JP2011241122A - Method for producing synthesis gas - Google Patents
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- JP2011241122A JP2011241122A JP2010116030A JP2010116030A JP2011241122A JP 2011241122 A JP2011241122 A JP 2011241122A JP 2010116030 A JP2010116030 A JP 2010116030A JP 2010116030 A JP2010116030 A JP 2010116030A JP 2011241122 A JP2011241122 A JP 2011241122A
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- ruthenium
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000007789 gas Substances 0.000 claims abstract description 106
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 68
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002407 reforming Methods 0.000 claims abstract description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 26
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 26
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 24
- 150000003304 ruthenium compounds Chemical class 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 9
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 110
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 14
- -1 RuCl 3 Chemical class 0.000 description 13
- 150000003377 silicon compounds Chemical class 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 230000001590 oxidative effect Effects 0.000 description 11
- 239000011261 inert gas Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 235000012149 noodles Nutrition 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical class O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- SUWCFTLKWQKEFZ-UHFFFAOYSA-M azane;ruthenium(3+);chloride Chemical compound N.N.N.N.N.[Cl-].[Ru+3] SUWCFTLKWQKEFZ-UHFFFAOYSA-M 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000002579 carboxylato group Chemical group [O-]C(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、改質用触媒の存在下、炭化水素を二酸化炭素により改質させて、水素及び一酸化炭素を含有する合成ガスを製造する方法に関する。水素と一酸化炭素を含有する合成ガスは、メタノール、ジメチルエーテル、合成石油等を製造する原料として有用である。 The present invention relates to a method for producing a synthesis gas containing hydrogen and carbon monoxide by reforming a hydrocarbon with carbon dioxide in the presence of a reforming catalyst. Syngas containing hydrogen and carbon monoxide is useful as a raw material for producing methanol, dimethyl ether, synthetic petroleum and the like.
将来の石油代替エネルギー源として、近年天然ガスが注目されている。一方で、近年、大気中の二酸化炭素による地球温暖化の懸念から、二酸化炭素の有効利用が課題となっている。そのような観点から、天然ガスに含まれる成分である炭化水素を、二酸化炭素と反応させて改質し、水素及び一酸化炭素を含む合成ガスを製造する方法が提案されている。例えば、特許文献1には、担体にロジウム、ルテニウム、イリジウム、白金からなる群から選ばれる少なくとも1種の金属を担持した触媒の存在下に、メタンを二酸化炭素によって改質させる方法が記載され、特許文献2には、担体にジルコニウム、ルテニウム、コバルト及びマグネシウムからなる群から選ばれる少なくとも1種を担持した触媒の存在下に、メタンを酸素、スチーム及び炭酸ガスの混合ガスにより改質させて、水素及び一酸化炭素を含む合成ガスを製造する方法が記載されている。 In recent years, natural gas has attracted attention as a future oil alternative energy source. On the other hand, in recent years, effective use of carbon dioxide has become a problem due to concerns about global warming due to carbon dioxide in the atmosphere. From such a viewpoint, a method has been proposed in which a hydrocarbon, which is a component contained in natural gas, is reformed by reacting with carbon dioxide to produce a synthesis gas containing hydrogen and carbon monoxide. For example, Patent Document 1 describes a method of reforming methane with carbon dioxide in the presence of a catalyst supporting at least one metal selected from the group consisting of rhodium, ruthenium, iridium, and platinum on a carrier, In Patent Document 2, methane is reformed by a mixed gas of oxygen, steam and carbon dioxide in the presence of a catalyst supporting at least one selected from the group consisting of zirconium, ruthenium, cobalt and magnesium on a carrier, A method for producing synthesis gas containing hydrogen and carbon monoxide is described.
しかしながら、上記従来の方法では、水素及び一酸化炭素を含む合成ガスの製造において、炭化水素を良好な転化率で改質させる点で、必ずしも充分なものではなかった。 However, the conventional method described above is not necessarily sufficient in terms of reforming hydrocarbons with a good conversion rate in the production of synthesis gas containing hydrogen and carbon monoxide.
そこで、本発明の目的は、炭化水素を二酸化炭素により良好な転化率で改質させて、水素及び一酸化炭素を含む合成ガスを製造する方法を提供することにある。 Therefore, an object of the present invention is to provide a method for producing a synthesis gas containing hydrogen and carbon monoxide by reforming hydrocarbons with carbon dioxide at a good conversion rate.
本発明者らは鋭意検討したところ、ルテニウム及びルテニウム化合物からなる群から選ばれる少なくとも一種とシリカとが担体に担持されてなる触媒の存在下で、炭化水素を二酸化炭素により改質させることにより、良好な転化率で炭化水素を改質させることができ、水素及び一酸化炭素を含む合成ガスを製造することができるという新たな知見を見出し、本発明を完成するに至った。 As a result of diligent examination, the inventors of the present invention have modified hydrocarbons with carbon dioxide in the presence of a catalyst in which at least one selected from the group consisting of ruthenium and ruthenium compounds and silica are supported on a carrier, The present inventors have found a new finding that hydrocarbons can be reformed with a good conversion rate and a synthesis gas containing hydrogen and carbon monoxide can be produced, and the present invention has been completed.
すなわち、本発明の合成ガスの製造方法は、以下の構成からなる。
(1)ルテニウム及びルテニウム化合物からなる群から選ばれる少なくとも一種とシリカとが担体に担持されてなる改質用触媒の存在下、炭化水素を二酸化炭素により改質させる水素及び一酸化炭素を含有する合成ガスの製造方法。
(2)前記担体がチタニアである前記(1)に記載の製造方法。
(3)前記チタニアが、ルチル結晶形チタニアを含有する前記(2)に記載の製造方法。
(4)X線回折法により測定される前記チタニア中のルチル結晶形チタニアの比率が、ルチル結晶形チタニア及びアナターゼ結晶形チタニアの合計に対し20%以上である前記(3)に記載の製造方法。
(5)前記炭化水素がメタン及びエタンからなる群から選ばれる少なくとも1種である前記(1)〜(4)のいずれかに記載の製造方法。
(6)改質温度が、350〜700℃である前記(1)〜(5)のいずれかに記載の製造方法。
That is, the synthesis gas production method of the present invention has the following configuration.
(1) Contains hydrogen and carbon monoxide for reforming hydrocarbons with carbon dioxide in the presence of a reforming catalyst in which at least one selected from the group consisting of ruthenium and ruthenium compounds and silica are supported on a carrier. A method for producing synthesis gas.
(2) The production method according to (1), wherein the carrier is titania.
(3) The production method according to (2), wherein the titania contains rutile crystal titania.
(4) The production method according to (3), wherein the ratio of rutile crystal titania in the titania measured by X-ray diffraction method is 20% or more with respect to the total of rutile crystal titania and anatase crystal titania. .
(5) The production method according to any one of (1) to (4), wherein the hydrocarbon is at least one selected from the group consisting of methane and ethane.
(6) The production method according to any one of (1) to (5), wherein the reforming temperature is 350 to 700 ° C.
本発明によれば、炭化水素を二酸化炭素により良好な転化率で改質させて、水素及び一酸化炭素を含む合成ガスを製造することができる。 According to the present invention, synthesis gas containing hydrogen and carbon monoxide can be produced by reforming hydrocarbons with carbon dioxide at a good conversion rate.
以下、本発明を詳細に説明する。本発明で使用される改質用触媒は、ルテニウム及びルテニウム化合物からなる群から選ばれる少なくとも一種(以下、「ルテニウム成分」と称することがある)とシリカとが担体に担持されてなる触媒である。ここでいうルテニウムとしては、金属単体のルテニウムである金属ルテニウムが挙げられ、ルテニウム化合物としては、RuO2、RuO(OH)、RuO(OH)2、Ru(OH)3、Ru(OH)4の如き酸化物、オキシ水酸化物又は水酸化物;RuCl3、RuBr3の如きハロゲン化物;K2RuO4の如きオキソ酸塩;Ru2OCl4、Ru2OCl5、Ru2OCl6の如きオキシハロゲン化物;K2[RuCl5(NO)]、[Ru(NH3)5(NO)]Cl3、[Ru(OH)(NH3)4(NO)](NO3)2、[Ru(NO)](NO3)3の如きニトロシル錯体;K2[RuCl5(H2O)4]、[RuCl2(H2O)4]Cl、K2[Ru2OCl10]、Cs2[Ru2OCl4]の如きハロゲノ錯体;[Ru(NH3)5H2O]Cl2、[Ru(NH3)5Cl]Cl2、[Ru(NH3)6]Cl2、[Ru(NH3)6]Cl3、[Ru(NH3)6]Br3の如きアンミン錯体;Ru(CO)5、Ru3(CO)12の如きカルボニル錯体;[Ru3O(OCOCH3)6(H2O)3]OCOCH3、[Ru2(OCOR)4]Cl(R=炭素数1〜3のアルキル基)の如きカルボキシラト錯体;ホスフィン錯体;アミン錯体;アセチルアセトナト錯体等が挙げられる。なお、ルテニウム化合物としては、その水和物であってもよいし、また、これらうちの任意の組み合わせよりなる2種以上の混合物であってもよい。中でも、酸化物が好ましく、すなわち、触媒として、担体に酸化ルテニウムとシリカとが担持されてなる触媒が好ましい。担持されている酸化ルテニウムにおけるルテニウムの酸化数は、通常+4であり、酸化ルテニウムとしては二酸化ルテニウム(RuO2)であるが、他の酸化数のルテニウムないし他の形態の酸化ルテニウムが含まれていてもよい。また、反応条件によっては、触媒において、担持されたルテニウムが反応後に酸化ルテニウムになることや、担持されたルテニウム化合物が金属ルテニウムになることがある。 The present invention will be described in detail below. The reforming catalyst used in the present invention is a catalyst in which at least one selected from the group consisting of ruthenium and a ruthenium compound (hereinafter sometimes referred to as “ruthenium component”) and silica are supported on a carrier. . Examples of ruthenium include metal ruthenium which is ruthenium of a simple metal, and examples of ruthenium compounds include RuO 2 , RuO (OH), RuO (OH) 2 , Ru (OH) 3 , and Ru (OH) 4 . Oxides such as oxides, oxyhydroxides or hydroxides; halides such as RuCl 3 , RuBr 3 ; oxoacid salts such as K 2 RuO 4 ; oxys such as Ru 2 OCl 4 , Ru 2 OCl 5 , Ru 2 OCl 6 Halide: K 2 [RuCl 5 (NO)], [Ru (NH 3 ) 5 (NO)] Cl 3 , [Ru (OH) (NH 3 ) 4 (NO)] (NO 3 ) 2 , [Ru ( Nitrosyl complexes such as NO)] (NO 3 ) 3 ; K 2 [RuCl 5 (H 2 O) 4 ], [RuCl 2 (H 2 O) 4 ] Cl, K 2 [Ru 2 OCl 10 ], Cs 2 [ Ru 2 O Halogeno complexes such as Cl 4 ]; [Ru (NH 3 ) 5 H 2 O] Cl 2 , [Ru (NH 3 ) 5 Cl] Cl 2 , [Ru (NH 3 ) 6 ] Cl 2 , [Ru (NH 3 ) 6 ] Cl 3 , [Ru (NH 3 ) 6 ] Br 3 ; Ammine complexes; Ru (CO) 5 , Ru 3 (CO) 12 carbonyl complexes; [Ru 3 O (OCOCH 3 ) 6 (H 2 Carboxylato complexes such as O) 3 ] OCOCH 3 and [Ru 2 (OCOR) 4 ] Cl (R = an alkyl group having 1 to 3 carbon atoms); phosphine complexes; amine complexes; acetylacetonato complexes and the like. In addition, as a ruthenium compound, the hydrate may be sufficient and the 2 or more types of mixture which consists of arbitrary combinations of these may be sufficient. Among these, an oxide is preferable, that is, a catalyst in which ruthenium oxide and silica are supported on a carrier is preferable as a catalyst. The ruthenium oxidation number in the supported ruthenium oxide is usually +4, and the ruthenium oxide is ruthenium dioxide (RuO 2 ), but other ruthenium oxides or other forms of ruthenium oxide are included. Also good. Depending on the reaction conditions, in the catalyst, the supported ruthenium may become ruthenium oxide after the reaction, or the supported ruthenium compound may become metal ruthenium.
前記改質用触媒における担体としては、例えば、チタニア、ジルコニア、酸化ニオブ、マグネシア、アルミナ、酸化カルシウム、酸化ランタン等の金属酸化物が挙げられ、必要に応じて、それらの2種以上を用いることもできる。中でも、チタニアが好ましい。かかる担体には、粉末状やゾル状の担体を混練、成形し、次いで焼成したものを用いることができる。焼成した担体は、公知の方法に基づいて調製することができ、例えば、粉末状の担体やゾル状の担体を、有機バインダー等の成形助剤及び水と混練し、ヌードル状に押出成形した後、乾燥、破砕して成形体を得、次いで得られた成形体を空気等の酸化性ガス雰囲気下で焼成することで調製できる。 Examples of the support in the reforming catalyst include metal oxides such as titania, zirconia, niobium oxide, magnesia, alumina, calcium oxide, and lanthanum oxide, and if necessary, use two or more of them. You can also. Of these, titania is preferable. As such a carrier, a powdery or sol-like carrier kneaded and molded, and then fired can be used. The calcined carrier can be prepared based on a known method. For example, a powdery carrier or a sol-like carrier is kneaded with a molding aid such as an organic binder and water, and extruded into a noodle shape. It can be prepared by drying, crushing to obtain a molded body, and then firing the obtained molded body in an oxidizing gas atmosphere such as air.
また、チタニアとしては、ルチル型チタニア(ルチル型の結晶構造を有するチタニア)、アナターゼ型チタニア(アナターゼ型の結晶構造を有するチタニア)、非晶質のチタニア等からなるものや、これらの混合物からなるものものであってもよい。本発明では、ルチル型チタニア及び/又はアナターゼ型チタニアからなるチタニア担体が好ましく、中でも、チタニア担体中のルチル型チタニア及びアナターゼ型チタニアの合計に対するルチル型チタニアの比率(以下、ルチル型チタニア比率ということがある。)が20%以上のチタニア担体が好ましく、30%以上のチタニア担体がより好ましく、90%以上のチタニア担体がさらにより好ましい。ルチル型チタニア比率が高くなるほど、得られる触媒の触媒活性もより良好となる。上記ルチル型チタニア比率は、X線回折法(以下XRD法)により測定でき、以下の式(1)で示される。 Further, as titania, it is composed of rutile type titania (titania having a rutile type crystal structure), anatase type titania (titania having anatase type crystal structure), amorphous titania, etc., or a mixture thereof. It may be a thing. In the present invention, a titania carrier composed of rutile titania and / or anatase titania is preferable. Among them, the ratio of rutile titania to the total of rutile titania and anatase titania in the titania carrier (hereinafter referred to as a rutile titania ratio). Is preferably 20% or more of titania carrier, more preferably 30% or more titania carrier, and still more preferably 90% or more titania carrier. The higher the rutile titania ratio, the better the catalytic activity of the resulting catalyst. The rutile-type titania ratio can be measured by an X-ray diffraction method (hereinafter referred to as XRD method) and is represented by the following formula (1).
ルチル型チタニア比率[%]=〔IR/(IA+IR)〕×100 (1) Rutile titania ratio [%] = [I R / (I A + I R) ] × 100 (1)
IR:ルチル型チタニア(110)面を示す回折線の強度
IA:アナターゼ型チタニア(101)面を示す回折線の強度
I R : Intensity of diffraction line showing rutile type titania (110) plane I A : Intensity of diffraction line showing anatase type titania (101) plane
本発明における改質用触媒としては、例えば、以下の(i)〜(iv)に示すものが挙げられる。
(i)担体にケイ素化合物を担持させた後、原料ルテニウム化合物を担持させ、次いで酸化性ガス雰囲気下で焼成して得られるもの。
(ii)チタン化合物とケイ素化合物とを酸化性ガス雰囲気下で熱処理して、シリカが担持されてなるチタニア担体を得、該担体に原料ルテニウム化合物を担持させた後、酸化性ガス、還元性ガス又は不活性ガス雰囲気下で焼成して得られるもの。
(iii)担体に原料ルテニウム化合物を担持させた後、ケイ素化合物を担持させ、次いで酸化性ガス雰囲気下で焼成して得られるもの。
(iv)担体に、ケイ素化合物及び原料ルテニウム化合物を担持させた後、酸化性ガス雰囲気下で焼成して得られるもの。
Examples of the reforming catalyst in the present invention include those shown in the following (i) to (iv).
(I) A material obtained by supporting a silicon compound on a carrier, then supporting a raw material ruthenium compound, and then firing in an oxidizing gas atmosphere.
(Ii) A titanium compound and a silicon compound are heat-treated in an oxidizing gas atmosphere to obtain a titania carrier on which silica is supported, and after the raw material ruthenium compound is supported on the carrier, an oxidizing gas and a reducing gas are obtained. Or obtained by firing in an inert gas atmosphere.
(Iii) A material obtained by supporting a raw material ruthenium compound on a carrier, then supporting a silicon compound, and then firing in an oxidizing gas atmosphere.
(Iv) What is obtained by supporting a silicon compound and a raw material ruthenium compound on a carrier and then firing in an oxidizing gas atmosphere.
前記(i)において、ケイ素化合物を担持させた後、酸化性ガス雰囲気下で焼成することもでき、前記(iii)において、原料ルテニウム化合物を担持させた後、酸化性ガス雰囲気下で焼成することもできる。また、前記(ii)において、チタン化合物としては、塩化チタン(TiCl4)、臭化チタン(TiBr4)等が挙げられる。前記(i)〜(iv)の処理の後、適宜還元性ガスを用いて担体に担持されているルテニウム化合物を還元し、ルテニウムとすることもできる。本発明においては、前記(i)〜(iv)で得られる触媒のうち、特に、前記(i)又は(ii)で得られる触媒が好ましい。 In (i), the silicon compound is supported and then fired in an oxidizing gas atmosphere. In (iii), the raw material ruthenium compound is supported and then fired in an oxidizing gas atmosphere. You can also. In (ii), examples of the titanium compound include titanium chloride (TiCl 4 ) and titanium bromide (TiBr 4 ). After the treatments (i) to (iv), the ruthenium compound supported on the carrier can be appropriately reduced to ruthenium using a reducing gas. In the present invention, among the catalysts obtained in (i) to (iv), the catalyst obtained in (i) or (ii) is particularly preferable.
前記ケイ素化合物としては、例えばSi(OR)4(以下、Rは炭素数1〜4のアルキル基を表す。)等のケイ素アルコキシド化合物、塩化ケイ素(SiCl4)、臭化ケイ素(SiBr4)等のハロゲン化ケイ素、SiCl(OR)3、SiCl2(OR)2、SiCl3(OR)等のケイ素ハロゲン化物アルコキシド化合物等が挙げられる。また、必要に応じて、その水和物を用いてもよいし、それらの2種以上を用いてもよい。本発明では、中でも、ケイ素アルコキシド化合物が好ましく、オルトケイ酸テトラエチル(Si(OC2H5)4)がより好ましい。 Examples of the silicon compound include silicon alkoxide compounds such as Si (OR) 4 (hereinafter, R represents an alkyl group having 1 to 4 carbon atoms), silicon chloride (SiCl 4 ), silicon bromide (SiBr 4 ), and the like. And silicon halide alkoxide compounds such as SiCl (OR) 3 , SiCl 2 (OR) 2 , and SiCl 3 (OR). Moreover, the hydrate may be used as needed and 2 or more types thereof may be used. In the present invention, among them, a silicon alkoxide compound is preferable, and tetraethyl orthosilicate (Si (OC 2 H 5 ) 4 ) is more preferable.
前記原料ルテニウム化合物としては、例えば、RuCl3、RuBr3の如きハロゲン化物、K3RuCl6、K2RuCl6の如きハロゲノ酸塩、K2RuO4の如きオキソ酸塩、Ru2OCl4、Ru2OCl5、Ru2OCl6の如きオキシハロゲン化物、K2[RuCl5(H2O)4]、[RuCl2(H2O)4]Cl、K2[Ru2OCl10]、Cs2[Ru2OCl4]の如きハロゲノ錯体、[Ru(NH3)5H2O]Cl2、[Ru(NH3)5Cl]Cl2、[Ru(NH3)6]Cl2、[Ru(NH3)6]Cl3、[Ru(NH3)6]Br3の如きアンミン錯体、Ru(CO)5、Ru3(CO)12の如きカルボニル錯体、[Ru3O(OCOCH3)6(H2O)3]OCOCH3、[Ru2(OCOR)4]Cl(R=炭素数1〜3のアルキル基)の如きカルボキシラト錯体、K2[RuCl5(NO)]、[Ru(NH3)5(NO)]Cl3、[Ru(OH)(NH3)4(NO)](NO3)2、[Ru(NO)](NO3)3の如きニトロシル錯体、ホスフィン錯体、アミン錯体、アセチルアセトナト錯体等が挙げられる。中でもハロゲン化物が好ましく用いられ、特に塩化物が好ましく用いられる。尚、原料ルテニウム化合物としては、必要に応じて、その水和物を使用してもよいし、また、それらの2種以上を使用してもよい。 Examples of the raw material ruthenium compound include a halide such as RuCl 3 and RuBr 3, a halogeno acid salt such as K 3 RuCl 6 and K 2 RuCl 6, an oxo acid salt such as K 2 RuO 4 , Ru 2 OCl 4 and Ru. Oxyhalides such as 2 OCl 5 and Ru 2 OCl 6 , K 2 [RuCl 5 (H 2 O) 4 ], [RuCl 2 (H 2 O) 4 ] Cl, K 2 [Ru 2 OCl 10 ], Cs 2 Halogeno complexes such as [Ru 2 OCl 4 ], [Ru (NH 3 ) 5 H 2 O] Cl 2 , [Ru (NH 3 ) 5 Cl] Cl 2 , [Ru (NH 3 ) 6 ] Cl 2 , [Ru Ammine complexes such as (NH 3 ) 6 ] Cl 3 , [Ru (NH 3 ) 6 ] Br 3 , carbonyl complexes such as Ru (CO) 5 and Ru 3 (CO) 12 , [Ru 3 O (OCOCH 3 ) 6 (H 2 O) 3] OCOCH 3, [Ru 2 (OCOR) 4 Cl (R = alkyl group having 1 to 3 carbon atoms) such as carboxylato complexes, K 2 [RuCl 5 (NO )], [Ru (NH 3) 5 (NO)] Cl 3, [Ru (OH) (NH 3 ) 4 (NO)] (NO 3 ) 2 , [Ru (NO)] (NO 3 ) 3 and the like, nitrosyl complexes, phosphine complexes, amine complexes, acetylacetonato complexes and the like. Of these, halides are preferably used, and chlorides are particularly preferably used. In addition, as a raw material ruthenium compound, the hydrate may be used as needed and those 2 or more types may be used.
前記改質用触媒の調製において、担体に、ケイ素化合物や原料ルテニウム化合物を担持させる方法としては、各化合物を適当な溶媒に溶解させてなる溶液を担体に含浸させる方法や、担体を該溶液に浸漬して、各化合物を吸着させる方法等が挙げられる。 In preparing the reforming catalyst, the carrier may be loaded with a silicon compound or a raw material ruthenium compound by impregnating the carrier with a solution obtained by dissolving each compound in an appropriate solvent, or by adding the carrier to the solution. Examples include a method of immersing and adsorbing each compound.
上記のごとく含浸又は浸漬する場合、その温度は、通常0〜100℃、好ましくは0〜50℃であり、その圧力は通常0.1〜1MPa、好ましくは大気圧である。また、かかる含浸又は浸漬は、空気雰囲気下や、窒素、ヘリウム、アルゴン、二酸化酸素の如き不活性ガス雰囲気下で行うことができ、この際、水蒸気を含んでいてもよい。取り扱いの観点から、上記不活性ガス雰囲気下で行うのが好ましい。 When impregnating or dipping as described above, the temperature is usually 0 to 100 ° C., preferably 0 to 50 ° C., and the pressure is usually 0.1 to 1 MPa, preferably atmospheric pressure. Further, such impregnation or immersion can be performed in an air atmosphere or an inert gas atmosphere such as nitrogen, helium, argon, oxygen dioxide, and may contain water vapor. From the viewpoint of handling, it is preferable to carry out in the inert gas atmosphere.
担体にケイ素化合物を担持させる場合、上記のごとく含浸又は浸漬した後、通常、乾燥し、その後、焼成する。かかる乾燥方法としては、従来公知の方法を採用することができ、その温度は、通常、室温から100℃程度であり、その圧力は、通常0.001〜1MPa、好ましくは大気圧である。かかる乾燥は、空気雰囲気下や、窒素、ヘリウム、アルゴン、二酸化酸素の如き不活性ガス雰囲気下で行うことができ、この際、水蒸気を含んでいてもよい。取り扱いの観点から、上記不活性ガス雰囲気下で行うのが好ましい。 When a silicon compound is supported on a carrier, it is usually dried and then fired after impregnation or immersion as described above. As the drying method, a conventionally known method can be adopted, and the temperature is usually from room temperature to about 100 ° C., and the pressure is usually from 0.001 to 1 MPa, preferably atmospheric pressure. Such drying can be performed in an air atmosphere or an inert gas atmosphere such as nitrogen, helium, argon, or oxygen dioxide, and may contain water vapor. From the viewpoint of handling, it is preferable to carry out in the inert gas atmosphere.
前記酸化性ガスとは、酸化性物質を含むガスであり、例えば酸素含有ガス等が挙げられ、その酸素濃度としては、通常、1〜30容量%程度である。この酸素源としては、通常、空気や純酸素が用いられ、必要に応じて不活性ガスや水蒸気で希釈される。酸化性ガスは、中でも、空気が好ましい。また、焼成温度は、通常、100〜1000℃、好ましくは250〜450℃である。 The oxidizing gas is a gas containing an oxidizing substance, and examples thereof include an oxygen-containing gas. The oxygen concentration is usually about 1 to 30% by volume. As the oxygen source, air or pure oxygen is usually used, and diluted with an inert gas or water vapor as necessary. Of these, air is preferable as the oxidizing gas. Moreover, a calcination temperature is 100-1000 degreeC normally, Preferably it is 250-450 degreeC.
前記還元性ガスとは、還元性物質を含むガスであり、例えば水素含有ガス、一酸化炭素含有ガス、炭化水素含有ガス等が挙げられる。その濃度としては、通常、1〜30容量%程度であり、例えば、不活性ガスや水蒸気で濃度調整される。還元性ガスは、中でも、水素含有ガス、一酸化炭素含有ガスが好ましい。また、焼成温度は、通常、100〜1000℃、好ましくは200〜500℃である。 The reducing gas is a gas containing a reducing substance, and examples thereof include a hydrogen-containing gas, a carbon monoxide-containing gas, and a hydrocarbon-containing gas. The concentration is usually about 1 to 30% by volume, and the concentration is adjusted with, for example, an inert gas or water vapor. Among them, the reducing gas is preferably a hydrogen-containing gas or a carbon monoxide-containing gas. Moreover, a calcination temperature is 100-1000 degreeC normally, Preferably it is 200-500 degreeC.
前記不活性ガスとしては、例えば窒素、二酸化炭素、ヘリウム、アルゴン等が挙げられ、必要に応じて水蒸気で希釈される。不活性ガスは、中でも、窒素、二酸化炭素が好ましい。また、前記(ii)において、不活性ガス雰囲気下に焼成を行う場合の焼成温度は、通常、100〜1000℃、好ましくは200〜600℃である。 Examples of the inert gas include nitrogen, carbon dioxide, helium, argon, and the like, and diluted with water vapor as necessary. Among these, nitrogen and carbon dioxide are preferable as the inert gas. In (ii) above, the firing temperature when firing in an inert gas atmosphere is usually 100 to 1000 ° C, preferably 200 to 600 ° C.
前記(ii)において、チタン化合物及びケイ素化合物を熱処理して、チタニアにシリカが担持されてなるチタニア担体を調製する方法としては、例えば、特開2004−210586号公報に記載の方法等に準ずることができる。その具体例としては、600℃以上でガス化したハロゲン化チタン及びハロゲン化ケイ素を、600℃以上の酸素の存在下又は酸素及び水蒸気の存在下で熱処理し、次いで、得られた粉体を300〜600℃で熱処理することで、シリカが担持された粉末状のチタニア担体を得る方法等が挙げられる。得られたチタニア担体を、混練、成形し、次いで焼成するのが好ましい。焼成したチタニア担体は、公知の方法に基づいて調製することができ、例えば、粉末状のチタニア担体を、有機バインダー等の成形助剤及び水と混練し、ヌードル状に押出成形した後、乾燥、破砕して成形体を得、次いで得られた成形体を空気等の酸化性ガス雰囲気下で焼成することで調製できる。また、上記ハロゲン化チタンとしては塩化チタン(TiCl4)が、上記ハロゲン化ケイ素としては塩化ケイ素(SiCl4)が、それぞれ好ましく採用される。 In the method (ii), a method for preparing a titania carrier in which silica is supported on titania by heat-treating a titanium compound and a silicon compound is, for example, according to the method described in JP-A-2004-210586. Can do. As a specific example thereof, titanium halide and silicon halide gasified at 600 ° C. or higher are heat-treated in the presence of oxygen at 600 ° C. or higher or in the presence of oxygen and water vapor, and then the obtained powder is 300 Examples include a method of obtaining a powdery titania carrier on which silica is supported by heat treatment at ˜600 ° C. The obtained titania carrier is preferably kneaded, molded, and then fired. The calcined titania carrier can be prepared based on a known method, for example, a powdery titania carrier is kneaded with a molding aid such as an organic binder and water, extruded into noodles, dried, It can be prepared by crushing to obtain a compact, and then firing the resulting compact in an oxidizing gas atmosphere such as air. Further, titanium chloride (TiCl 4 ) is preferably used as the titanium halide, and silicon chloride (SiCl 4 ) is preferably used as the silicon halide.
前記改質用触媒において、担体に対するシリカの担持量は、担体1モルに対し、通常、0.001〜0.3モルであり、好ましくは0.004〜0.03モルであり、この範囲になるようにケイ素化合物と担体の使用割合が適宜調整される。 In the reforming catalyst, the amount of silica supported on the support is usually 0.001 to 0.3 mol, preferably 0.004 to 0.03 mol, relative to 1 mol of the support. The usage ratio of the silicon compound and the carrier is adjusted as appropriate.
前記改質用触媒において、担体に対するルテニウム及びルテニウム化合物からなる群から選ばれる少なくとも一種の含有割合(ルテニウム成分/担体)は、重量比として、通常0.1/99.9〜20/80、好ましくは0.5/99.5〜15/85であり、この範囲になるように原料ルテニウム化合物と担体の使用割合が適宜調整される。ルテニウム成分があまり少ないと触媒活性が十分でないことがあり、あまり多いとコスト的に不利となる。 In the reforming catalyst, the content ratio (ruthenium component / support) selected from the group consisting of ruthenium and a ruthenium compound with respect to the support is usually 0.1 / 99.9 to 20/80, preferably as a weight ratio. Is 0.5 / 99.5 to 15/85, and the use ratio of the raw material ruthenium compound and the carrier is appropriately adjusted so as to be in this range. If the ruthenium component is too small, the catalytic activity may not be sufficient, and if it is too much, the cost is disadvantageous.
加えて、担持されているシリカ1モルに対し前記改質用触媒中のルテニウム及びルテニウム化合物からなる群から選ばれる少なくとも一種が0.1〜4モルとなるようにケイ素化合物と原料ルテニウム化合物の使用量を調整するのが好ましく、0.3〜2モルとなるように調整するのがより好ましい。シリカ1モルに対するルテニウム成分のモル数が高すぎると、得られる触媒の熱安定性が低くなることがあり、低すぎると、触媒活性が低くなることがある。 In addition, the silicon compound and the raw material ruthenium compound are used so that at least one selected from the group consisting of ruthenium and a ruthenium compound in the reforming catalyst is 0.1 to 4 mol per 1 mol of supported silica. The amount is preferably adjusted, and more preferably adjusted to 0.3 to 2 mol. If the number of moles of the ruthenium component relative to 1 mole of silica is too high, the thermal stability of the resulting catalyst may be low, and if it is too low, the catalyst activity may be low.
前記改質用触媒のBET比表面積は、通常1〜300m2/gであり、好ましくは5〜50m2/gである。前記BET比表面積が大きすぎると、得られる触媒における担体やルテニウム成分が焼結しやすくなり、熱安定性が低くなることがある。一方、前記BET比表面積が小さすぎると、得られる触媒におけるルテニウム成分が分散しにくくなり、触媒活性が低くなることがある。前記BET比表面積は、窒素吸着法を原理とする比表面積測定装置を用いて測定して得られる値である。 The BET specific surface area of the reforming catalyst is usually 1 to 300 m 2 / g, preferably 5 to 50 m 2 / g. If the BET specific surface area is too large, the carrier and ruthenium component in the resulting catalyst are likely to sinter and thermal stability may be lowered. On the other hand, if the BET specific surface area is too small, the ruthenium component in the resulting catalyst is difficult to disperse and the catalyst activity may be lowered. The BET specific surface area is a value obtained by measurement using a specific surface area measuring device based on a nitrogen adsorption method.
前記改質用触媒の細孔容積としては、通常、0.05〜1.5ml/g、好ましくは0.1〜1.0ml/gである。細孔容積が小さすぎると、細孔径が小さくなりすぎるため、活性が低くなることがある。また、細孔容積が大きすぎると、触媒強度が低下して安定的な合成ガスの製造を妨げることがある。前記細孔容積は、Hg圧入法で測定して得られる値である。 The pore volume of the reforming catalyst is usually 0.05 to 1.5 ml / g, preferably 0.1 to 1.0 ml / g. If the pore volume is too small, the pore diameter is too small, and the activity may be low. On the other hand, if the pore volume is too large, the strength of the catalyst may be reduced, which may hinder stable synthesis gas production. The pore volume is a value obtained by measurement by the Hg intrusion method.
触媒の形状は、球形粒状、円柱形ペレット状、押出形状、リング形状、ハニカム状あるいは成型後に粉砕分級した適度の大きさの顆粒状等で用いられる。この際、触媒の直径としては5mm以下が好ましい。触媒の直径が大きすぎると、炭化水素の転化率が低くなることがある。触媒の直径の下限は特に制限はないが、過度に小さくなると、触媒層での圧力損失が大きくなるため、通常は0.5mm以上のものが用いられる。なお、ここでいう触媒の直径とは、球形粒状では球の直径、円柱形ペレット状では円形断面の直径、その他の形状では断面の最大直径を意味する。 The catalyst may be used in the form of a spherical particle, a cylindrical pellet, an extruded shape, a ring shape, a honeycomb shape, or an appropriately sized granule that has been pulverized and classified after molding. At this time, the diameter of the catalyst is preferably 5 mm or less. If the catalyst diameter is too large, the conversion of hydrocarbons may be low. The lower limit of the diameter of the catalyst is not particularly limited, but if it becomes excessively small, pressure loss in the catalyst layer increases, and therefore, a catalyst having a diameter of 0.5 mm or more is usually used. The diameter of the catalyst here means the diameter of a sphere in the case of spherical particles, the diameter of a circular cross section in the case of a cylindrical pellet, and the maximum diameter of the cross section in other shapes.
なお、改質用触媒を使用する際、チタニア、アルミナ、ジルコニア、シリカ等で希釈して使用することもできる。 When the reforming catalyst is used, it can be diluted with titania, alumina, zirconia, silica or the like.
かくして製造される改質用触媒の存在下で炭化水素を二酸化炭素で改質させることにより、水素及び一酸化炭素を含む合成ガスを効率的に製造することができる。改質用触媒がルテニウム成分と共にシリカとが担体に担持されてなることにより、長時間改質反応に用いられる等の熱負荷が掛かることによる担体や担体に担持されたルテニウム成分の焼結(シンタリング)が抑制され、かかる焼結により生じる触媒活性の低下を抑えることができる。 By reforming the hydrocarbon with carbon dioxide in the presence of the reforming catalyst thus produced, a synthesis gas containing hydrogen and carbon monoxide can be efficiently produced. When the reforming catalyst is supported on the support together with the ruthenium component and silica, the support or the ruthenium component supported on the support is sintered (sintered) by applying a heat load such as being used for a long-time reforming reaction. Ring) is suppressed, and a decrease in catalytic activity caused by such sintering can be suppressed.
炭化水素としては、例えば、メタン、エタン、エチレン、プロパン、プロピレン、ブタン、ブテン、イソブタン、イソブチレン、ペンタン、ペンテン、イソペンタン、イソペンテン等の炭素数1〜5の炭化水素が用いられ、それらの2種以上を使用してもよいが、メタン及び/又はエタンを主成分とする炭化水素が好ましく用いられる。メタン及び/又はエタンを主成分とする炭化水素中のメタン及び/又はエタンの合計含有量は、通常50体積%を超える量であり、好ましくは90体積%以上であり、さらに好ましくは100体積%である。本発明においては、二酸化炭素が含まれる天然ガスも反応原料として用いることができる。 Examples of the hydrocarbon include hydrocarbons having 1 to 5 carbon atoms such as methane, ethane, ethylene, propane, propylene, butane, butene, isobutane, isobutylene, pentane, pentene, isopentane, isopentene, and the like. Although the above may be used, hydrocarbons mainly composed of methane and / or ethane are preferably used. The total content of methane and / or ethane in the hydrocarbon mainly composed of methane and / or ethane is usually an amount exceeding 50% by volume, preferably 90% by volume or more, more preferably 100% by volume. It is. In the present invention, natural gas containing carbon dioxide can also be used as a reaction raw material.
炭化水素は、窒素ガスやアルゴンガスといった改質反応に不活性なガスで希釈して用いてもよく、その場合、希釈された炭化水素ガスにおける炭化水素の濃度は、通常1体積%以上、好ましくは2体積%以上である。 The hydrocarbon may be diluted with a gas inert to the reforming reaction such as nitrogen gas or argon gas. In that case, the concentration of hydrocarbon in the diluted hydrocarbon gas is usually 1% by volume or more, preferably Is 2% by volume or more.
原料の炭化水素に対する二酸化炭素の使用割合は、原料中の炭素1モル当り、二酸化炭素0.1〜20モル、好ましくは0.5〜10モルである。二酸化炭素の量が過少であると、改質反応が進行しにくくなり、効率的に合成ガスを製造できないことがある。 The ratio of carbon dioxide to the raw material hydrocarbon is 0.1 to 20 moles, preferably 0.5 to 10 moles of carbon dioxide per mole of carbon in the raw material. If the amount of carbon dioxide is too small, the reforming reaction will hardly proceed, and synthesis gas may not be produced efficiently.
改質における反応温度は、通常300〜1200℃、好ましくは350〜700℃、より好ましくは450〜650℃である。反応温度が低すぎると活性が低くなると同時に、平衡転化率も低下することがある。一方、高すぎると触媒の活性劣化を引き起こすことがある。 The reaction temperature in the reforming is usually 300 to 1200 ° C, preferably 350 to 700 ° C, more preferably 450 to 650 ° C. If the reaction temperature is too low, the activity may be lowered and the equilibrium conversion rate may be lowered. On the other hand, if it is too high, the activity of the catalyst may be deteriorated.
改質における反応圧力は、通常0.01〜5MPa、好ましくは0.01〜2MPaである。反応圧力が0.01MPaより低いと生産性が低くなることがあり、5MPaより高いと平衡的に不利となることがある。 The reaction pressure in the reforming is usually 0.01 to 5 MPa, preferably 0.01 to 2 MPa. When the reaction pressure is lower than 0.01 MPa, productivity may be lowered, and when it is higher than 5 MPa, it may be disadvantageous in equilibrium.
改質における反応方式としては、固定床方式、流動床方式、移動床方式等の各種の方式が採用可能であり、固定床方式が好ましい。また、反応を固定床方式で行う場合、炭化水素及び二酸化炭素の供給速度は、触媒1Lあたりのガス供給速度(L/h;0℃、1気圧換算)、すなわちGHSV(Gas Hourly Space Velocity)で表して、10〜20000h−1、好ましくは1000〜10000h−1である。 As a reaction method in reforming, various methods such as a fixed bed method, a fluidized bed method, and a moving bed method can be adopted, and a fixed bed method is preferable. When the reaction is carried out in a fixed bed system, the supply rate of hydrocarbons and carbon dioxide is the gas supply rate per liter of catalyst (L / h; 0 ° C., converted to 1 atm), that is, GHSV (Gas Hourly Space Velocity). represent, 10~20000h -1, preferably 1000~10000h -1.
以上、本発明にかかる好ましい実施形態について示したが、本発明は上述した実施形態
に限定されるものではなく、本発明の要旨を逸脱しない範囲で変更や改良したものにも適
用できることは言うまでもない。
As mentioned above, although preferred embodiment concerning this invention was shown, it cannot be overemphasized that this invention is applicable to what was changed and improved in the range which is not limited to embodiment mentioned above and does not deviate from the summary of this invention. .
以下、実施例を挙げて本発明を詳細に説明するが、本発明は以下の実施例のみに限定されるものではない。なお、以下の実施例中、含有量ないし使用量を表す部は、特記ない限り、重量基準である。また、以下の実施例中、ガスの供給速度である(ml/分)は、特記ない限り、0℃、1気圧の換算値である。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to a following example. In the following examples, the part representing the content or amount used is based on weight unless otherwise specified. In the following examples, the gas supply rate (ml / min) is a converted value of 0 ° C. and 1 atm unless otherwise specified.
参考例1
(担体の調製)
まず、チタニア粉末〔昭和タイタニウム(株)製の「F−1R」、ルチル型チタニア比率93%〕100部と、有機バインダー2部〔ユケン工業(株)製の「YB−152A」〕とを混合し、次いで純水29部と、チタニアゾル〔堺化学(株)製の「CSB」、チタニア含有量40重量%〕12.5部とを加えて混練し、混合物を得た。
Reference example 1
(Preparation of carrier)
First, 100 parts of titania powder [“F-1R” manufactured by Showa Titanium Co., Ltd., rutile-type titania ratio 93%] and 2 parts of organic binder [“YB-152A” manufactured by Yuken Industry Co., Ltd.] were mixed. Next, 29 parts of pure water and 12.5 parts of titania sol [“CSB” manufactured by Sakai Chemical Co., Ltd., titania content 40 wt%] were added and kneaded to obtain a mixture.
この混合物を直径3.0mmφのヌードル状に押出し、60℃で2時間乾燥した後、回転式ノンバブリングニーダー〔(株)日本精機製作所製の「NBK−1」〕を破砕機として使用し、長さ3〜5mm程度に破砕して成形体を得た。得られた成形体を、空気中で室温から600℃まで1.7時間かけて昇温した後、同温度で3時間保持して焼成した。 This mixture was extruded into a noodle shape having a diameter of 3.0 mmφ, dried at 60 ° C. for 2 hours, and then a rotary non-bubbling kneader (“NBK-1” manufactured by Nippon Seiki Seisakusho Co., Ltd.) was used as a crusher. The compact was obtained by crushing to a thickness of about 3 to 5 mm. The obtained molded body was heated in air from room temperature to 600 ° C. over 1.7 hours and then calcined by holding at the same temperature for 3 hours.
(担体へのケイ素化合物の含浸)
得られた焼成物の内100.0gに、オルトケイ酸テトラエチル〔和光純薬工業(株)製のSi(OC2H5)4〕3.55gをエタノール14.6gに溶解して調製した溶液を含浸させた。
(Impregnation of silicon compound into support)
A solution prepared by dissolving 3.55 g of tetraethyl orthosilicate [Si (OC 2 H 5 ) 4 ] manufactured by Wako Pure Chemical Industries, Ltd. in 14.6 g of ethanol in 100.0 g of the obtained fired product. Impregnated.
前記(担体へのケイ素化合物の含浸)と同様の操作を合計8回繰り返し、合計934gの白色固体を得た。この白色固体を、空気雰囲気下、20〜30℃で20時間静置した。得られた固体808gを、空気雰囲気下、室温から300℃まで0.8時間かけて昇温した後、同温度で2時間保持して焼成し、シリカの含有量が1.0重量%である白色のチタニア担体を得た。この担体は、該担体総量に対して99%の割合でチタニアを含有している。また、該担体に含有される前記チタニアにおいて、ルチル型チタニアの占める割合は90%以上である。 The same operation as the above (impregnation of the silicon compound into the carrier) was repeated a total of 8 times to obtain a total of 934 g of a white solid. This white solid was allowed to stand at 20 to 30 ° C. for 20 hours in an air atmosphere. 808 g of the obtained solid was heated from room temperature to 300 ° C. over 0.8 hours in an air atmosphere and then calcined by holding at the same temperature for 2 hours. The silica content was 1.0% by weight. A white titania carrier was obtained. This carrier contains titania in a ratio of 99% with respect to the total amount of the carrier. Further, in the titania contained in the carrier, the ratio of the rutile type titania is 90% or more.
(担持酸化ルテニウムの製造)
上記で得られたチタニア担体100.0gに、塩化ルテニウム水和物〔NEケムキャット(株)製のRuCl3・nH2O、Ru含有量40.0重量%〕2.43gを純水22.1gに溶解して調製した水溶液を含浸させ、空気雰囲気下、20〜33℃で15時間以上静置して風乾した。得られた固体103.3gを、空気流通下、室温から250℃まで1.3時間かけて昇温した後、同温度で2時間保持して焼成した。これにより、酸化ルテニウムの含有量が1.25重量%である青灰色の固体、すなわち担体に酸化ルテニウム及びシリカが担持されてなる担持酸化ルテニウム100.7gを得た。
(Production of supported ruthenium oxide)
To 100.0 g of the titania carrier obtained above, 2.43 g of ruthenium chloride hydrate (RuCl 3 · nH 2 O manufactured by NE Chemcat Co., Ltd., Ru content 40.0 wt%) was added to 22.1 g of pure water. It was impregnated with an aqueous solution prepared by dissolving in, and allowed to stand at 20 to 33 ° C. in an air atmosphere for 15 hours or more and air-dried. The obtained solid (103.3 g) was heated from room temperature to 250 ° C. over 1.3 hours under air flow, and then held at the same temperature for 2 hours and calcined. As a result, 100.7 g of supported ruthenium oxide having a ruthenium oxide content of 1.25% by weight, that is, a supported ruthenium oxide in which ruthenium oxide and silica are supported on a support was obtained.
そして、前記(担持酸化ルテニウムの製造)と同様の操作を合計8回繰り返し、合計806gの担持酸化ルテニウムを得た。 Then, the same operation as the above (manufacture of supported ruthenium oxide) was repeated a total of 8 times to obtain a total of 806 g of supported ruthenium oxide.
実施例1
<触媒充填>
外径3mmの温度計鞘管が設けられた内径14mmのSUS製の反応管の下部に石英ウールを仕切り材として充填し、次いで2mmφのα−アルミナボール〔ニッカトー(株)製の「SSA995」、BET比表面積0.1m2/g未満〕20gを反応管上部より充填した。さらに上記で得られた担持酸化ルテニウム1g(0.74ml)を反応管上部より充填した。次いで2mmφのα−アルミナボール〔ニッカトー(株)製の「SSA995」、BET比表面積0.1m2/g未満〕20gを反応管上部より充填した。
Example 1
<Catalyst filling>
The lower part of a 14 mm inner diameter SUS reaction tube provided with a thermometer sheath tube with an outer diameter of 3 mm was filled with quartz wool as a partition material, and then a 2 mmφ α-alumina ball [“SSA995” manufactured by Nikkato Corporation, BET specific surface area of less than 0.1 m 2 / g] was charged from the top of the reaction tube. Further, 1 g (0.74 ml) of the supported ruthenium oxide obtained above was charged from the upper part of the reaction tube. Next, 20 g of α-alumina balls having a diameter of 2 mm (“SSA995” manufactured by Nikkato Co., Ltd., BET specific surface area of less than 0.1 m 2 / g) were charged from the upper part of the reaction tube.
<合成ガスの製造>
触媒充填済みの反応管の入口から窒素ガスを143ml/分の速度で供給しながら、反応管を電気炉で加熱し、触媒層の温度を600℃にした。そして、窒素ガスの供給を停止し、反応管入口から二酸化炭素ガスを25ml/分(0.067mol/h)、及び窒素で3.5体積%に希釈されたメタンガスを143ml/分(メタンとして0.013mol/h)供給し、反応圧力0.1MPaで反応を開始した。
<Manufacture of synthesis gas>
While supplying nitrogen gas at a rate of 143 ml / min from the inlet of the reaction tube filled with the catalyst, the reaction tube was heated in an electric furnace to bring the temperature of the catalyst layer to 600 ° C. Then, the supply of nitrogen gas was stopped, carbon dioxide gas from the inlet of the reaction tube was 25 ml / min (0.067 mol / h), and methane gas diluted to 3.5% by volume with nitrogen was 143 ml / min (0 as methane). .013 mol / h), and the reaction was started at a reaction pressure of 0.1 MPa.
反応開始後、触媒層の温度は吸熱により581〜585℃に維持された。反応開始から5分、30分、60分経過した時点で、反応管出口ガスをガスシリンジにて採取し、TCD検出器を有するガスクロマトグラフィーにて分析し、反応管出口ガスに含まれる各成分を定量した。反応管出口ガス中の成分は、一酸化炭素、水素、メタン、二酸化炭素及び窒素が確認された。メタンの供給流量(mol/h)と反応管出口ガス中のメタン流量(mol/h)とから、下式(I)によりメタンの転化率(%)を算出した。また、反応管出口ガス中の水素の生成速度(mol/h)と一酸化炭素の生成速度(mol/h)とから、下式(II)によりH2/CO比(モル比)を算出した。結果を表1に示す。 After the start of the reaction, the temperature of the catalyst layer was maintained at 581 to 585 ° C. by endotherm. When 5 minutes, 30 minutes, and 60 minutes have elapsed from the start of the reaction, the reaction tube outlet gas is collected with a gas syringe, analyzed by gas chromatography having a TCD detector, and each component contained in the reaction tube outlet gas Was quantified. The components in the reaction tube outlet gas were confirmed to be carbon monoxide, hydrogen, methane, carbon dioxide and nitrogen. From the methane supply flow rate (mol / h) and the methane flow rate (mol / h) in the reaction tube outlet gas, the conversion rate (%) of methane was calculated by the following equation (I). Further, the H 2 / CO ratio (molar ratio) was calculated from the following formula (II) from the hydrogen production rate (mol / h) and the carbon monoxide production rate (mol / h) in the reaction tube outlet gas. . The results are shown in Table 1.
メタンの転化率(%)=〔(a−b)/a〕×100 (I) Methane conversion rate (%) = [(ab) / a] × 100 (I)
a:メタンの供給流量(mol/h)
b:反応管出口ガス中のメタン流量(mol/h)
a: Supply flow rate of methane (mol / h)
b: Methane flow rate in reaction tube outlet gas (mol / h)
H2/CO比(モル比)=c/d (II) H 2 / CO ratio (molar ratio) = c / d (II)
c:水素の生成速度(mol/h)
d:一酸化炭素の生成速度(mol/h)
c: Hydrogen production rate (mol / h)
d: Carbon monoxide production rate (mol / h)
実施例2
<合成ガスの製造>において、触媒充填済みの反応管の入口から窒素ガスを143ml/分の速度で供給しながら、反応管を電気炉で加熱し、触媒層の温度を410℃にした以外は、実施例1と同様の操作で合成ガスの製造を行った。反応開始後、触媒層の温度は吸熱により404℃に維持された。メタンの転化率(%)及びH2/CO比(モル比)を算出した結果を表2に示す。
Example 2
In <Production of synthesis gas>, the reaction tube was heated in an electric furnace while supplying nitrogen gas at a rate of 143 ml / min from the inlet of the catalyst-filled reaction tube, and the temperature of the catalyst layer was 410 ° C. The synthesis gas was produced in the same manner as in Example 1. After the start of the reaction, the temperature of the catalyst layer was maintained at 404 ° C. by endotherm. Table 2 shows the results of calculating the conversion rate (%) of methane and the H 2 / CO ratio (molar ratio).
実施例3
<合成ガスの製造>において、触媒充填済みの反応管の入口から窒素ガスを143ml/分の速度で供給しながら、反応管を電気炉で加熱し、触媒層の温度を510℃にした以外は、実施例1と同様の操作で反応を行った。反応開始後、触媒層の温度は吸熱により502〜503℃に維持された。メタンの転化率(%)及びH2/CO比(モル比)を算出した結果を表3に示す。
Example 3
In <Production of synthesis gas>, except that nitrogen gas was supplied from the inlet of the reaction tube filled with catalyst at a rate of 143 ml / min, the reaction tube was heated in an electric furnace, and the temperature of the catalyst layer was changed to 510 ° C. The reaction was performed in the same manner as in Example 1. After the start of the reaction, the temperature of the catalyst layer was maintained at 502 to 503 ° C. by endotherm. Table 3 shows the results of calculating the conversion rate (%) of methane and the H 2 / CO ratio (molar ratio).
実施例4
<触媒充填>
実施例1と同様の操作で触媒充填を行った。
<合成ガスの製造>
触媒充填済みの反応管の入口から窒素ガスを100ml/分の速度で供給しながら、反応管を電気炉で加熱し、触媒層の温度を620℃にした。そして、窒素ガスの供給を停止し、反応管入口から二酸化炭素ガスを90ml/分(0.24mol/h)、及びエタンガスを10ml/分(エタンとして0.027mol/h)供給し、反応圧力0.1MPaで反応を開始した。
Example 4
<Catalyst filling>
Catalyst filling was carried out in the same manner as in Example 1.
<Manufacture of synthesis gas>
While supplying nitrogen gas at a rate of 100 ml / min from the inlet of the reaction tube filled with the catalyst, the reaction tube was heated in an electric furnace to bring the temperature of the catalyst layer to 620 ° C. Then, the supply of nitrogen gas was stopped, carbon dioxide gas was supplied from the inlet of the reaction tube at 90 ml / min (0.24 mol / h), and ethane gas was supplied at 10 ml / min (ethane as 0.027 mol / h), and the reaction pressure was 0 The reaction was started at 1 MPa.
反応開始後、触媒層の温度は吸熱により600℃に維持された。反応開始から15分、131分経過した時点で、反応管出口ガスをガスシリンジにて採取し、TCD検出器を有するガスクロマトグラフィーにて分析し、反応管出口ガスに含まれる各成分を定量した。反応管出口ガス中の成分は、一酸化炭素、水素、メタン及び二酸化炭素が確認された。反応管出口ガス組成を表4に示す。エタンの供給流量(mol/h)と反応管出口ガス中のエタン流量(mol/h)とから、下式(III)によりエタンの転化率(%)を算出した。また、反応管出口ガス中の水素の生成速度(mol/h)と一酸化炭素の生成速度(mol/h)とから、上記式(II)によりH2/CO比(モル比)を算出した。結果を表4に示す。 After the start of the reaction, the temperature of the catalyst layer was maintained at 600 ° C. by endotherm. When 15 minutes and 131 minutes had elapsed from the start of the reaction, the reaction tube outlet gas was collected with a gas syringe and analyzed by gas chromatography having a TCD detector to quantify each component contained in the reaction tube outlet gas. . The components in the reaction tube outlet gas were confirmed to be carbon monoxide, hydrogen, methane and carbon dioxide. The reaction tube outlet gas composition is shown in Table 4. From the ethane supply flow rate (mol / h) and the ethane flow rate (mol / h) in the reaction tube outlet gas, the conversion rate (%) of ethane was calculated by the following formula (III). Further, the H 2 / CO ratio (molar ratio) was calculated from the above formula (II) from the hydrogen production rate (mol / h) and the carbon monoxide production rate (mol / h) in the reaction tube outlet gas. . The results are shown in Table 4.
エタンの転化率(%)=〔(e−f)/e〕×100 (III) Conversion of ethane (%) = [(e−f) / e] × 100 (III)
e:エタンの供給流量(mol/h)
f:反応管出口ガス中のエタン流量(mol/h)
e: Supply flow rate of ethane (mol / h)
f: Flow rate of ethane in the reaction tube outlet gas (mol / h)
実施例5
実施例4に引き続いて反応を行った。実施例4における反応開始から140分経過した時点で、電気炉の温度を調整して、30分かけて触媒層の温度を500℃に下げ、さらに25分経過した時点で、反応管出口ガスをガスシリンジにて採取し、TCD検出器を有するガスクロマトグラフィーにて分析し、反応管出口ガスに含まれる各成分を定量した。反応管出口ガス中の成分は、一酸化炭素、水素、メタン及び二酸化炭素が確認された。反応管出口ガス組成とともに、エタンの転化率(%)及びH2/CO比(モル比)を実施例4と同様にして算出した結果を表5に示す。
Example 5
Following Example 4, the reaction was carried out. When 140 minutes passed from the start of the reaction in Example 4, the temperature of the electric furnace was adjusted, the temperature of the catalyst layer was lowered to 500 ° C. over 30 minutes, and when 25 minutes passed, the reaction tube outlet gas was changed to Each component contained in the reaction tube outlet gas was quantified by collecting with a gas syringe and analyzing with a gas chromatography having a TCD detector. The components in the reaction tube outlet gas were confirmed to be carbon monoxide, hydrogen, methane and carbon dioxide. Table 5 shows the results of calculating the ethane conversion rate (%) and H 2 / CO ratio (molar ratio) in the same manner as in Example 4 together with the reaction tube outlet gas composition.
実施例6
実施例5に引き続いて反応を行った。実施例4における反応開始から215分経過した時点で、電気炉の温度を調整して、30分かけて触媒層の温度を400℃に下げ、さらに25分経過した時点で、反応管出口ガスをガスシリンジにて採取し、TCD検出器を有するガスクロマトグラフィーにて分析し、反応管出口ガスに含まれる各成分を定量した。反応管出口ガス中の成分は、一酸化炭素、水素、メタン、二酸化炭素及びエタンが確認された。反応管出口ガス組成とともに、エタンの転化率(%)及びH2/CO比(モル比)を実施例4と同様にして算出した結果を表5に示す。
Example 6
Subsequent to Example 5, the reaction was performed. When 215 minutes have passed since the start of the reaction in Example 4, the temperature of the electric furnace was adjusted, the temperature of the catalyst layer was lowered to 400 ° C. over 30 minutes, and when 25 minutes passed, the reaction tube outlet gas was changed to Each component contained in the reaction tube outlet gas was quantified by collecting with a gas syringe and analyzing with a gas chromatography having a TCD detector. The components in the reaction tube outlet gas were confirmed to be carbon monoxide, hydrogen, methane, carbon dioxide and ethane. Table 5 shows the results of calculating the ethane conversion rate (%) and H 2 / CO ratio (molar ratio) in the same manner as in Example 4 together with the reaction tube outlet gas composition.
実施例7
実施例6に引き続いて反応を行った。実施例4における反応開始から270分経過した時点で、電気炉の温度を調整して、10分かけて触媒層の温度を600℃に上げ、さらに5分経過した時点で、反応管出口ガスをガスシリンジにて採取し、TCD検出器を有するガスクロマトグラフィーにて分析し、反応管出口ガスに含まれる各成分を定量した。反応管出口ガス中の成分は、一酸化炭素、水素、メタン及び二酸化炭素が確認された。反応管出口ガス組成とともに、エタンの転化率(%)及びH2/CO比(モル比)を実施例4と同様にして算出した結果を表6に示す。
Example 7
The reaction was carried out following Example 6. When 270 minutes passed from the start of the reaction in Example 4, the temperature of the electric furnace was adjusted, the temperature of the catalyst layer was raised to 600 ° C. over 10 minutes, and when 5 minutes passed, the reaction tube outlet gas was changed to Each component contained in the reaction tube outlet gas was quantified by collecting with a gas syringe and analyzing with a gas chromatography having a TCD detector. The components in the reaction tube outlet gas were confirmed to be carbon monoxide, hydrogen, methane and carbon dioxide. Table 6 shows the results of calculating the ethane conversion rate (%) and the H 2 / CO ratio (molar ratio) in the same manner as in Example 4 together with the reaction tube outlet gas composition.
実施例8
実施例7に引き続いて反応を行った。実施例4における反応開始から335分経過した時点で、反応圧力を0.5MPaに調整して、さらに16分経過した時点で、反応管出口ガスをガスシリンジにて採取し、TCD検出器を有するガスクロマトグラフィーにて分析し、反応管出口ガスに含まれる各成分を定量した。反応管出口ガス中の成分は、一酸化炭素、水素、メタン及び二酸化炭素が確認された。反応管出口ガス組成とともに、エタンの転化率(%)及びH2/CO比(モル比)を実施例4と同様にして算出した結果を表6に示す。
Example 8
The reaction was carried out following Example 7. When 335 minutes have elapsed since the start of the reaction in Example 4, the reaction pressure was adjusted to 0.5 MPa, and when 16 minutes had elapsed, the reaction tube outlet gas was collected with a gas syringe and had a TCD detector. Each component contained in the reaction tube outlet gas was quantitatively analyzed by gas chromatography. The components in the reaction tube outlet gas were confirmed to be carbon monoxide, hydrogen, methane and carbon dioxide. Table 6 shows the results of calculating the ethane conversion rate (%) and the H 2 / CO ratio (molar ratio) in the same manner as in Example 4 together with the reaction tube outlet gas composition.
実施例9
実施例8に引き続いて反応を行った。実施例4における反応開始から360分経過した時点で、反応圧力を0.25MPaに調整して、さらに18分経過した時点で、反応管出口ガスをガスシリンジにて採取し、TCD検出器を有するガスクロマトグラフィーにて分析し、反応管出口ガスに含まれる各成分を定量した。反応管出口ガス中の成分は、一酸化炭素、水素、メタン及び二酸化炭素が確認された。反応管出口ガス組成とともに、エタンの転化率(%)及びH2/CO比(モル比)を実施例4と同様にして算出した結果を表6に示す。
Example 9
Subsequent to Example 8, the reaction was performed. When 360 minutes have elapsed since the start of the reaction in Example 4, the reaction pressure was adjusted to 0.25 MPa, and when 18 minutes had elapsed, the reaction tube outlet gas was sampled with a gas syringe and had a TCD detector. Each component contained in the reaction tube outlet gas was quantitatively analyzed by gas chromatography. The components in the reaction tube outlet gas were confirmed to be carbon monoxide, hydrogen, methane and carbon dioxide. Table 6 shows the results of calculating the ethane conversion rate (%) and the H 2 / CO ratio (molar ratio) in the same manner as in Example 4 together with the reaction tube outlet gas composition.
実施例10
実施例9に引き続いて反応を行った。実施例4における反応開始から380分経過した時点で、電気炉の温度を調整して、20分かけて触媒層の温度を500℃に下げ、二酸化炭素ガスの供給量を30ml/分(0.08mol/h)に調整して、さらに60分経過した時点で、反応管出口ガスをガスシリンジにて採取し、TCD検出器を有するガスクロマトグラフィーにて分析し、反応管出口ガスに含まれる各成分を定量した。反応管出口ガス中の成分は、一酸化炭素、水素、メタン、二酸化炭素及びエタンが確認された。反応管出口ガス組成とともに、エタンの転化率(%)及びH2/CO比(モル比)を実施例4と同様にして算出した結果を表7に示す。
Example 10
Following Example 9, the reaction was carried out. When 380 minutes passed from the start of the reaction in Example 4, the temperature of the electric furnace was adjusted, the temperature of the catalyst layer was lowered to 500 ° C. over 20 minutes, and the supply amount of carbon dioxide gas was 30 ml / minute (0. The reaction tube outlet gas was sampled with a gas syringe at the time when another 60 minutes had passed, and analyzed by gas chromatography having a TCD detector, and each contained in the reaction tube outlet gas. Ingredients were quantified. The components in the reaction tube outlet gas were confirmed to be carbon monoxide, hydrogen, methane, carbon dioxide and ethane. Table 7 shows the results of calculating the ethane conversion rate (%) and the H 2 / CO ratio (molar ratio) in the same manner as in Example 4 together with the reaction tube outlet gas composition.
実施例11
実施例10に引き続いて反応を行った。実施例4における反応開始から460分経過した時点で、二酸化炭素ガスの供給量を10ml/分(0.03mol/h)に調整して、さらに46分経過した時点で、反応管出口ガスをガスシリンジにて採取し、TCD検出器を有するガスクロマトグラフィーにて分析し、反応管出口ガスに含まれる各成分を定量した。反応管出口ガス中の成分は、一酸化炭素、水素、メタン、二酸化炭素及びエタンが確認された。反応管出口ガス組成とともに、エタンの転化率(%)及びH2/CO比(モル比)を実施例4と同様にして算出した結果を表7に示す。
Example 11
Subsequent to Example 10, the reaction was performed. When 460 minutes have elapsed from the start of the reaction in Example 4, the supply amount of carbon dioxide gas was adjusted to 10 ml / min (0.03 mol / h), and when 46 minutes had elapsed, the reaction tube outlet gas was gas. It collected with the syringe and analyzed with the gas chromatography which has a TCD detector, and quantified each component contained in reaction tube exit gas. The components in the reaction tube outlet gas were confirmed to be carbon monoxide, hydrogen, methane, carbon dioxide and ethane. Table 7 shows the results of calculating the ethane conversion rate (%) and the H 2 / CO ratio (molar ratio) in the same manner as in Example 4 together with the reaction tube outlet gas composition.
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