JP5129037B2 - Fischer-Tropsch synthesis catalyst and method for producing hydrocarbons - Google Patents
Fischer-Tropsch synthesis catalyst and method for producing hydrocarbons Download PDFInfo
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- JP5129037B2 JP5129037B2 JP2008164458A JP2008164458A JP5129037B2 JP 5129037 B2 JP5129037 B2 JP 5129037B2 JP 2008164458 A JP2008164458 A JP 2008164458A JP 2008164458 A JP2008164458 A JP 2008164458A JP 5129037 B2 JP5129037 B2 JP 5129037B2
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- 239000003054 catalyst Substances 0.000 title claims description 147
- 229930195733 hydrocarbon Natural products 0.000 title claims description 54
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 52
- 238000003786 synthesis reaction Methods 0.000 title claims description 39
- 230000015572 biosynthetic process Effects 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 109
- 239000007789 gas Substances 0.000 claims description 56
- 229910052751 metal Inorganic materials 0.000 claims description 54
- 239000002184 metal Substances 0.000 claims description 54
- 239000011656 manganese carbonate Substances 0.000 claims description 53
- 229940093474 manganese carbonate Drugs 0.000 claims description 53
- 235000006748 manganese carbonate Nutrition 0.000 claims description 53
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 53
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 53
- 230000000694 effects Effects 0.000 claims description 29
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 25
- 229910052707 ruthenium Inorganic materials 0.000 claims description 25
- 229910017052 cobalt Inorganic materials 0.000 claims description 19
- 239000010941 cobalt Substances 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 description 34
- 239000000126 substance Substances 0.000 description 25
- 239000002002 slurry Substances 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 230000009467 reduction Effects 0.000 description 16
- 238000001035 drying Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 150000003303 ruthenium Chemical class 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000001868 cobalt Chemical class 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012916 structural analysis Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- -1 naphtha Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 230000005068 transpiration Effects 0.000 description 2
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 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
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002303 thermal reforming Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Description
本発明は、水素と一酸化炭素を主成分とする混合ガス（以下「合成ガス」という）から炭化水素類を製造するための、フィッシャー・トロプシュ合成用触媒、及び該触媒を用いた炭化水素類の製造方法に関する。さらに詳しくは、主として炭酸マンガンからなる担体に、フィッシャー・トロプシュ反応に対する活性を有する金属（以下「ＦＴ活性金属」という）を含有させてなる触媒、及び該触媒に合成ガスを接触させ、ナフサ、灯油、軽油、ワックスといった炭化水素類を製造する方法に関する。 The present invention relates to a Fischer-Tropsch synthesis catalyst for producing hydrocarbons from a mixed gas containing hydrogen and carbon monoxide as main components (hereinafter referred to as “synthesis gas”), and hydrocarbons using the catalyst. It relates to the manufacturing method. More specifically, a catalyst mainly comprising manganese carbonate containing a metal having activity against the Fischer-Tropsch reaction (hereinafter referred to as “FT active metal”), and a synthetic gas brought into contact with the catalyst, naphtha, kerosene The present invention relates to a method for producing hydrocarbons such as diesel oil and wax.
合成ガスから炭化水素類を合成する方法として、フィッシャー・トロプシュ反応（Fischer-Tropsch反応）、メタノール合成反応、Ｃ２含酸素（エタノール、アセトアルデヒド等）合成反応などが良く知られている。そして、フィッシャー・トロプシュ反応は鉄、コバルト、ニッケルの鉄族元素やルテニウム等の白金族元素を活性金属とする触媒で、メタノール合成反応は銅系触媒で、Ｃ２含酸素合成反応はロジウム系触媒で進行することが知られている（例えば、非特許文献１参照）。 As methods for synthesizing hydrocarbons from synthesis gas, Fischer-Tropsch reaction (Fischer-Tropsch reaction), methanol synthesis reaction, C2 oxygen-containing (ethanol, acetaldehyde, etc.) synthesis reaction and the like are well known. The Fischer-Tropsch reaction is a catalyst using iron group elements such as iron, cobalt and nickel and platinum group elements such as ruthenium as active metals, the methanol synthesis reaction is a copper catalyst, and the C2 oxygen-containing synthesis reaction is a rhodium catalyst. It is known to proceed (see, for example, Non-Patent Document 1).
ところで、近年、大気環境保全の観点から、低硫黄分の軽油が望まれており、今後その傾向はますます強くなるものと考えられる。また、原油資源は有限であるとの観点やエネルギーセキュリティーの面から、石油代替燃料の開発が望まれており、今後ますます強く望まれるようになるものと考えられる。これらの要望に応える技術として、エネルギー換算で原油に匹敵する可採埋蔵量があるといわれる天然ガス（主成分メタン）から灯軽油等の液体燃料を合成する技術であるＧＴＬ（gas to liquids）がある。 By the way, in recent years, gas oil with low sulfur content has been desired from the viewpoint of the preservation of the air environment, and this trend is expected to become stronger in the future. In addition, from the viewpoint that crude oil resources are limited and from the viewpoint of energy security, the development of alternative fuels for oil is desired, and it is expected that this will become increasingly desirable in the future. As a technology that meets these demands, GTL (gas to liquids), a technology that synthesizes liquid fuels such as kerosene from natural gas (main component methane), which is said to have recoverable reserves equivalent to crude oil in terms of energy, is used. is there.
天然ガスは、硫黄分を含まないか、含んでいても脱硫が容易な硫化水素（Ｈ２Ｓ）等であるため、得られる灯軽油等の液体燃料には、その中に殆ど硫黄分が無く、またセタン価の高い高性能ディーゼル燃料に利用できるなどの利点があるため、このＧＴＬは近年ますます注目されるようになってきている。 Since natural gas does not contain sulfur or is hydrogen sulfide (H 2 S) or the like that is easy to desulfurize even if it contains, liquid fuel such as kerosene obtained has almost no sulfur in it. In addition, because of the advantage that it can be used for high-performance diesel fuel having a high cetane number, this GTL has been increasingly attracting attention in recent years.
上記ＧＴＬの一環として、合成ガスからフィッシャー・トロプシュ反応（以下「ＦＴ反応」という）によって炭化水素類を製造する方法（以下「ＦＴ法」という）が盛んに研究されている。このＦＴ法において炭化水素類の収率を高めるためには、炭化水素類の製造能力、すなわち活性が高く、ガス成分の生成が少なく、長時間安定した活性を示すといった優れた性能を有する触媒を用いることが有効と考えられる。 As part of the GTL, methods for producing hydrocarbons from synthesis gas by the Fischer-Tropsch reaction (hereinafter referred to as “FT reaction”) (hereinafter referred to as “FT method”) have been actively studied. In order to increase the yield of hydrocarbons in this FT method, a catalyst having excellent performance such as high production capacity of hydrocarbons, that is, high activity, little generation of gas components, and stable activity for a long time. Use is considered effective.
そして、従来から、種々のＦＴ反応用の触媒が提案されており、例えば、コバルトや鉄といったＦＴ活性金属種をアルミナや、シリカ、シリカ-アルミナ、チタニアなどの金属酸化物担体に担持した触媒が提案されている（例えば、特許文献１、特許文献２、特許文献３参照）。また、オレフィン類への高選択性を目的とした触媒として、マンガン酸化物担体にルテニウムを担持させた触媒、このルテニウム担持触媒にさらに第三成分を加えた触媒などのルテニウム系触媒が提案されている（例えば、特許文献４、特許文献５参照）。 Conventionally, various FT reaction catalysts have been proposed. For example, a catalyst in which an FT active metal species such as cobalt or iron is supported on a metal oxide carrier such as alumina, silica, silica-alumina, titania, or the like. It has been proposed (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3). Ruthenium catalysts such as a catalyst in which ruthenium is supported on a manganese oxide support and a catalyst in which a third component is further added to the ruthenium supported catalyst have been proposed as catalysts for high selectivity to olefins. (For example, refer to Patent Document 4 and Patent Document 5).
これらの従来提案されている触媒は、それを用いたＦＴ法において、相応に優れたオレフィン類の選択性や、相応の触媒活性を示すが、更なる触媒活性の向上が望まれる。一般に、触媒の活性が高いほど、触媒重量当たりの目的物の生産性が高く、同じ量の目的物を得るための触媒使用重量は少なくて済み、それに伴い反応器を小型化できるなど、触媒費用や装置費用の軽減が期待できる。また、ＦＴ反応用の触媒には、生成物中のメタン等のガス成分の生成が少なく、灯油や軽油といった有用な液状の炭化水素類の得率が高いことが望まれる。 These conventionally proposed catalysts show correspondingly excellent selectivity of olefins and corresponding catalytic activity in the FT method using the catalyst, but further improvement in catalytic activity is desired. In general, the higher the activity of the catalyst, the higher the productivity of the target product per catalyst weight, and the smaller the amount of catalyst used to obtain the same amount of target product, the smaller the reactor cost. And equipment costs can be reduced. Further, it is desired that the catalyst for the FT reaction has a low yield of gas components such as methane in the product and has a high yield of useful liquid hydrocarbons such as kerosene and light oil.
本発明は、上記従来の状況に鑑み、ＦＴ法において、ＣＯ転化率が高く、ガス成分の生成が少なく、かつ安定してＦＴ合成反応を行うことができ、炭化水素類の生産性を向上させることができるＦＴ合成用触媒、及びその触媒を用いる炭化水素類の製造方法を提供することを目的とする。 In view of the above-described conventional situation, the present invention has a high CO conversion rate, a small amount of gas component generation, and a stable FT synthesis reaction in the FT method, thereby improving the productivity of hydrocarbons. It is an object of the present invention to provide a catalyst for FT synthesis that can be produced, and a method for producing hydrocarbons using the catalyst.
本発明者らは、上記目的を達成すべく鋭意研究をしたところ、ＦＴ活性金属を、炭酸マンガンを主成分とする担体に含有させた触媒が、従来提案されている金属酸化物系の担体を用いる触媒に比較して、活性が大幅に高く、かつ、ガス成分の生成が少ないことを見出し、本発明を完成するに至った。 The inventors of the present invention have intensively studied to achieve the above object. As a result, a catalyst in which an FT active metal is contained in a carrier mainly composed of manganese carbonate is a conventional metal oxide carrier. It was found that the activity was significantly higher than that of the catalyst used, and the generation of gas components was small, and the present invention was completed.
本発明の触媒の活性向上やガスの生成の低下の詳細なメカニズムについては解明されておらず、現在、鋭意検討中ではあるが、ＦＴ反応に対しては不活性である担体主成分の炭酸マンガンが何らかの形でＦＴ活性金属種に作用し、活性を向上させるとともに、ガスの生成を抑制する作用を有するものと推察している。 The detailed mechanism of the improvement in the activity of the catalyst of the present invention and the decrease in the generation of gas has not been elucidated and is currently under intensive study, but is a carrier-based manganese carbonate that is inert to the FT reaction. Is presumed to act on the FT active metal species in some form to improve the activity and suppress the generation of gas.
すなわち、本発明は、上記目的を達成するために、下記構成のＦＴ合成用触媒、及びその触媒を用いる炭化水素類の製造方法に提供する。
１．炭酸マンガンを主成分とする担体に、フィッシャー・トロプシュ反応に活性を有する金属の少なくとも１種以上を含有させてなることを特徴とするフィッシャー・トロプシュ合成用触媒。
２．フィッシャー・トロプシュ反応に対する活性を有する金属が、ルテニウム及びコバルトから選ばれた少なくとも１種であることを特徴とする上記１に記載のフィッシャー・トロプシュ合成用触媒。
３．ルテニウムの含有量が触媒基準、金属換算で０．５〜５質量％であることを特徴とする上記２に記載のフィッシャー・トロプシュ合成用触媒。
４．コバルトの含有量が触媒基準、金属換算で５〜４０質量％であることを特徴とする上記２に記載のフィッシャー・トロプシュ合成用触媒。
５．上記１〜４のいずれかに記載のフィッシャー・トロプシュ合成用触媒に、水素及び一酸化炭素を主成分とするガスを接触させることを特徴とする炭化水素類の製造方法。
That is, in order to achieve the above object, the present invention provides a catalyst for FT synthesis having the following constitution and a method for producing hydrocarbons using the catalyst.
1. A Fischer-Tropsch synthesis catalyst comprising a carrier comprising manganese carbonate as a main component and containing at least one metal having activity in a Fischer-Tropsch reaction.
2. 2. The Fischer-Tropsch synthesis catalyst as described in 1 above, wherein the metal having activity for the Fischer-Tropsch reaction is at least one selected from ruthenium and cobalt.
3. 3. The Fischer-Tropsch synthesis catalyst according to 2 above, wherein the ruthenium content is 0.5 to 5% by mass in terms of a catalyst, in terms of metal.
4). 3. The Fischer-Tropsch synthesis catalyst as described in 2 above, wherein the cobalt content is 5 to 40% by mass in terms of catalyst, in terms of metal.
5. A method for producing hydrocarbons, comprising bringing the gas mainly composed of hydrogen and carbon monoxide into contact with the Fischer-Tropsch synthesis catalyst according to any one of 1 to 4 above.
本発明の炭酸マンガンを担体とする触媒は、従来のアルミナやシリカを担体とする触媒に比較してＣＯ転化率が高く、また、ガス成分であるＣＨ４などの生成割合を低下させることができる。また、本発明によれば、触媒の活性が高く、炭化水素類の生産性が高い触媒が提供され、触媒コストや反応器のサイズダウン等の効果が見込まれる。 The catalyst using manganese carbonate as a carrier of the present invention has a higher CO conversion rate than conventional catalysts using alumina or silica as a carrier, and can reduce the production ratio of CH 4 as a gas component. . Further, according to the present invention, a catalyst having high catalyst activity and high hydrocarbon productivity is provided, and effects such as catalyst cost and reactor size reduction are expected.
以下に本発明を詳細に説明する。
本発明のフィッシャー・トロプシュ合成用触媒（以下「本発明の触媒」とも言う。）は、炭酸マンガンを主成分とする担体（以下「炭酸マンガン担体」とも言う。）に、ＦＴ活性金属種を含有させてなるものである。以下、本発明の触媒、及びその調製からそれを用いた炭化水素類の製造方法までを順次詳しく説明する。
The present invention is described in detail below.
The Fischer-Tropsch synthesis catalyst of the present invention (hereinafter also referred to as “the catalyst of the present invention”) contains an FT active metal species in a carrier containing manganese carbonate as a main component (hereinafter also referred to as “manganese carbonate carrier”). It is something to be made. Hereinafter, the catalyst of the present invention and the preparation thereof to the production method of hydrocarbons using the same will be described in detail.
＜触媒及びその調製＞
本発明の触媒における炭酸マンガン担体の主成分である炭酸マンガンとしては、工業的に生産販売されているものを用いることもできるし、また、従来公知の方法で製造することもできる。炭酸マンガンを公知方法で得る場合、可溶性マンガン塩溶液と炭酸アンモニアあるいはアルカリの炭酸塩（たとえば炭酸ナトリウム）を反応させることで得られる。また、二価のマンガンイオンと炭酸イオンあるいは重炭酸イオンとの反応によっても得ることができる。また、炭酸マンガン担体は、炭酸マンガンのみからなるものでも、本発明における所期の炭酸マンガンの効果を阻害しない限りにおいて、炭酸マンガン以外の他の成分を含んでいても良い。この他の成分としては、シリカ、アルミナ、シリカ−アルミナなど、通常担体として用いられる無機酸化物が挙げられる。また、この他の成分の含有量は、本発明における所期の炭酸マンガンの効果を阻害しない限りにおいて適宜設定できるが、一般に、担体基準で５〜５０質量％が適当である。
<Catalyst and its preparation>
As manganese carbonate which is the main component of the manganese carbonate support in the catalyst of the present invention, those produced and sold industrially can be used, and can also be produced by a conventionally known method. When manganese carbonate is obtained by a known method, it can be obtained by reacting a soluble manganese salt solution with ammonia carbonate or an alkali carbonate (for example, sodium carbonate). It can also be obtained by reaction of divalent manganese ions with carbonate ions or bicarbonate ions. Further, the manganese carbonate carrier may be composed only of manganese carbonate or may contain other components other than manganese carbonate as long as the effect of the intended manganese carbonate in the present invention is not inhibited. Examples of other components include inorganic oxides that are usually used as carriers, such as silica, alumina, silica-alumina, and the like. The content of the other components can be appropriately set as long as the desired effect of manganese carbonate in the present invention is not impaired, but generally 5 to 50% by mass is appropriate based on the carrier.
本発明の触媒におけるＦＴ活性金属種としては、ニッケル、コバルト、鉄、ルテニウムが挙げられるが、中でも高活性な金属種としてルテニウムやコバルトが好ましく選択される。また、これらの金属種は単独で用いることもできるし、２種以上を複合させて用いることも可能である。 Examples of the FT active metal species in the catalyst of the present invention include nickel, cobalt, iron, and ruthenium. Among them, ruthenium and cobalt are preferably selected as highly active metal species. Moreover, these metal seed | species can also be used independently and can also be used in mixture of 2 or more type.
本発明の触媒を調製するための、炭酸マンガン担体にＦＴ活性金属種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担体に含浸担持させる方法がある。以下、この含浸担持について、ＦＴ活性金属種が好ましく用いられるルテニウムやコバルトである場合について説明する。この含浸担持は、通常の含浸担持方法で行うことができる。例えば、炭酸マンガン担体にルテニウム塩やコバルト塩の水溶液を含浸させ、その後、乾燥、焼成することによって行うことができる。このとき、ＦＴ活性金属種として２種以上の金属を担持する場合、例えばルテニウム塩とコバルト塩の両方含む水溶液を調製し、ルテニウム塩とコバルト塩を同時に含浸させ、その後、乾燥、焼成することもできるし、各々を別途に順次含浸させ、その後、乾燥、焼成しても良い。炭酸マンガン担体へのＦＴ活性金属種の含浸担持方法は、特に限定されない。 One method for preparing the catalyst of the present invention is to impregnate and support a FT active metal species on a manganese carbonate carrier as one of the methods for incorporating a FT active metal species into a manganese carbonate carrier. Hereinafter, this impregnation support will be described in the case where the FT active metal species is ruthenium or cobalt which is preferably used. This impregnation support can be performed by a normal impregnation support method. For example, it can be carried out by impregnating a manganese carbonate carrier with an aqueous solution of ruthenium salt or cobalt salt, and then drying and baking. At this time, when two or more metals are supported as FT active metal species, for example, an aqueous solution containing both a ruthenium salt and a cobalt salt may be prepared, impregnated with a ruthenium salt and a cobalt salt at the same time, and then dried and fired. Alternatively, each may be impregnated separately and then dried and fired. The method for impregnating and supporting the FT active metal species on the manganese carbonate support is not particularly limited.
上記含浸担持に用いるルテニウム塩としては、塩化ルテニウム、硝酸ルテニウム、酢酸ルテニウム、塩化六アンモニアルテニウムなどの水溶性ルテニウム塩が挙げられる。また、コバルト塩としては、塩化コバルト、硝酸コバルト、酢酸コバルト、硫酸コバルト、ギ酸コバルトが好ましく用いられる。また、含浸担持に用いるルテニウム塩やコバルト塩の溶液の溶媒に、水ではなく、アルコール、エーテル、ケトンなどの有機溶媒を用いることも可能であり、この場合は、ルテニウム塩やコバルト塩として各種有機溶媒に可溶な塩を選択する。 Examples of the ruthenium salt used for the impregnation support include water-soluble ruthenium salts such as ruthenium chloride, ruthenium nitrate, ruthenium acetate, and ruthenium hexaammonium chloride. Further, as the cobalt salt, cobalt chloride, cobalt nitrate, cobalt acetate, cobalt sulfate, and cobalt formate are preferably used. In addition, it is possible to use an organic solvent such as alcohol, ether or ketone instead of water as a solvent for the ruthenium salt or cobalt salt solution used for impregnation support. In this case, various organic compounds such as ruthenium salt and cobalt salt can be used. Select a salt that is soluble in the solvent.
本発明の触媒におけるルテニウムの含有量は、触媒基準、金属量換算で好ましくは０．５〜５質量％、より好ましくは０．８〜４．５質量％、特に好ましくは１〜４質量％である。ルテニウムの担持量は活性点数と関連する。ルテニウムの担持量を０．５質量％以上とすることにより、活性点数が保たれ十分な触媒活性を得ることができる。また、ルテニウムの担持量を５質量％以下とすることにより、ルテニウムの分散性の低下や、担体成分と相互作用を持たないルテニウム種が発現するのを抑制できる。 The ruthenium content in the catalyst of the present invention is preferably 0.5 to 5% by mass, more preferably 0.8 to 4.5% by mass, and particularly preferably 1 to 4% by mass in terms of catalyst and metal amount. is there. The amount of ruthenium supported is related to the number of active sites. By setting the supported amount of ruthenium to 0.5% by mass or more, the number of active sites is maintained and sufficient catalytic activity can be obtained. Further, by setting the amount of ruthenium supported to 5% by mass or less, it is possible to suppress a decrease in the dispersibility of ruthenium and the expression of ruthenium species that do not interact with the carrier component.
また、コバルトの含有量は、触媒基準、金属量換算で好ましくは５〜４０質量％、より好ましくは５〜３５質量％、特に好ましくは５〜３０質量％である。コバルトの含有量を５質量％以上とすることにより、活性金属としての顕著な活性向上の効果が認められる。また、４０質量％以下とすることにより、触媒調製の際の乾燥工程、焼成処理工程や、ＦＴ反応に供した際の反応条件下において、コバルトの凝集を抑制することができ、また、触媒の比表面積や細孔容積の低下を抑制することができ、さらにまた、ＦＴ反応における生成物中のガス生成量を抑制することができる。 Further, the content of cobalt is preferably 5 to 40% by mass, more preferably 5 to 35% by mass, and particularly preferably 5 to 30% by mass in terms of catalyst and metal amount. By making the cobalt content 5% by mass or more, a remarkable activity improvement effect as an active metal is recognized. Moreover, by setting it as 40 mass% or less, it can suppress agglomeration of cobalt under the drying process, the calcination process, and the reaction conditions when subjected to the FT reaction in preparing the catalyst. A decrease in specific surface area and pore volume can be suppressed, and furthermore, the amount of gas generated in the product in the FT reaction can be suppressed.
ＦＴ活性金属種を炭酸マンガン担体に含浸した後は、乾燥、焼成を行う。このときの乾燥は、原則、水を蒸散させるために行い、その温度は８０〜２００℃が好ましく、１００〜１５０℃がより好ましい。乾燥温度を８０℃以上とすることで、水の蒸散を十分に促進することが可能であり、２００℃以下であれば急激な水の蒸散による活性金属成分の不均一化を抑制することができるため好ましい。 After impregnating the manganese carbonate support with the FT active metal species, drying and firing are performed. In principle, the drying is performed to evaporate water, and the temperature is preferably 80 to 200 ° C, more preferably 100 to 150 ° C. By setting the drying temperature to 80 ° C. or higher, it is possible to sufficiently promote the transpiration of water, and if it is 200 ° C. or lower, it is possible to suppress the non-uniformity of the active metal component due to the rapid transpiration of water. Therefore, it is preferable.
また、焼成温度は１５０〜３００℃が好ましく、１５０〜２５０℃がより好ましい。焼成温度を３００℃以内とすることにより、担体成分の炭酸マンガンがマンガン酸化物と炭酸ガスに分解することを抑制することができる。本発明においては、担体成分の炭酸マンガンは、炭酸塩の形態で存在することが必須であり、後記比較例に具体的に示すように、酸化マンガンでは本発明の所期の効果は得られない。また、ＦＴ活性金属種の活性化を図るためには相応の温度が必要であるので、焼成温度は上記範囲が好ましい。また、乾燥や焼成の処理時間は、処理量によって一概には決まらないが、通常１〜１０時間である。処理時間を１時間以上とすることにより、水分の蒸散を確実に行い、ＦＴ活性金属種の活性化が希薄となることを抑制できる。また、処理時間が１０時間を超えても、触媒活性は、１０時間以下の場合とほとんど変わらないため、作業性や生産性を考慮すると１０時間以下が好ましい。なお、この乾燥や焼成処理は空気中で行うことも、あるいは窒素やヘリウムといった不活性ガス雰囲気でも、水素などの還元ガス雰囲気でもよく、特に限定はされない。 The firing temperature is preferably 150 to 300 ° C, more preferably 150 to 250 ° C. By setting the firing temperature within 300 ° C., it is possible to suppress decomposition of manganese carbonate as a carrier component into manganese oxide and carbon dioxide gas. In the present invention, manganese carbonate as a carrier component must be present in the form of a carbonate, and as specifically shown in Comparative Examples described later, manganese oxide does not provide the intended effect of the present invention. . In addition, since an appropriate temperature is required to activate the FT active metal species, the firing temperature is preferably within the above range. Moreover, although the processing time of drying or baking is not decided unconditionally by a processing amount, it is 1 to 10 hours normally. By setting the treatment time to 1 hour or longer, it is possible to reliably evaporate moisture and to suppress the activation of the FT active metal species from being diluted. Further, even if the treatment time exceeds 10 hours, the catalytic activity is almost the same as when the treatment time is 10 hours or less. Therefore, considering workability and productivity, 10 hours or less is preferable. The drying or baking treatment may be performed in the air, or may be an inert gas atmosphere such as nitrogen or helium, or a reducing gas atmosphere such as hydrogen, and is not particularly limited.
上述の含浸担持法以外の、本発明の炭酸マンガン担体にＦＴ活性金属種を含有させてなる触媒の製造方法としては、炭酸マンガンとＦＴ活性金属種を含む水系のスラリーを調製し、それをスプレードライする方法が挙げられる。このスプレードライ法におけるスラリーの濃度は特に限定はされないが、スラリー濃度が低すぎると炭酸マンガンの沈殿が発生し、触媒成分が不均一となり好ましくなく、また、スラリー濃度が高すぎるとスラリーの送液が困難となるため、適度なスラリー濃度を選択する。さらにこのとき、スラリーの濃度調整や触媒の成形性の向上、球状化を目的にシリカゾル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５〜２０質量%の範囲で選択される。 In addition to the above impregnation support method, as a method for producing a catalyst in which an FT active metal species is contained in a manganese carbonate support of the present invention, an aqueous slurry containing manganese carbonate and an FT active metal species is prepared and sprayed. The method of drying is mentioned. The concentration of the slurry in this spray drying method is not particularly limited. However, if the slurry concentration is too low, precipitation of manganese carbonate occurs and the catalyst components are not uniform, which is not preferable. If the slurry concentration is too high, the slurry is fed. Therefore, an appropriate slurry concentration is selected. Further, at this time, silica sol 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% by mass.
また、スプレードライ法で触媒を製造する場合、スラリー中に炭酸マンガン、ＦＴ活性金属種、バインダー成分を同時に含有させて、スプレーする方法や、炭酸マンガンとバインダーを含むスラリーをスプレーし、その後、上述の含浸担持方法に則って、ＦＴ活性金属種を添加する方法がある。また、スプレードライ法における送風温度は上述の含浸担持法における乾燥及び焼成温度内で実施することが好ましい。 In addition, when a catalyst is produced by a spray drying method, manganese carbonate, an FT active metal species, and a binder component are simultaneously contained in the slurry and sprayed, or a slurry containing manganese carbonate and a binder is sprayed. There is a method of adding an FT active metal species in accordance with the impregnation supporting method. Moreover, it is preferable to implement the ventilation temperature in the spray-drying method within the drying and baking temperature in the above-mentioned impregnation supporting method.
さらに他の、本発明の炭酸マンガン担体にＦＴ活性金属を含有させた触媒の製造方法としては、炭酸マンガン担体あるいはスプレードライによって調製された炭酸マンガンとバインダーを含む担体を、ＦＴ活性金属種の水溶液に浸漬し担体上へ活性金属を吸着させる方法（平衡吸着法）や、担体をＦＴ活性金属種の水溶液に浸漬させた後、アンモニア水等のアルカリ性の沈殿剤溶液を加えて担体上に活性金属を沈殿させる方法（沈着法）等がある。 As another method for producing a catalyst in which an FT active metal is contained in a manganese carbonate carrier of the present invention, a manganese carbonate carrier or a carrier containing manganese carbonate and a binder prepared by spray drying is used as an aqueous solution of an FT active metal species. Or by adsorbing the active metal on the support (equilibrium adsorption method), or after immersing the support in an aqueous solution of FT active metal species, adding an alkaline precipitant solution such as ammonia water to the active metal on the support There is a method of precipitating (deposition method).
＜炭化水素類の製造方法＞
本発明の炭化水素類の製造方法は、上記の如くして調製された本発明の触媒をＦＴ反応に供して、すなわち該触媒に水素及び一酸化炭素を主成分とする合成ガスを接触させて行われる。本発明の炭化水素類の製造方法においては、ＦＴ反応の反応器の形式に関しては、固定床、流動床、懸濁床、スラリー床などが挙げられ、特に限定はしないが、その一例として、以下に、スラリー床による本発明の炭化水素類の製造方法を説明する。
<Method for producing hydrocarbons>
In the method for producing hydrocarbons of the present invention, the catalyst of the present invention prepared as described above is subjected to the FT reaction, that is, the catalyst is brought into contact with synthesis gas mainly composed of hydrogen and carbon monoxide. Done. In the method for producing hydrocarbons of the present invention, the type of the reactor for the FT reaction includes a fixed bed, a fluidized bed, a suspension bed, a slurry bed, and the like, and is not particularly limited. Next, a method for producing the hydrocarbons of the present invention using a slurry bed will be described.
スラリー床にて本発明の炭化水素類の製造方法を行う場合は、触媒の形状としては、球状が好ましく、また、触媒粒子分布として好ましい範囲は１μｍ以上１５０μｍ以下、さらに好ましくは５μｍ以上１２０μｍ以下、最も好ましくは１０μｍ以上１１０μｍ以下である。スラリー床反応形式の場合は、液状の炭化水素中などに触媒を分散させて使用するため、触媒粒子径を１μｍ以上とすることにより、粒子が細かすぎることによる下流側への触媒粒子の流出を抑制し、反応容器内の触媒濃度の低下を抑制し、下流側機器が触媒微粒子によって障害を受けるなどを抑制することができる。また、触媒粒子径を１５０μｍ以内とすることにより、反応容器内全体に触媒粒子が分散せずに、スラリーが不均一となることによる反応活性の低下を抑制することができる。また、触媒形状が凹凸がなく球状であることは、スラリー床の反応形式において、触媒同士の接触や触媒と反応器内壁等との接触による触媒の割れや粉化による微粉の発生が低減されるため好ましい。 When the method for producing the hydrocarbons of the present invention is performed in a slurry bed, the shape of the catalyst is preferably spherical, and the preferred range for the catalyst particle distribution is 1 μm or more and 150 μm or less, more preferably 5 μm or more and 120 μm or less, Most preferably, it is 10 μm or more and 110 μm or less. In the case of the slurry bed reaction mode, the catalyst is dispersed in a liquid hydrocarbon and used. Therefore, by setting the catalyst particle diameter to 1 μm or more, the outflow of the catalyst particles to the downstream side due to the particles being too fine. It is possible to suppress the decrease in the catalyst concentration in the reaction vessel and to suppress the downstream device from being damaged by the catalyst fine particles. In addition, by setting the catalyst particle diameter within 150 μm, the catalyst particles are not dispersed throughout the reaction vessel, and the decrease in reaction activity due to non-uniform slurry can be suppressed. The spherical shape of the catalyst with no irregularities reduces the generation of fine particles due to catalyst cracking or pulverization due to contact between the catalysts or contact between the catalyst and the inner wall of the reactor in the reaction mode of the slurry bed. Therefore, it is preferable.
本発明の炭化水素類の製造方法においては、上記の如くして調製された本発明の触媒は、ＦＴ反応に供する前に予め還元処理（活性化処理）される。この還元処理により、触媒がＦＴ反応において所望の触媒活性を示すように活性化される。この還元処理を行わなかった場合には、ＦＴ活性金属種が十分に還元されず、ＦＴ反応において所望の触媒活性を示さない。 In the method for producing hydrocarbons of the present invention, the catalyst of the present invention prepared as described above is subjected to a reduction treatment (activation treatment) in advance before being subjected to the FT reaction. By this reduction treatment, the catalyst is activated so as to exhibit a desired catalytic activity in the FT reaction. If this reduction treatment is not performed, the FT active metal species are not sufficiently reduced and do not exhibit the desired catalytic activity in the FT reaction.
この還元処理は、触媒を液状炭化水素類に分散させたスラリー状態で還元性ガスと接触させる方法でも、炭化水素類を用いず単に触媒に還元性ガスを通気、接触させる方法でも好ましく行うことができる。前者の方法における触媒を分散させる液状炭化水素類としては、処理条件下において液状のものであれば、オレフィン類、アルカン類、脂環式炭化水素類、芳香族炭化水素類を始めとする種々の炭化水素類を使用できる。また、含酸素、含窒素等のヘテロ元素を含む炭化水素であっても良い。これらの炭化水素類の炭素数は、処理条件下において液状のものであれば特に制限する必要はないが、一般にＣ６〜Ｃ４０のものが好ましく、Ｃ９〜Ｃ４０のものがより好ましく、Ｃ９〜Ｃ３５のものが最も好ましい。Ｃ６の炭化水素類より重質なものであれば、溶媒の蒸気圧が高くなり過ぎず、処理条件幅が制限されないため好ましい。また、Ｃ４０の炭化水素類より軽質なものであれば、還元性ガスの溶解度が低下せず、十分な還元処理ができるため好ましい。 This reduction treatment is preferably performed by a method in which the catalyst is brought into contact with the reducing gas in a slurry state dispersed in liquid hydrocarbons, or a method in which the reducing gas is simply vented and brought into contact with the catalyst without using hydrocarbons. it can. As the liquid hydrocarbons in which the catalyst is dispersed in the former method, various liquids such as olefins, alkanes, alicyclic hydrocarbons, and aromatic hydrocarbons can be used as long as they are liquid under the processing conditions. Hydrocarbons can be used. Further, it may be a hydrocarbon containing a hetero element such as oxygen-containing or nitrogen-containing. The number of carbons of these hydrocarbons is not particularly limited as long as they are liquid under the processing conditions, but generally those of C6 to C40 are preferred, those of C9 to C40 are more preferred, and those of C9 to C35 are preferred. Is most preferred. If it is heavier than C6 hydrocarbons, the vapor pressure of the solvent does not become too high, and the range of processing conditions is not limited, which is preferable. Moreover, if it is lighter than C40 hydrocarbons, the solubility of the reducing gas does not decrease, and sufficient reduction treatment can be performed, which is preferable.
また、この還元処理に当たり炭化水素類中に分散させる触媒量は、１〜５０質量％の濃度が適当あり、好ましくは２〜４０質量％、より好ましくは３〜３０質量％の濃度である。触媒量が１質量％以上であれば、触媒の還元効率が低下し過ぎることを防ぐことができる。したがって、触媒の還元効率の低下を防ぐ方法として、還元性ガスの通気量を減少させる方法が挙げられる。これにより、気（還元性ガス）−液（溶媒）−固（触媒）の分散が損なわれることを回避することができる。また、触媒量が５０質量％以下であれば、炭化水素類に触媒を分散させたスラリーの粘性が高くなり過ぎず、気泡分散が良好で、触媒の還元が十分なされるため好ましい。 In addition, the amount of catalyst dispersed in the hydrocarbons in the reduction treatment is appropriately 1 to 50% by mass, preferably 2 to 40% by mass, more preferably 3 to 30% by mass. If the amount of catalyst is 1% by mass or more, it is possible to prevent the reduction efficiency of the catalyst from being excessively lowered. Therefore, as a method for preventing a reduction in the reduction efficiency of the catalyst, there is a method for reducing the flow rate of the reducing gas. Thereby, it can be avoided that the dispersion of gas (reducing gas) -liquid (solvent) -solid (catalyst) is impaired. A catalyst amount of 50% by mass or less is preferable because the viscosity of the slurry in which the catalyst is dispersed in hydrocarbons does not become too high, the bubble dispersion is good, and the catalyst is sufficiently reduced.
また、この還元処理の処理温度は、１４０〜２５０℃が好ましく、１５０〜２００℃がより好ましく、１６０〜２００℃が最も好適である。１４０℃以上であれば、ＦＴ活性金属種が十分に還元され、十分な反応活性が得られる。また、２５０℃以下であれば、担体成分の炭酸マンガンの酸化マンガンへの分解が進行して活性低下を招く危険を回避できる。 Moreover, 140-250 degreeC is preferable, the processing temperature of this reduction process has more preferable 150-200 degreeC, and its 160-200 degreeC is the most suitable. If it is 140 degreeC or more, FT active metal seed | species will fully be reduce | restored and sufficient reaction activity will be obtained. Moreover, if it is 250 degrees C or less, the danger that the decomposition | disassembly to manganese oxide of the manganese carbonate of a support component will advance and an activity fall will be avoided.
この還元処理には、水素を主成分とする還元性ガスが好ましく用いられる。用いる還元性ガスには、水素以外の成分、例えば水蒸気、窒素、希ガスなどを、還元を妨げない範囲である程度の量を含んでいても良い。 For this reduction treatment, a reducing gas mainly containing hydrogen is preferably used. The reducing gas to be used may contain a certain amount of components other than hydrogen, for example, water vapor, nitrogen, rare gas, etc. within a range that does not hinder the reduction.
また、この還元処理は、上記処理温度と共に、水素分圧及び処理時間にも影響されるが、水素分圧は、０．１〜１０ＭＰａが好ましく、０．５〜６ＭＰａがより好ましく、１〜５ＭＰａが最も好ましい。還元処理時間は、触媒量、水素通気量等によっても異なるが、一般に、０．１〜７２時間が好ましく、１〜４８時間がより好ましく、４〜４８時間が最も好ましい。処理時間が０．１時間以上であれば、触媒の活性化が不十分となることを回避できる。また、７２時間以下であれば、触媒性能の向上に十分である。 Moreover, although this reduction process is influenced also by hydrogen partial pressure and process time with the said process temperature, 0.1-10 MPa is preferable, as for hydrogen partial pressure, 0.5-6 MPa is more preferable, and 1-5 MPa. Is most preferred. The reduction treatment time varies depending on the amount of catalyst, the amount of hydrogen flow, etc., but is generally preferably 0.1 to 72 hours, more preferably 1 to 48 hours, and most preferably 4 to 48 hours. If the treatment time is 0.1 hour or longer, it is possible to avoid insufficient activation of the catalyst. Moreover, if it is 72 hours or less, it is enough for the improvement of catalyst performance.
本発明の炭化水素類の製造方法においては、上記の如く還元処理した本発明の触媒がＦＴ反応、すなわち炭化水素類の合成反応に供せられる。
本発明の炭化水素類の製造方法におけるＦＴ反応は、触媒を液状炭化水素類中に分散せしめた分散状態となし、この分散状態の触媒に水素と一酸化炭素からなる合成ガスを接触させる。この際、触媒を分散させる炭化水素類としては、上記の予め行う還元処理で用いられる炭化水素類と同様のものを用いることができる。すなわち、反応条件下において液状のものであれば、オレフィン類、アルカン類、脂環式炭化水素類、芳香族炭化水素類を始めとする種々の炭化水素類を使用でき、含酸素、含窒素等のヘテロ元素を含む炭化水素であっても良く、その炭素数は特に制限する必要はないが、一般にＣ６〜Ｃ４０のものが好ましく、Ｃ９〜Ｃ４０のものがより好ましく、Ｃ９〜Ｃ３５のものが最も好ましい。Ｃ６の炭化水素類より重質なものであれば、溶媒の蒸気圧が高くなり過ぎず、反応条件幅が制限されないため好ましい。また、Ｃ４０の炭化水素類より軽質なものであれば、原料の合成ガスの溶解度が低下せず、反応活性の低下を回避することができる。上記の予め行う還元処理において、触媒を液状炭化水素類に分散させて行う方法が採用されている場合は、該還元処理で用いられた液状炭化水素類をそのままこのＦＴ反応において用いることができる。
In the method for producing hydrocarbons of the present invention, the catalyst of the present invention reduced as described above is used for the FT reaction, that is, the hydrocarbon synthesis reaction.
The FT reaction in the method for producing hydrocarbons of the present invention is in a dispersed state in which a catalyst is dispersed in liquid hydrocarbons, and a synthesis gas comprising hydrogen and carbon monoxide is brought into contact with the dispersed catalyst. At this time, as the hydrocarbons in which the catalyst is dispersed, the same hydrocarbons used in the reduction treatment performed in advance can be used. That is, various hydrocarbons including olefins, alkanes, alicyclic hydrocarbons, aromatic hydrocarbons can be used as long as they are liquid under the reaction conditions, including oxygen, nitrogen, etc. The number of carbons does not need to be particularly limited, but is generally preferably C6 to C40, more preferably C9 to C40, and most preferably C9 to C35. preferable. If it is heavier than C6 hydrocarbons, the vapor pressure of the solvent does not become too high, and the reaction condition width is not limited, which is preferable. Moreover, if it is lighter than C40 hydrocarbons, the solubility of the raw material synthesis gas will not decrease, and a decrease in reaction activity can be avoided. In the reduction treatment performed in advance, in the case where a method in which the catalyst is dispersed in liquid hydrocarbons is employed, the liquid hydrocarbons used in the reduction treatment can be used as they are in this FT reaction.
ＦＴ反応に当たって炭化水素類中に分散させる触媒量は、好ましくは１〜５０質量％の濃度であり、より好ましくは２〜４０質量％、最も好ましくは３〜３０質量％の濃度である。触媒量が１質量％以上であれば、触媒の活性が不足することを回避できる。なお、活性が不足するとその活性の不足を補うために、合成ガスの通気量を減少させ、その合成ガスの通気量の低下により気（合成ガス）−液（溶媒）−固（触媒）の分散が損なわれる。また、触媒量が５０質量％以下であれば、炭化水素類に触媒を分散させたスラリーの粘性が高くなりすぎ、気泡分散が悪くなり、反応活性が十分得られなくなることを回避することができる。 The amount of the catalyst dispersed in the hydrocarbons in the FT reaction is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and most preferably 3 to 30% by mass. If the amount of catalyst is 1% by mass or more, it is possible to avoid a lack of catalyst activity. In addition, if the activity is insufficient, in order to make up for the lack of activity, the aeration amount of the synthesis gas is decreased, and the gas (synthesis gas) -liquid (solvent) -solid (catalyst) dispersion is caused by the decrease in the aeration amount of the synthesis gas. Is damaged. Further, if the amount of catalyst is 50% by mass or less, it is possible to avoid that the viscosity of the slurry in which the catalyst is dispersed in hydrocarbons becomes too high, resulting in poor bubble dispersion and insufficient reaction activity. .
ＦＴ反応に用いる合成ガスは、水素及び一酸化炭素を主成分としていれば良く、ＦＴ反応を妨げない他の成分が混入されていても差し支えない。また、ＦＴ反応の速度（ｋ）は、水素分圧に約一次で依存するので、水素及び一酸化炭素の分圧比（Ｈ２／ＣＯモル比）が０．６以上であることが望まれる。この反応は、体積減少を伴う反応であるため、水素及び一酸化炭素の分圧の合計値が高いほど好ましい。水素及び一酸化炭素の分圧比は、その上限は特に制限されないが、現実的なこの分圧比の範囲としては０．６〜２．７が好ましく、より好ましくは０．８〜２．５、特に好ましくは１〜２．３である。この分圧比が０．６以上であれば、生成する炭化水素類の収量が低下することを防ぐことができ、また、この分圧比が２．７以下であれば、生成する炭化水素類においてガス成分や軽質分が増える傾向を抑止することができる。 The synthesis gas used for the FT reaction only needs to contain hydrogen and carbon monoxide as main components, and other components that do not interfere with the FT reaction may be mixed. Further, since the rate (k) of the FT reaction depends on the first order of the hydrogen partial pressure, it is desirable that the partial pressure ratio of hydrogen and carbon monoxide (H 2 / CO molar ratio) is 0.6 or more. Since this reaction is a reaction accompanied by volume reduction, it is preferable that the total value of the partial pressures of hydrogen and carbon monoxide is higher. The upper limit of the partial pressure ratio of hydrogen and carbon monoxide is not particularly limited, but the practical range of the partial pressure ratio is preferably 0.6 to 2.7, more preferably 0.8 to 2.5, and particularly Preferably it is 1-2. If this partial pressure ratio is 0.6 or more, it is possible to prevent the yield of produced hydrocarbons from decreasing, and if this partial pressure ratio is 2.7 or less, gas is produced in the produced hydrocarbons. The tendency to increase the components and light components can be suppressed.
上記合成ガス中に混入していても差し支えないＦＴ反応を妨げない他の成分としては、二酸化炭素が挙げられる。本発明の炭化水素類の製造方法では、天然ガスや石油製品などの改質反応により得られる二酸化炭素の混入している合成ガスも何ら問題なく用いることができる。また、二酸化炭素以外のＦＴ反応を妨げない他の成分が混入されていても差し支えなく、例えば、天然ガスや石油製品等の水蒸気改質反応あるいは自己熱改質反応から得られるようなメタンや水蒸気や部分酸化された窒素等が含有された合成ガスでも良い。また、この二酸化炭素は、二酸化炭素の含有されてない合成ガスに積極的に添加することもできる。本発明の炭化水素類の製造方法の実施に当たって、天然ガスや石油製品を自己熱改質法あるいは水蒸気改質法等で改質して得られた二酸化炭素を含有する合成ガスを、その中の二酸化炭素を除去するための脱炭酸処理をすることなくそのままＦＴ反応に供すれば、脱炭酸処理に要する設備建設コスト及び運転コストを削減することができ、ＦＴ反応で得られる炭化水素類の製造コストを低減することができる。 Another component that does not interfere with the FT reaction that may be mixed in the synthesis gas includes carbon dioxide. In the method for producing hydrocarbons of the present invention, synthesis gas mixed with carbon dioxide obtained by a reforming reaction of natural gas or petroleum products can be used without any problem. Also, other components that do not interfere with the FT reaction other than carbon dioxide may be mixed. For example, methane or steam obtained from steam reforming reaction or autothermal reforming reaction of natural gas, petroleum products, etc. Or a synthesis gas containing partially oxidized nitrogen or the like may be used. The carbon dioxide can also be positively added to synthesis gas that does not contain carbon dioxide. In carrying out the method for producing hydrocarbons of the present invention, a synthesis gas containing carbon dioxide obtained by reforming natural gas or petroleum products by a self-thermal reforming method or a steam reforming method is contained therein. If the FT reaction is used as it is without decarboxylation to remove carbon dioxide, the equipment construction cost and operation cost required for the decarboxylation treatment can be reduced, and the hydrocarbons obtained by the FT reaction can be produced. Cost can be reduced.
本発明の炭化水素類の製造方法において、ＦＴ反応に供する合成ガス（混合ガス）の全圧（全成分の分圧の合計値）は、０．５〜１０ＭＰａが好ましく、０．７〜７ＭＰａがさらに好ましく、０．８〜５ＭＰａがなおさらに好ましい。この全圧が０．５ＭＰａ以上であれば、連鎖成長が十分となり、ガソリン分、灯軽油分、ワックス分などの収率が低下することを防ぐことができる。平衡上は、水素及び一酸化炭素の分圧が高いほど有利になるが、上記全圧が１０ＭＰａ以下であれば、プラント建設コスト等が高まったり、圧縮に必要な圧縮機などの大型化により運転コストが上昇するなどの産業上の観点からの不利益を相応に抑止することができる。 In the method for producing hydrocarbons of the present invention, the total pressure of the synthesis gas (mixed gas) subjected to the FT reaction (total value of partial pressures of all components) is preferably 0.5 to 10 MPa, and 0.7 to 7 MPa. More preferably, 0.8-5 MPa is still more preferable. If this total pressure is 0.5 MPa or more, chain growth is sufficient, and it is possible to prevent the yield of gasoline, kerosene, wax, and the like from decreasing. In terms of equilibrium, the higher the partial pressure of hydrogen and carbon monoxide, the more advantageous. However, if the total pressure is 10 MPa or less, the plant construction cost increases and the operation is increased by increasing the size of the compressor required for compression. The disadvantages from the industrial point of view, such as rising costs, can be suppressed accordingly.
このＦＴ反応においては、一般に、合成ガスのＨ２／ＣＯモル比が同一であれば、反応温度が低いほど連鎖成長確率やＣ５＋選択性（ＦＴ反応性生物中の炭素数５以上の生成物の割合）が高くなるが、ＣＯ転化率は低くなる。逆に、反応温度が高くなれば、連鎖成長確率、Ｃ５＋選択性は低くなるが、ＣＯ転化率は高くなる。また、Ｈ２／ＣＯ比が高くなれば、ＣＯ転化率が高くなり、連鎖成長確率、Ｃ５＋選択性は低下し、Ｈ２／ＣＯ比が低くなれば、その逆となる。これらのファクターが反応に及ぼす効果は、用いる触媒の種類等によってその大小が異なるが、本発明の触媒を用いる方法においては、反応温度は、２００〜３５０℃が適当であり、２１０〜３１０℃が好ましく、２２０〜２９０℃がさらに好ましい。なお、ＣＯ転化率は下記式で定義されるものである。
〔ＣＯ転化率〕
ＣＯ転化率＝［（単位時間当たりの原料ガス中のＣＯモル数）−（単位時間当たりの出口ガス中のＣＯモル数）］／単位時間当たりの原料ガス中のＣＯモル数×１００
Generally, in this FT reaction, if the H 2 / CO molar ratio of the synthesis gas is the same, the lower the reaction temperature, the higher the chain growth probability and the C5 + selectivity (for products having 5 or more carbon atoms in the FT-reactive organism). Ratio) increases, but CO conversion decreases. Conversely, if the reaction temperature is increased, the chain growth probability and C5 + selectivity are lowered, but the CO conversion is increased. In addition, the higher the H 2 / CO ratio, the higher the CO conversion rate, the lower the chain growth probability and C5 + selectivity, and vice versa when the H 2 / CO ratio is low. The effect of these factors on the reaction varies depending on the type of catalyst used, but in the method using the catalyst of the present invention, the reaction temperature is suitably 200 to 350 ° C, and 210 to 310 ° C. Preferably, 220 to 290 ° C is more preferable. The CO conversion rate is defined by the following formula.
[CO conversion rate]
CO conversion rate = [(number of moles of CO in raw material gas per unit time) − (number of moles of CO in outlet gas per unit time)] / number of moles of CO in raw material gas per unit time × 100
以下、実施例及び比較例によりさらに具体的に本発明を説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.
以下の実施例において、ＣＯ分析は、Active Carbon（60/80mesh）を分離カラムに用いた熱伝導度型ガスクロマトグラフ（ＴＣＤ−ＧＣ）で行った。なお、原料ガスには、Ａｒを内部標準として２５ｖｏｌ％添加した合成ガス（Ｈ２とＣＯの混合ガス）を用いた。ＣＯのピーク位置、ピーク面積をＡｒと比較することで定性及び定量分析した。触媒の化学成分の同定はＩＣＰ（CQM-10000P、島津製作所製）により求めた。 In the following Examples, CO analysis was performed by a thermal conductivity gas chromatograph (TCD-GC) using Active Carbon (60 / 80mesh) as a separation column. Incidentally, the raw material gas used was 25 vol% added syngas as an internal standard (mixed gas of H 2 and CO) to Ar. Qualitative and quantitative analysis was performed by comparing the peak position and peak area of CO with Ar. The chemical component of the catalyst was identified by ICP (CQM-10000P, manufactured by Shimadzu Corporation).
また、ＣＨ４選択率は下記式により算出した。
ＣＨ４選択率（％）＝（単位時間当たりの出口ガス中のＣＨ４モル数）／｛（単位時間当たりの原料ガス中のＣＯモル数）−（単位時間当たりの出口ガス中のＣＯモル数）｝×１００
Further, CH 4 selectivity was calculated by the following equation.
CH 4 selectivity (%) = (CH 4 moles in outlet gas per unit time) / {(number of CO moles in raw material gas per unit time) − (number of CO moles in outlet gas per unit time) )} × 100
実施例１
炭酸マンガンとして和光純薬工業製の炭酸マンガン（II）ｎ水和物を使用した。
予め１５０℃で５時間乾燥した後、炭酸マンガン４．９２５ｇを秤量し、それに、水３．０ｇに塩化ルテニウム（小島化学製Ru Assay 40.79質量％）０．１８４ｇを溶解した水溶液を含浸させ、１時間放置した後、空気中、８０℃で３時間乾燥し、その後１５０℃で３時間焼成し触媒Ａを得た。
触媒ＡについてＸ線回折にて構造分析を行った結果、マンガンは炭酸マンガンを維持していた。また、ＩＣＰにて触媒Ａの化学組成分析を行った結果、ルテニウムは金属換算で１．５質量％であった。
Example 1
Manganese carbonate (II) n hydrate manufactured by Wako Pure Chemical Industries was used as manganese carbonate.
After drying at 150 ° C. for 5 hours in advance, 4.925 g of manganese carbonate was weighed and impregnated with an aqueous solution in which 0.184 g of ruthenium chloride (Ru Assay 40.79% by mass made by Kojima Chemical) was dissolved in 3.0 g of water. After standing for a period of time, it was dried in air at 80 ° C. for 3 hours and then calcined at 150 ° C. for 3 hours to obtain Catalyst A.
As a result of structural analysis of the catalyst A by X-ray diffraction, manganese maintained manganese carbonate. Moreover, as a result of conducting the chemical composition analysis of the catalyst A by ICP, ruthenium was 1.5 mass% in metal conversion.
触媒Ａ、２．４ｇを分散媒のノルマルヘキサデカン４０ｍｌ（スラリー濃度７．２重量％）と共に内容積１００ｍｌの反応器に充填し、水素分圧０．９ＭＰａ・Ｇ、温度１７０℃、流量１００（ＳＴＰ）ｍｌ／ｍｉｎ（ＳＴＰ：standard temperature and pressure）で水素を触媒Ａに接触させて３時間還元した。還元後、Ｈ２／ＣＯ比約２の合成ガス（Ａｒ約２５ｖｏｌ．％含む）に切り換え、温度２６０℃、Ｈ２＋ＣＯ圧力０．９ＭＰａ・ＧにしてＦＴ反応を行った。
Ｗ／Ｆ（weight／flow）［ｇ・ｈｒ／ｍｏｌ］は約１１ｇ・ｈｒ／ｍｏｌであった。ＦＴ反応開始２０時間後のＣＯ転化率は約５１．５％、ＣＨ４選択率は約１０．５％、１００時間後のＣＯ転化率は約５０．２％であった。
Catalyst A (2.4 g) was charged into a reactor having an internal volume of 100 ml together with 40 ml of normal hexadecane (slurry concentration: 7.2 wt%) as a dispersion medium, a hydrogen partial pressure of 0.9 MPa · G, a temperature of 170 ° C., and a flow rate of 100 (STP). ) Hydrogen was brought into contact with catalyst A at ml / min (STP: standard temperature and pressure) and reduced for 3 hours. After the reduction, the FT reaction was carried out at a temperature of 260 ° C. and a H 2 + CO pressure of 0.9 MPa · G by switching to a synthesis gas having an H 2 / CO ratio of about 2 (including about 25 vol. Ar).
W / F (weight / flow) [g · hr / mol] was about 11 g · hr / mol. The CO conversion 20 hours after the start of the FT reaction was about 51.5%, the CH 4 selectivity was about 10.5%, and the CO conversion after 100 hours was about 50.2%.
実施例２
ルテニウムの含有量が３．０質量％となるように炭酸マンガン及び塩化ルテニウムの量を調節した以外は実施例１と同様にして触媒Ｂを得た。
ＩＣＰにて触媒Ｂの化学組成分析を行った結果、ルテニウムは金属換算で２．９質量％であった。この触媒Ｂを実施例１と同様の方法でＦＴ反応に供した。ＦＴ反応開始２０時間後のＣＯ転化率は約７０．９％、ＣＨ４選択率は１１．５％、１００時間後のＣＯ転化率は約７０．３％であった。
Example 2
Catalyst B was obtained in the same manner as in Example 1 except that the amounts of manganese carbonate and ruthenium chloride were adjusted so that the content of ruthenium was 3.0% by mass.
As a result of analyzing the chemical composition of the catalyst B by ICP, ruthenium was 2.9% by mass in terms of metal. This catalyst B was subjected to the FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 70.9%, the CH 4 selectivity was 11.5%, and the CO conversion after 100 hours was about 70.3%.
実施例３
炭酸マンガンとして、実施例１と同様の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、それに、水３．０ｇに硝酸コバルト（和光純薬工業製Co(NO3)2・6H2O）２．４６３ｇを溶解した水溶液を含浸させ、１時間放置した後、空気中、８０℃で３時間乾燥し、その後２００℃で３時間焼成し触媒Ｃを得た。
触媒ＣについてＸ線回折にて構造分析を行った結果、マンガンは炭酸マンガンを維持していた。また、ＩＣＰ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１０．１質量％であった。この触媒Ｃを実施例１と同様の方法でＦＴ反応に供した。ＦＴ反応開始２０時間後のＣＯ転化率は約６２．４％、ＣＨ４選択率は約１１．８％、１００時間後のＣＯ転化率は約６０．１％であった。
Example 3
As manganese carbonate, the same manganese carbonate (II) n hydrate manufactured by Wako Pure Chemical Industries, Ltd. as in Example 1 was used.
After drying at 150 ° C. for 5 hours in advance, 4.5 g of manganese carbonate is weighed, and 2.463 g of cobalt nitrate (Co (NO 3 ) 2 · 6H 2 O manufactured by Wako Pure Chemical Industries) is dissolved in 3.0 g of water. The obtained aqueous solution was impregnated and allowed to stand for 1 hour, dried in air at 80 ° C. for 3 hours, and then calcined at 200 ° C. for 3 hours to obtain Catalyst C.
As a result of structural analysis of the catalyst C by X-ray diffraction, manganese maintained manganese carbonate. Moreover, as a result of conducting the chemical composition analysis of the catalyst C in ICP, cobalt was 10.1 mass% in metal conversion. This catalyst C was subjected to the FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 62.4%, the CH 4 selectivity was about 11.8%, and the CO conversion after 100 hours was about 60.1%.
実施例４
コバルトの含有量が３０質量％となるように炭酸マンガン及び硝酸コバルトの量を調節した以外は実施例３と同様にして触媒Ｄを得た。
ＩＣＰにて触媒Ｄの化学組成分析を行った結果、コバルトは金属換算で３０．２質量％であった。この触媒Ｄを実施例１と同様の方法でＦＴ反応に供した。ＦＴ反応開始２０時間後のＣＯ転化率は約６８．２％、ＣＨ４選択率は約２０．８％、１００時間後のＣＯ転化率は約６７．１％であった。
Example 4
Catalyst D was obtained in the same manner as in Example 3, except that the amounts of manganese carbonate and cobalt nitrate were adjusted so that the cobalt content was 30% by mass.
As a result of conducting the chemical composition analysis of the catalyst D by ICP, cobalt was 30.2 mass% in metal conversion. This catalyst D was subjected to FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 68.2%, the CH 4 selectivity was about 20.8%, and the CO conversion after 100 hours was about 67.1%.
実施例５
炭酸マンガンとして、実施例１と同様の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４．４２５ｇを秤量し、それに、水３．０ｇに塩化ルテニウム（小島化学製Ru Assay 40.79質量％）０．１８４ｇ及び硝酸コバルト（和光純薬工業製Co(NO3)2・6H2O）２．４６３ｇを溶解した水溶液を含浸させ、１時間放置した後、空気中、８０℃で３時間乾燥し、その後２００℃で３時間焼成し触媒Ｅを得た。
触媒ＥについてＸ線回折にて構造分析を行った結果、マンガンは炭酸マンガンを維持していた。また、ＩＣＰにて触媒Ｅの化学組成分析を行った結果、ルテニウムは金属換算で１．５質量％、コバルトは金属換算で１０．１質量％であった。この触媒Ｅを実施例１と同様の方法でＦＴ反応に供した。ＦＴ反応開始２０時間後のＣＯ転化率は約７６．７％、ＣＨ４選択率は約３５．４％、１００時間後のＣＯ転化率は約７６．２％であった。
Example 5
As manganese carbonate, the same manganese carbonate (II) n hydrate manufactured by Wako Pure Chemical Industries, Ltd. as in Example 1 was used.
After drying at 150 ° C. for 5 hours in advance, 4.425 g of manganese carbonate was weighed, and 0.184 g of ruthenium chloride (Ru Assay 40.79% by mass made by Kojima Chemical) and cobalt nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) in 3.0 g of water. After impregnating an aqueous solution in which 2.463 g of Co (NO 3 ) 2 · 6H 2 O) was dissolved, the mixture was allowed to stand for 1 hour, dried in air at 80 ° C. for 3 hours, and then calcined at 200 ° C. for 3 hours to obtain catalyst E. Obtained.
As a result of structural analysis of the catalyst E by X-ray diffraction, manganese maintained manganese carbonate. Moreover, as a result of conducting the chemical composition analysis of the catalyst E in ICP, ruthenium was 1.5 mass% in metal conversion, and cobalt was 10.1 mass% in metal conversion. This catalyst E was subjected to FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 76.7%, the CH 4 selectivity was about 35.4%, and the CO conversion after 100 hours was about 76.2%.
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Ｆを得た。
触媒ＦについてＸ線回折にて構造分析を行った結果、マンガンはＭｎ２Ｏ３であった。ＩＣＰにて触媒Ｆの化学組成分析を行った結果、ルテニウムは金属換算で１．６質量％であった。この触媒Ｆを実施例１と同様の方法でＦＴ反応に供した。ＦＴ反応開始２０時間後のＣＯ転化率は約３１．０％、ＣＨ４選択率は約８．５％、１００時間後のＣＯ転化率は約２３．１％であった。
Comparative Example 1
Catalyst F 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 of the catalyst F by X-ray diffraction, manganese was Mn 2 O 3 . As a result of analyzing the chemical composition of the catalyst F by ICP, ruthenium was 1.6% by mass in terms of metal. This catalyst F was subjected to FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 31.0%, the CH 4 selectivity was about 8.5%, and the CO conversion after 100 hours was about 23.1%.
比較例２
炭酸マンガンに代えて和光純薬工業製の酸化マンガン（II）（MnO）を使用した以外は実施例１と同様にして触媒Ｇを得た。
触媒ＧについてＸ線回折にて構造分析を行った結果、マンガンはＭｎＯであった。ＩＣＰにて触媒Ｇの化学組成分析を行った結果、ルテニウムは金属換算で１．５質量％であった。この触媒Ｇを実施例１と同様の方法でＦＴ反応に供した。ＦＴ反応開始２０時間後のＣＯ転化率は約１１．２％、ＣＨ４選択率は約７．２％、１００時間後のＣＯ転化率は約９．３％であった。
Comparative Example 2
Catalyst G was obtained in the same manner as in Example 1 except that manganese oxide (II) (MnO) manufactured by Wako Pure Chemical Industries, Ltd. was used instead of manganese carbonate.
As a result of structural analysis of the catalyst G by X-ray diffraction, manganese was MnO. As a result of analyzing the chemical composition of the catalyst G by ICP, ruthenium was 1.5% by mass in terms of metal. This catalyst G was subjected to the FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 11.2%, the CH 4 selectivity was about 7.2%, and the CO conversion after 100 hours was about 9.3%.
比較例３
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）を予め充分乾燥した後、４．９２５ｇを秤量し、それに、水６．０６ｇに塩化ルテニウム（小島化学製Ru Assay 40.79質量％）０．１８４ｇを溶解した水溶液を含浸させ、１時間放置した後、空気中、８０℃で３時間乾燥し、その後２００℃で３時間焼成し触媒Ｈを得た。
ＩＣＰにて触媒Ｈの化学組成分析を行った結果、ルテニウムは金属換算で１．６質量％であった。この触媒Ｈを実施例１と同様の方法でＦＴ反応に供した。ＦＴ反応開始２０時間後のＣＯ転化率は約１５．７％、ＣＨ４選択率は約１６．６％、１００時間後のＣＯ転化率は約１４．８％であった。
Comparative Example 3
After sufficiently drying spherical silica (Q-30) manufactured by Fuji Silysia Chemical instead of manganese carbonate, 4.925 g was weighed, and then ruthenium chloride in 6.06 g of water (Ru Assay 40.79% by mass manufactured by Kojima Chemical). An aqueous solution in which 0.184 g was dissolved was impregnated and left for 1 hour, then dried in air at 80 ° C. for 3 hours, and then calcined at 200 ° C. for 3 hours to obtain Catalyst H.
As a result of analyzing the chemical composition of the catalyst H by ICP, ruthenium was 1.6% by mass in terms of metal. This catalyst H was subjected to FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 15.7%, the CH 4 selectivity was about 16.6%, and the CO conversion after 100 hours was about 14.8%.
比較例４
炭酸マンガンに代えて酸化アルミニウム粉末（Pural SB, Condea製）を予め充分乾燥した後、４．９２５ｇを秤量し、それに、水４．４３ｇに塩化ルテニウム（小島化学製Ru Assay 40.79質量％）０．１８４ｇを溶解した水溶液を含浸させ、１時間放置した後、空気中、８０℃で３時間乾燥し、その後２００℃で３時間焼成し触媒Ｉを得た。
ＩＣＰにて触媒Ｉの化学組成分析を行った結果、ルテニウムは金属換算で１．５質量％であった。この触媒Ｉを実施例１と同様の方法でＦＴ反応に供した。ＦＴ反応開始２０時間後のＣＯ転化率は約３０．２％、ＣＨ４選択率は約２１．０％、１００時間後のＣＯ転化率は約１８．９％であった。
Comparative Example 4
Aluminum oxide powder (manufactured by Pural SB, Condea) was sufficiently dried in place of manganese carbonate, and 4.925 g was weighed. Then, 4.43 g of water was mixed with ruthenium chloride (Ru Assay 40.79% by mass, manufactured by Kojima Chemical). An aqueous solution in which 184 g was dissolved was impregnated, left for 1 hour, dried in air at 80 ° C. for 3 hours, and then calcined at 200 ° C. for 3 hours to obtain Catalyst I.
As a result of analyzing the chemical composition of the catalyst I by ICP, ruthenium was 1.5% by mass in terms of metal. This catalyst I was subjected to the FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 30.2%, the CH 4 selectivity was about 21.0%, and the CO conversion after 100 hours was about 18.9%.
比較例５
炭酸マンガンに代えて富士シリシア化学製の球状シリカ（Q-30）を予め充分乾燥した後、４．５ｇを秤量し、それに、水５．５４ｇに硝酸コバルト（和光純薬工業製Co(NO3)2・6H2O）２．４６３ｇを溶解した水溶液を含浸させ、１時間放置した後、空気中、８０℃で３時間乾燥し、その後２００℃で３時間焼成し触媒Ｊを得た。
ＩＣＰにて触媒Ｊの化学組成分析を行った結果、コバルトは金属換算で１０．２質量％であった。この触媒Ｊを実施例１と同様の方法でＦＴ反応に供した。ＦＴ反応開始２０時間後のＣＯ転化率は約３６．２％、ＣＨ４選択率は約４３．５％、１００時間後のＣＯ転化率は約３０．７％であった。
Comparative Example 5
After spherical silica (Q-30) manufactured by Fuji Silysia Chemical Co., Ltd. was sufficiently dried instead of manganese carbonate, 4.5 g was weighed, and cobalt nitrate (Co (NO 3 manufactured by Wako Pure Chemical Industries) was added to 5.54 g of water. 2 ) 6H 2 O) An aqueous solution in which 2.463 g was dissolved was impregnated and allowed to stand for 1 hour, dried in air at 80 ° C. for 3 hours, and then calcined at 200 ° C. for 3 hours to obtain Catalyst J.
As a result of analyzing the chemical composition of the catalyst J by ICP, cobalt was 10.2% by mass in terms of metal. This catalyst J was subjected to the FT reaction in the same manner as in Example 1. The CO conversion after 20 hours from the start of the FT reaction was about 36.2%, the CH 4 selectivity was about 43.5%, and the CO conversion after 100 hours was about 30.7%.
比較例６
コバルトの含有量が３０質量％となるように球状シリカ、水及び硝酸コバルトの量を調節した以外は比較例５と同様にして触媒Ｋを得た。
ＩＣＰにて触媒Ｋの化学組成分析を行った結果、コバルトは金属換算で３０．１質量％であった。この触媒Ｋを実施例１と同様の方法でＦＴ反応に供した。ＦＴ反応開始２０時間後のＣＯ転化率は約６１．６％、ＣＨ４選択率は約５０．７％、１００時間後のＣＯ転化率は約５７．５％であった。
Comparative Example 6
Catalyst K was obtained in the same manner as in Comparative Example 5 except that the amounts of spherical silica, water and cobalt nitrate were adjusted so that the cobalt content was 30% by mass.
As a result of analyzing the chemical composition of the catalyst K by ICP, cobalt was 30.1% by mass in terms of metal. This catalyst K was subjected to the FT reaction in the same manner as in Example 1. The CO conversion 20 hours after the start of the FT reaction was about 61.6%, the CH 4 selectivity was about 50.7%, and the CO conversion after 100 hours was about 57.5%.
上記実施例１〜５及び比較例１〜６の実験結果を表１及び表２に示す。表１及び表２から、本発明の炭酸マンガン担体を用いた触媒は、従来のアルミナやシリカを担体とする触媒に比較してＣＯ転化率が高く、また、ガス成分であるＣＨ４の生成割合が低いことが明らかである。さらに、本発明の触媒の性能は長時間安定的に発揮されることが分かる。また、本発明のこのような効果は、酸化マンガンの担体を用いたのでは認められず、炭酸マンガンの担体を用いることで発現していることが分かる。 The experimental results of Examples 1 to 5 and Comparative Examples 1 to 6 are shown in Tables 1 and 2. From Tables 1 and 2, the catalyst using the manganese carbonate carrier of the present invention has a higher CO conversion rate than the conventional catalyst using alumina or silica as a carrier, and the production ratio of CH 4 which is a gas component. Is clearly low. Furthermore, it turns out that the performance of the catalyst of this invention is exhibited stably for a long time. Further, it can be seen that such an effect of the present invention is not observed when a manganese oxide carrier is used, but is manifested by using a manganese carbonate carrier.
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