of 10 mm, hydrogen partial pressure 0.9 MPa · G, temperature 170 ° C., flow rate 100 (STP) Reduction was performed for 3 hours by bubbling hydrogen at ml / min (STP: standard temperature and pressure). After the reduction, the reaction was carried out by switching to a synthesis gas having an H 2 / CO ratio of about 2 (containing about 25 vol% Ar) and setting the temperature to 260 ° C. and the total pressure to 0.9 MPa · G.
The contact time (W / F: weight / flow [g · h / mol]) of the synthesis gas (H 2 + CO) to the catalyst A was about 13.4 g · h / mol. Since the mixed H-ZSM-5 has no activity for the FT reaction, W / F is represented by the contact time of the synthesis gas with the catalyst a which is the FT synthesis catalyst in the catalyst A. The reaction results and the composition analysis results of the product obtained at this time are shown in Table 1 and FIG. 1, and the analysis results of the products by hydrocarbon type are shown in Table 2, respectively. In FIG. 1, “●” indicates the result of Example 1.
［比較例１］
炭酸マンガンに代えて和光純薬工業製の酸化マンガン（III）（Ｍｎ２Ｏ３）を使用した以外は実施例１と同様にして触媒ｂを得た。Ｘ線回折法にて構造分析を行った結果、マンガンはＭｎ２Ｏ３であった。ＩＣＰ発光分光分析法にて触媒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３．０ｍａｓｓ％であった。この触媒ｂを、ゼオライトとは混合せずにそのままＦＴ反応に供した。ＦＴ反応は、実施例１と同様の方法で行った。反応結果及びこの時得られた生成物の組成分析結果を表１及び図１に、さらに生成物の炭化水素タイプ別分析結果を表２に示す。なお、図１中、「◆」が比較例１の結果を示す。
[Comparative Example 1]
Catalyst b was obtained in the same manner as in Example 1 except that manganese oxide (III) (Mn 2 O 3 ) manufactured by Wako Pure Chemical Industries, Ltd. was used instead of manganese carbonate. As a result of structural analysis by X-ray diffraction method, manganese was Mn 2 O 3 . As a result of analyzing the chemical composition of the catalyst b by ICP emission spectroscopy, ruthenium was 3.0 mass% in terms of metal. This catalyst b was subjected to the FT reaction as it was without being mixed with zeolite. The FT reaction was performed in the same manner as in Example 1. The reaction results and the composition analysis results of the product obtained at this time are shown in Table 1 and FIG. 1, and the analysis results of the products by hydrocarbon type are shown in Table 2. In FIG. 1, “♦” indicates the result of Comparative Example 1.
［実施例２］
触媒Ａを用いて、反応温度を２７０℃で実施した以外は、実施例１と同様の方法で反応を行った。反応結果及びこの時得られた生成物の組成分析結果を表１に示す。
[Example 2]
The reaction was performed in the same manner as in Example 1 except that the reaction temperature was 270 ° C. using Catalyst A. The reaction results and the composition analysis results of the product obtained at this time are shown in Table 1.
［実施例３］
触媒Ａを用いて、反応温度を２８０℃で実施した以外は、実施例１と同様の方法で反応を行った。反応結果及びこの時得られた生成物の組成分析結果を表１に示す。
[Example 3]
The reaction was performed in the same manner as in Example 1 except that the reaction temperature was 280 ° C. using Catalyst A. The reaction results and the composition analysis results of the product obtained at this time are shown in Table 1.
［実施例４］
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。予め１５０℃で５時間乾燥した後、炭酸マンガン４．５ｇを秤量し、水３．０ｇに硝酸コバルト（和光純薬工業製、Ｃｏ(ＮＯ３)２・６Ｈ２Ｏ）２．４６ｇを溶解した水溶液を含浸させて１時間放置した。その後、空気中、８０℃で３時間乾燥し、さらに２００℃で５時間焼成し、ＦＴ合成触媒である触媒ｃを得た。Ｘ線回折法にて構造分析を行った結果、触媒ｃ中のマンガンは炭酸マンガンの状態を維持していた。また、ＩＣＰ発光分光分析法にて触媒ｃの化学組成分析を行った結果、コバルトは金属換算で１０．０ｍａｓｓ％であった。
触媒ｃ４ｇとＨ−ＺＳＭ−５（ズードケミー製ＭＦＩ−９０）４ｇとを乳鉢で十分混合し、ＦＴ合成触媒とゼオライトの両方を含む触媒組成物である触媒Ｂを得た。触媒Ｂを用いて、還元温度を３５０℃で実施した以外は、実施例１と同様の方法で反応を行った。結果を表３に示す。
[Example 4]
Manganese carbonate (II) n hydrate manufactured by Wako Pure Chemical Industries was used as manganese carbonate. After 5 hours previously dried by 0.99 ° C., manganese carbonate was weighed 4.5 g, cobalt nitrate in water 3.0g were dissolved (manufactured by Wako Pure Chemical Industries, Co (NO 3) 2 · 6H 2 O) 2.46g It was impregnated with an aqueous solution and left for 1 hour. Thereafter, it was dried in air at 80 ° C. for 3 hours and further calcined at 200 ° C. for 5 hours to obtain a catalyst c as an FT synthesis catalyst. As a result of structural analysis by the X-ray diffraction method, manganese in the catalyst c maintained the state of manganese carbonate. Further, as a result of chemical composition analysis of the catalyst c by ICP emission spectroscopic analysis, cobalt was 10.0 mass% in terms of metal.
Catalyst c4g and H-ZSM-5 (MFI-90 manufactured by Zude Chemie) 4g were sufficiently mixed in a mortar to obtain Catalyst B, which is a catalyst composition containing both the FT synthesis catalyst and zeolite. The reaction was performed in the same manner as in Example 1 except that the reduction temperature was 350 ° C. using catalyst B. The results are shown in Table 3.
［比較例２］
炭酸マンガンに代えて富士シリシア化学製の球状シリカ（Ｑ−３０）を用いて、ＦＴ合成触媒を製造した。具体的には、予め充分乾燥させた球状シリカ（Ｑ−３０）４．５ｇを秤量し、水５．５４ｇに硝酸コバルト（和光純薬工業製、Ｃｏ(ＮＯ３)２・６Ｈ２Ｏ）２．４６ｇを溶解した水溶液を含浸させて１時間放置した。その後、空気中、８０℃で３時間乾燥し、さらに２００℃で３時間焼成し、触媒ｄを得た。ＩＣＰ発光分光分析法にて触媒ｄの化学組成分析を行った結果、コバルトは金属換算で１０．１ｍａｓｓ％であった。
[Comparative Example 2]
An FT synthesis catalyst was produced using spherical silica (Q-30) manufactured by Fuji Silysia Chemical instead of manganese carbonate. Specifically, 4.5 g of spherical silica (Q-30) that has been sufficiently dried in advance is weighed, and water is added to 5.54 g of cobalt nitrate (manufactured by Wako Pure Chemical Industries, Co (NO 3 ) 2 · 6H 2 O) 2. An aqueous solution in which .46 g was dissolved was impregnated and left for 1 hour. Thereafter, it was dried in air at 80 ° C. for 3 hours and further calcined at 200 ° C. for 3 hours to obtain catalyst d. As a result of chemical composition analysis of the catalyst d by ICP emission spectroscopic analysis, cobalt was 10.1 mass% in terms of metal.
［比較例３］
触媒ｄ４ｇとＨ−ＺＳＭ−５（ズードケミー製ＭＦＩ−９０）４ｇとを乳鉢で十分混合して触媒ｅを得た。触媒ｅを用いて、実施例４と同様の方法で反応を行った結果を表３に示す。
[Comparative Example 3]
The catalyst d was sufficiently mixed with 4 g of catalyst d and 4 g of H-ZSM-5 (MFI-90 manufactured by Zude Chemie) in a mortar to obtain a catalyst e. Table 3 shows the results of the reaction performed in the same manner as in Example 4 using the catalyst e.
表１の結果より、ＦＴ活性金属と炭酸マンガンとを含有するＦＴ合成触媒とゼオライトとを含む触媒組成物を用いた場合（実施例１）には、ＦＴ活性金属と酸化マンガンとを含有するＦＴ合成触媒を含み、ゼオライトは含まない触媒組成物を用いた場合（比較例１）に比べて、ガス選択率やＣ５＋選択率には大きな違いは認められないが、ＣＯ転化率が非常に高く、かつ生成物中のガソリン留分の割合が非常に高くなることが明白である。特に、図１に示す通り、ゼオライトを触媒組成物中に含有することによって、炭素数の長い炭化水素が選択的に分解され、ガソリン留分へ転換されていることが明らかである。
また、炭酸マンガンを含むＦＴ合成触媒を用いることにより、反応温度が２６０〜２８０℃という高温であっても十分に反応が進行することも明らかである。
From the results of Table 1, when a catalyst composition containing an FT synthesis catalyst containing FT active metal and manganese carbonate and a zeolite was used (Example 1), FT containing an FT active metal and manganese oxide. Compared to the case of using a catalyst composition containing a synthesis catalyst and no zeolite (Comparative Example 1), no significant difference is observed in gas selectivity or C5 + selectivity, but the CO conversion is very high, And it is clear that the proportion of gasoline fraction in the product is very high. In particular, as shown in FIG. 1, it is clear that hydrocarbons having a long carbon number are selectively decomposed and converted into gasoline fractions by containing zeolite in the catalyst composition.
It is also clear that the reaction proceeds sufficiently even when the reaction temperature is as high as 260 to 280 ° C. by using an FT synthesis catalyst containing manganese carbonate.
表２に示すように、反応により得られた生成物の炭化水素タイプを比較すると、ゼオライトとの混合によって、オクタン価の高い芳香族やナフテン、オレフィン、分岐状パラフィンの割合が高くなることが分かる。 As shown in Table 2, when the hydrocarbon types of the products obtained by the reaction are compared, it can be seen that the ratio of aromatic, naphthene, olefin, and branched paraffin having a high octane number is increased by mixing with zeolite.
表３から明らかな通り、炭酸マンガンを含有しコバルトをＦＴ活性金属とするＦＴ合成触媒を用いた場合（実施例４）においても、ＦＴ活性金属としてルテニウムを用いた場合（実施例１）と同様に、ゼオライトの混合によって効率的にガソリン留分を製造することが可能である。さらに、炭酸マンガンの代わりにシリカを用いた場合（比較例２及び３）には、ゼオライトと混合させることによって生成物中のガソリン留分の割合は高められるものの（比較例３）、ガス成分の生成が非常に高く（Ｃ５＋選択率が非常に低い）、ＣＯ転化率も低いことが明らかである。これらの結果から、ガソリン留分を効率的に製造するためには、炭酸マンガンを含有するＦＴ合成触媒とゼオライトとの両方を含有する触媒組成物を用いることが非常に重要であることが明らかとなった。 As is apparent from Table 3, the case of using an FT synthesis catalyst containing manganese carbonate and using cobalt as the FT active metal (Example 4) is the same as the case of using ruthenium as the FT active metal (Example 1). In addition, it is possible to efficiently produce a gasoline fraction by mixing zeolite. Further, when silica is used instead of manganese carbonate (Comparative Examples 2 and 3), the ratio of gasoline fraction in the product is increased by mixing with zeolite (Comparative Example 3), but the gas component It is clear that the production is very high (C5 + selectivity is very low) and the CO conversion is low. From these results, it is clear that in order to efficiently produce a gasoline fraction, it is very important to use a catalyst composition containing both an FT synthesis catalyst containing manganese carbonate and a zeolite. became.
［実施例５］
触媒Ａを用いて、原料合成ガスとしてＨ２／ＣＯ比約１．５の合成ガス（Ａｒを約３８ｖｏｌ％含む）を導入した以外は、実施例１と同様の方法で反応を行った。反応結果及びこのとき得られた生成物の組成分析結果を表４に示す。
[Example 5]
The reaction was performed in the same manner as in Example 1 except that the catalyst A was used and a synthesis gas having an H 2 / CO ratio of about 1.5 (containing about 38 vol% Ar) was introduced as a raw material synthesis gas. Table 4 shows the reaction results and the composition analysis results of the product obtained at this time.
［比較例４］
触媒ｅを用いた以外は、実施例５と同様な反応を行った。反応結果及びこのとき得られた生成物の組成分析結果を表４に示す。
[Comparative Example 4]
The same reaction as in Example 5 was carried out except that the catalyst e was used. Table 4 shows the reaction results and the composition analysis results of the product obtained at this time.
［実施例６］
触媒Ａを用いて、原料合成ガスとしてＨ２／ＣＯ比約２．５の合成ガス（Ａｒを約１３ｖｏｌ％含む）を導入した以外は、実施例１と同様の方法で反応を行った。反応結果及びこのとき得られた生成物の組成分析結果を表４に示す。
[Example 6]
The reaction was carried out in the same manner as in Example 1 except that catalyst A was used and a synthesis gas having an H 2 / CO ratio of about 2.5 (containing about 13 vol% Ar) was introduced as a raw material synthesis gas. Table 4 shows the reaction results and the composition analysis results of the product obtained at this time.
［比較例５］
触媒ｅを用いた以外は、実施例６と同様な反応を行った。反応結果及びこのとき得られた生成物の組成分析結果を表４に示す。
[Comparative Example 5]
The same reaction as in Example 6 was carried out except that the catalyst e was used. Table 4 shows the reaction results and the composition analysis results of the product obtained at this time.
表４から明らかな通り、本発明によると、原料合成ガスのＨ２／ＣＯ比が多少変動しても効率的に液状炭化水素を得ることができる。すなわち、本発明の炭化水素類の製造方法は、原料合成ガスとして種々の由来する合成ガスを用いることができる。 As is apparent from Table 4, according to the present invention, liquid hydrocarbons can be efficiently obtained even if the H 2 / CO ratio of the raw synthesis gas varies somewhat. That is, the hydrocarbons production method of the present invention can use various derived syngas as the raw syngas.
Claims (6)
前記ＦＴ反応により得られた炭化水素類を、固体酸を示すゼオライトに接触させる変換反応と、
を有することを特徴とする炭化水素類の製造方法。 An FT reaction for synthesizing hydrocarbons from a gas mainly composed of hydrogen and carbon monoxide using a Fischer-Tropsch synthesis catalyst containing one or more metals and manganese carbonate that are active in the Fischer-Tropsch reaction;
A conversion reaction in which the hydrocarbons obtained by the FT reaction are brought into contact with a zeolite showing a solid acid;
A process for producing hydrocarbons characterized by comprising:
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| AU2010331418A AU2010331418B2 (en) | 2009-12-18 | 2010-12-07 | Catalyst composition for production of hydrocarbons and method for producing hydrocarbons |
| EP10837473.7A EP2514525B1 (en) | 2009-12-18 | 2010-12-07 | Catalyst composition for production of hydrocarbons and method for producing hydrocarbons |
| PCT/JP2010/071906 WO2011074444A1 (en) | 2009-12-18 | 2010-12-07 | Catalyst composition for production of hydrocarbons and method for producing hydrocarbons |
| US13/503,671 US9656252B2 (en) | 2009-12-18 | 2010-12-07 | Catalyst composition for producing hydrocarbons and method for producing hydrocarbons |
| ES10837473T ES2870852T3 (en) | 2009-12-18 | 2010-12-07 | Catalyst composition for hydrocarbon production and method for hydrocarbon production |
| MYPI2012700209A MY162446A (en) | 2009-12-18 | 2010-12-07 | Catalyst composition for producing hydrocarbons and method for producing hydrocarbons |
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