JP4339134B2 - Desulfurizing agent molded body of gaseous hydrocarbon compound and desulfurization method - Google Patents
Desulfurizing agent molded body of gaseous hydrocarbon compound and desulfurization method Download PDFInfo
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- JP4339134B2 JP4339134B2 JP2004003961A JP2004003961A JP4339134B2 JP 4339134 B2 JP4339134 B2 JP 4339134B2 JP 2004003961 A JP2004003961 A JP 2004003961A JP 2004003961 A JP2004003961 A JP 2004003961A JP 4339134 B2 JP4339134 B2 JP 4339134B2
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- molded body
- desulfurization
- agent molded
- gaseous hydrocarbon
- hydrocarbon compound
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- 238000006477 desulfuration reaction Methods 0.000 title claims description 50
- 230000023556 desulfurization Effects 0.000 title claims description 50
- 239000003795 chemical substances by application Substances 0.000 title claims description 45
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 28
- 230000003009 desulfurizing effect Effects 0.000 title claims description 19
- 239000003054 catalyst Substances 0.000 claims description 38
- 239000000446 fuel Substances 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 150000003464 sulfur compounds Chemical class 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 19
- 239000010457 zeolite Substances 0.000 claims description 19
- 238000002407 reforming Methods 0.000 claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 15
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000000629 steam reforming Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000002453 autothermal reforming Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003345 natural gas Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000002303 thermal reforming Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006057 reforming reaction Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000002828 fuel tank Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- XYWDPYKBIRQXQS-UHFFFAOYSA-N di-isopropyl sulphide Natural products CC(C)SC(C)C XYWDPYKBIRQXQS-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WXEHBUMAEPOYKP-UHFFFAOYSA-N methylsulfanylethane Chemical compound CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 description 1
- -1 naphtha Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Hydrogen, Water And Hydrids (AREA)
- Fuel Cell (AREA)
- Gas Separation By Absorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明は、ガス状炭化水素化合物の脱硫剤成形体及び脱硫方法、並びに該脱硫剤成形体を用いて脱硫処理したガス状炭化水素化合物から水素を効果的に製造する方法、更にその水素を用いる燃料電池システムに関する。 The present invention relates to a desulfurizing agent molded body and a desulfurization method for a gaseous hydrocarbon compound, a method for effectively producing hydrogen from a gaseous hydrocarbon compound desulfurized using the desulfurizing agent molded body, and further using the hydrogen. The present invention relates to a fuel cell system.
近年、環境問題から新エネルギー技術が脚光を浴びており、この新エネルギー技術の一つとして燃料電池が注目されている。この燃料電池は、水素と酸素を電気化学的に反応させることにより、化学エネルギーを電気エネルギーに変換するものであって、エネルギーの利用効率が高いという特徴を有しており、民生用、産業用あるいは自動車用などとして、実用化研究が積極的になされている。
この燃料電池には、使用する電解質の種類に応じて、リン酸型、溶融炭酸塩型、固体酸化物型、固体高分子型などのタイプが知られている。一方、水素源としては、メタノール、メタンを主体とする液化天然ガス、この天然ガスを主成分とする都市ガス、天然ガスを原料とする合成液体燃料、さらにはＬＰＧ、ジメチルエーテル、ナフサ、灯油などの石油系炭化水素の使用が研究されている。
In recent years, new energy technology has attracted attention due to environmental problems, and fuel cells are attracting attention as one of the new energy technologies. This fuel cell converts chemical energy into electrical energy by electrochemically reacting hydrogen and oxygen, and has a feature of high energy use efficiency. Alternatively, research into practical use is actively conducted for automobiles and the like.
For this fuel cell, types such as a phosphoric acid type, a molten carbonate type, a solid oxide type, and a solid polymer type are known depending on the type of electrolyte used. On the other hand, as a hydrogen source, liquefied natural gas mainly composed of methanol and methane, city gas mainly composed of this natural gas, synthetic liquid fuel using natural gas as a raw material, LPG, dimethyl ether, naphtha, kerosene, etc. The use of petroleum-based hydrocarbons has been studied.
これらのガス状又は液状炭化水素を用いて水素を製造する場合、一般に、該炭化水素を、改質触媒の存在下に部分酸化改質、オートサーマル改質又は水蒸気改質などで処理する方法が用いられている。
ＬＰＧ、都市ガス、灯油などの炭化水素燃料を改質して燃料用水素を製造する場合、改質触媒の被毒を抑制するためには、燃料中の硫黄分を０．０５ｐｐｍ以下に低減させることが要求される。また、プロピレンやブテンなどは、石油化学製品の原料として使用する場合、やはり触媒の被毒を防ぐためには、硫黄分を０．０５ｐｐｍ以下に低減させることが要求される。
前記ＬＰＧ中には、硫黄化合物として、一般にメチルメルカプタンや硫化カルボニル（ＣＯＳ）などに加えて、着臭剤として添加されたジメチルサルファイド（ＤＭＳ）、ｔ−ブチルメルカプタン（ＴＢＭ）、メチルエチルサルファイドなどが含まれている。また、最近ジメチルエーテルを燃料として利用する計画が進められている。このジメチルエーテル自体は、硫黄化合物を含有していないが、漏洩対策から意図的に上記着臭剤の添加が検討されている。
When producing hydrogen using these gaseous or liquid hydrocarbons, generally, there is a method of treating the hydrocarbons by partial oxidation reforming, autothermal reforming or steam reforming in the presence of a reforming catalyst. It is used.
When reforming hydrocarbon fuels such as LPG, city gas, and kerosene to produce hydrogen for fuel, the sulfur content in the fuel is reduced to 0.05 ppm or less in order to suppress poisoning of the reforming catalyst. Is required. Further, when propylene, butene, etc. are used as a raw material for petrochemical products, it is required to reduce the sulfur content to 0.05 ppm or less in order to prevent poisoning of the catalyst.
In the LPG, as a sulfur compound, dimethyl sulfide (DMS), t-butyl mercaptan (TBM), methyl ethyl sulfide, etc. added as an odorant in addition to methyl mercaptan and carbonyl sulfide (COS) are generally included. include. Recently, a plan to use dimethyl ether as a fuel is underway. Although this dimethyl ether itself does not contain a sulfur compound, the addition of the above odorant has been studied intentionally in order to prevent leakage.
ところで、上記の炭化水素燃料の中で、ガス状炭化水素化合物の方が液状炭化水素化合物に比べて、脱硫において、運転条件が低温、低圧で穏やかであるため、ガス状炭化水素化合物の方が多く採用されつつある。
ＬＰＧや都市ガスなどの炭化水素含有ガス中の硫黄化合物を吸着除去する各種吸着剤が知られているが（例えば、特許文献１、特許文献２参照）、従来の吸着剤は吸着容量が十分ではなく、長期間使用するには、しばしば取り替える必要があり実用的ではなかった。
特許文献１には、金属成分と、無機酸化物および／または活性炭とからなる複合化合物を含む燃料ガス処理剤が開示されているが、実施例においては、平均粒径２ｍｍのものしか使用されておらず、長時間吸着活性が持続できないものであった。
特許文献２には、多孔質担体に銅成分が担持された比表面積１５０ｍ2／ｇ以上の吸着剤と、硫黄化合物を含有する気相成分を接触させる硫黄化合物の除去方法が開示されているが、実施例においては、粒径１〜３ｍｍ（平均粒径は１ｍｍ超）のものしか使用されておらず、長時間吸着活性が持続できないものであった。
By the way, among the above hydrocarbon fuels, the gaseous hydrocarbon compound is more gentle at low temperature and low pressure in the desulfurization operation than the gaseous hydrocarbon compound, so the gaseous hydrocarbon compound is more preferable. Many are being adopted.
Various adsorbents that adsorb and remove sulfur compounds in hydrocarbon-containing gases such as LPG and city gas are known (see, for example, Patent Document 1 and Patent Document 2), but conventional adsorbents do not have sufficient adsorption capacity. In order to use it for a long period of time, it often needs to be replaced and is not practical.
Patent Document 1 discloses a fuel gas treating agent containing a composite compound composed of a metal component and an inorganic oxide and / or activated carbon. In the examples, only those having an average particle diameter of 2 mm are used. The adsorption activity could not be sustained for a long time.
Patent Document 2 discloses a method for removing a sulfur compound in which an adsorbent having a specific surface area of 150 m 2 / g or more in which a copper component is supported on a porous carrier and a gas phase component containing a sulfur compound are brought into contact with each other. In Examples, only particles having a particle size of 1 to 3 mm (average particle size exceeding 1 mm) were used, and the adsorption activity could not be sustained for a long time.
本発明は、このような状況下でなされたもので、同一の充填質量で長時間にわたり微量の硫黄化合物の流出を抑制できる、ガス状炭化水素化合物中の硫黄化合物を除去する脱硫剤成形体及び脱硫方法、並びにその脱硫剤成形体を用いて脱硫処理したガス状炭化水素化合物から、水素を効果的に製造する方法、更にその水素を用いる燃料電池システムを提供することを目的とするものである。 The present invention was made under such circumstances, and a desulfurization agent molded body for removing sulfur compounds in a gaseous hydrocarbon compound, which can suppress outflow of a trace amount of sulfur compounds over a long period of time with the same filling mass, and It is an object of the present invention to provide a desulfurization method, a method for effectively producing hydrogen from a gaseous hydrocarbon compound desulfurized using the desulfurization agent molding, and a fuel cell system using the hydrogen. .
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、多孔質担体に活性金属が担持されている脱硫剤成形体の平均粒径が０．０３〜１．０ｍｍであるものが本発明の目的を効率的に達成できることを見出した。本発明は、かかる知見に基づいて完成したものである。 As a result of intensive studies to achieve the above object, the inventors of the present invention have an average particle diameter of 0.03-1.0 mm of a desulfurization agent molded body in which an active metal is supported on a porous carrier. Has found that the object of the present invention can be efficiently achieved. The present invention has been completed based on such findings.
すなわち、本発明は、
（１）ガス状炭化水素化合物中の硫黄化合物を除去する脱硫剤であって、多孔質担体に活性金属が担持されてなり、かつ、平均粒径が０．０３〜１．０ｍｍである脱硫剤成形体であって、該多孔質担体がゼオライト、アルミニウム、ケイ素及び周期律表第３族に属する金属から選ばれる少なくとも一種の金属の酸化物であることを特徴とする脱硫剤成形体、
（２）平均粒径が０．０３〜０．５ｍｍである上記（１）に記載の脱硫剤成形体、
（３）多孔質担体が、ＦＡＵ、ＢＥＡ、ＬＴＬ、ＭＯＲ、ＭＴＷ、ＧＭＥ、ＯＦＦ、ＭＦＩ、ＭＥＬ、ＦＥＲ、ＴＯＮ、ＭＴＴ及びＬＴＡ構造を有するゼオライトの中から選ばれる少なくとも一種である上記（１）又は（２）に記載の脱硫剤成形体、
（４）周期律表第３族に属する金属が、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｎｄ、Ｐｒ、Ｓｍ、Ｇｄ及びＹｂから選ばれる少なくとも一種である上記（１）又は（２）に記載の脱硫剤成形体、
（５）活性金属が、Ａｇ、Ｃｕ、Ｃｏ、Ｎｉ、Ｚｎ、Ｍｎ、Ｆｅ及びＣｅから選ばれる少なくとも一種である上記（１）〜（４）のいずれかに記載の脱硫剤成形体、
（６）ガス状炭化水素化合物が、天然ガス、都市ガス、ＬＰＧ、エタン、プロパン、プロピレン、ブタン、ブチレン、ブタジエン及びジメチルエーテルから選ばれる少なくとも一種である上記（１）〜（５）のいずれかに記載の脱硫剤成形体、
（７）上記（１）〜（６）のいずれかに記載の脱硫剤成形体を用いてガス状炭化水素化合物中の硫黄化合物を除去することを特徴とする脱硫方法、
（８）上記（１）〜（６）のいずれかに記載の脱硫剤成形体を１００リットル未満の小型脱硫器に充填して用いる上記（７）に記載の脱硫方法、
（９）上記（１）〜（６）のいずれかに記載の脱硫剤成形体を用いて、ガス状炭化水素化合物中の硫黄化合物を脱硫処理したのち、この脱硫処理ガス状炭化水素化合物を部分酸化改質触媒、オートサーマル改質触媒又は水蒸気改質触媒と接触させることを特徴とする水素の製造方法、
(１０)部分酸化改質触媒、オートサーマル改質触媒又は水蒸気改質触媒がルテニウム系又はニッケル系触媒である上記（９）に記載の水素の製造方法、
(１１)上記（９）又は（１０）に記載の方法で製造された水素を用いることを特徴とする燃料電池システム、
を提供するものである。
That is, the present invention
(1) a desulfurizing agent to remove sulfur compounds in the gaseous hydrocarbon compound, becomes in active metal on a porous support is supported, and an average particle size of Ru 0.03~1.0mm der de A desulfurizing agent molded body, wherein the porous carrier is an oxide of at least one metal selected from zeolite, aluminum, silicon and a metal belonging to Group 3 of the periodic table,
(2) The desulfurization agent molded body according to (1) , wherein the average particle diameter is 0.03 to 0.5 mm,
(3) The above (1), wherein the porous support is at least one selected from zeolites having a FAU, BEA, LTL, MOR, MTW, GME, OFF, MFI, MEL, FER, TON, MTT and LTA structure. Or the desulfurization agent molded product according to (2),
( 4 ) The desulfurization according to (1) or (2), wherein the metal belonging to Group 3 of the periodic table is at least one selected from Sc, Y, La, Ce, Nd, Pr, Sm, Gd, and Yb Agent molded body,
( 5 ) The desulfurization agent molded body according to any one of (1) to (4) , wherein the active metal is at least one selected from Ag, Cu, Co, Ni, Zn, Mn, Fe, and Ce,
( 6 ) In any one of the above (1) to (5), the gaseous hydrocarbon compound is at least one selected from natural gas, city gas, LPG, ethane, propane, propylene, butane, butylene, butadiene and dimethyl ether. Desulfurizing agent molded body according to the description ,
( 7 ) A desulfurization method comprising removing a sulfur compound in a gaseous hydrocarbon compound using the desulfurization agent molded body according to any one of (1) to (6 ) above,
( 8 ) The desulfurization method according to ( 7 ), wherein the desulfurization agent molded body according to any one of (1) to (6) is used by filling in a small desulfurizer of less than 100 liters,
( 9 ) After desulfurizing the sulfur compound in the gaseous hydrocarbon compound using the desulfurizing agent molded body according to any one of (1) to (6) above , the desulfurized gaseous hydrocarbon compound is partially A method for producing hydrogen, characterized by contacting with an oxidation reforming catalyst, an autothermal reforming catalyst or a steam reforming catalyst,
( 10 ) The method for producing hydrogen according to the above (9), wherein the partial oxidation reforming catalyst, autothermal reforming catalyst or steam reforming catalyst is a ruthenium-based or nickel-based catalyst,
( 11 ) A fuel cell system using hydrogen produced by the method according to (9) or (10 ) above,
Is to provide.
本発明によれば、ガス状炭化水素化合物中の硫黄化合物を、同一の充填質量で長時間にわたり微量の硫黄化合物の流出を抑制できる脱硫剤成形体及び脱硫方法、並びにその脱硫剤成形体を用いて脱硫処理したガス状炭化水素化合物から、水素を効果的に製造する方法、更にその水素を用いる燃料電池システムを提供することができる。 According to the present invention, a sulfur compound in a gaseous hydrocarbon compound is used with a desulfurization agent molded body and a desulfurization method capable of suppressing the outflow of a trace amount of a sulfur compound for a long time with the same filling mass, and the desulfurization agent molded body is used. Thus, it is possible to provide a method for effectively producing hydrogen from a gaseous hydrocarbon compound subjected to desulfurization treatment, and a fuel cell system using the hydrogen.
本発明は、ガス状炭化水素化合物中の硫黄化合物を除去する脱硫剤であって、多孔質担体に活性金属が担持されてなり、かつ、平均粒径が０．０３〜１．０ｍｍであることを特徴とする脱硫剤成形体である。
まず、本発明の脱硫剤成形体に使用される多孔質担体として、（ａ）ゼオライト、（ｂ）アルミニウム、ケイ素及び周期律表第３族に属する金属から選ばれる少なくとも一種の金属の酸化物、（ｃ）その他の多孔質担体が挙げられる。
（ａ）成分のゼオライトとして、ＦＡＵ、ＢＥＡ、ＬＴＬ、ＭＯＲ、ＭＴＷ、ＧＭＥ、ＯＦＦ、ＭＦＩ、ＭＥＬ、ＦＥＲ、ＴＯＮ、ＭＴＴ及びＬＴＡ構造を有するものの中から選ばれる少なくとも一種を用いることができる。これらの中で、１０員環細孔を有するＦＡＵ、ＢＥＡ、ＬＴＬ、ＭＯＲ、ＭＴＷ、ＧＭＥ及びＯＦＦ構造を有するゼオライトが好ましく、特に吸着性能の点から、ＦＡＵ、ＢＥＡ及びＬＴＬ構造を有するゼオライトが好適である。また、上記のゼオライトは、アルカリ金属／アルミニウム（原子比）が０．５以下のもの好ましい。
（ｂ）成分のうち、アルミニウム、ケイ素の酸化物として、アルミナ、シリカ、シリカ−アルミナ、珪藻土などが挙げられる。（ｂ）成分のうち、周期律表第３族に属する金属の酸化物として、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｎｄ、Ｐｒ、Ｓｍ、Ｇｄ、Ｙｂなどの酸化物が挙げられる。これらの中で、効果の点でＣｅの酸化物が好ましい。さらに、（ｃ）成分のその他の多孔質担体として、チタニア、ジルコニア、マグネシア、酸化亜鉛、白土、粘土、活性炭などが挙げられる。
次に、上記多孔質担体に担持される活性金属として、Ａｇ、Ｃｕ、Ｃｏ、Ｎｉ、Ｚｎ、Ｍｎ、Ｆｅ、Ｃｅなどが挙げられる。すなわち、Ｃｅは活性金属と担体の両方に機能することがわかる。
上記の活性金属を上記の担体に担持させる方法には、公知の方法、例えばポアフィリング法、浸漬法、沈着法、蒸発乾固法、イオン交換法を用いることができる。この際、乾燥温度は、通常５０〜２００℃程度であり、焼成温度は、通常２５０〜５００℃程度である。また、脱硫剤中の活性金属の量は金属として、１〜４０質量％、好ましくは、３〜３０質量％に調整すればよい。
The present invention is a desulfurization agent for removing a sulfur compound in a gaseous hydrocarbon compound, wherein an active metal is supported on a porous carrier, and an average particle diameter is 0.03 to 1.0 mm. Is a desulfurizing agent molded body characterized by
First, as a porous carrier used in the desulfurization agent molded body of the present invention, (a) an oxide of at least one metal selected from (a) zeolite, (b) aluminum, silicon and a metal belonging to Group 3 of the periodic table, (C) Other porous carriers may be mentioned.
As the zeolite of component (a), at least one selected from those having FAU, BEA, LTL, MOR, MTW, GME, OFF, MFI, MEL, FER, TON, MTT and LTA structures can be used. Among these, zeolites having FAU, BEA, LTL, MOR, MTW, GME and OFF structures having 10-membered ring pores are preferable, and zeolites having FAU, BEA and LTL structures are particularly preferable in terms of adsorption performance. It is. Further, the above zeolite preferably has an alkali metal / aluminum (atomic ratio) of 0.5 or less.
Among the components (b), examples of aluminum and silicon oxides include alumina, silica, silica-alumina, and diatomaceous earth. Among the components (b), oxides of metals belonging to Group 3 of the periodic table include oxides such as Sc, Y, La, Ce, Nd, Pr, Sm, Gd, and Yb. Among these, Ce oxide is preferable in terms of effects. Furthermore, as the other porous carrier of the component (c), titania, zirconia, magnesia, zinc oxide, clay, clay, activated carbon and the like can be mentioned.
Next, examples of the active metal supported on the porous carrier include Ag, Cu, Co, Ni, Zn, Mn, Fe, and Ce. That is, it can be seen that Ce functions as both an active metal and a support.
As a method for supporting the active metal on the carrier, a known method such as a pore filling method, an immersion method, a deposition method, an evaporation to dryness method, or an ion exchange method can be used. Under the present circumstances, drying temperature is about 50-200 degreeC normally, and a calcination temperature is about 250-500 degreeC normally. Moreover, what is necessary is just to adjust the quantity of the active metal in a desulfurizing agent to 1-40 mass% as a metal, Preferably, it is 3-30 mass%.
なお、多孔質担体がゼオライトの場合、金属アンミン錯イオンを含む溶液を用いて金属イオン交換してゼオライトに活性金属を担持させて金属イオン交換ゼオライトを調製するのが好ましく、この点について詳述する。金属アンミン錯イオンを含む溶液としては、水溶性の金属アンミン錯イオンを水に溶解させた溶液、あるいは金属の硝酸塩や塩化物などの水溶性金属化合物を水に溶解させ、これに過剰のアンモニア水を加え、金属のアミン錯イオンを形成させてなる溶液などを用いることができる。ここで、金属アンミン錯イオンを含む溶液の金属種としては、Ａｇ、Ｃｕ、Ｃｏ、Ｎｉ及びＺｎの中から選ばれる少なくとも一種が好ましく、特に硫黄化合物の吸着性能の点から、Ａｇ、Ｃｕ、Ｎｉが好適である。 When the porous carrier is zeolite, it is preferable to prepare a metal ion-exchanged zeolite by carrying out a metal ion exchange using a solution containing a metal ammine complex ion and supporting the active metal on the zeolite, and this point will be described in detail. . As a solution containing a metal ammine complex ion, a solution in which a water-soluble metal ammine complex ion is dissolved in water, or a water-soluble metal compound such as a metal nitrate or chloride is dissolved in water, and excess ammonia water is added thereto. And a solution formed by forming a metal amine complex ion can be used. Here, the metal species of the solution containing the metal ammine complex ion is preferably at least one selected from Ag, Cu, Co, Ni and Zn, and particularly Ag, Cu, Ni from the viewpoint of the adsorption performance of the sulfur compound. Is preferred.
金属イオン交換ゼオライトを調製するには、まず上記の金属アンミン錯イオンを含む溶液に、前述のゼオライトを加え、通常０〜９０℃、好ましくは２０〜７０℃の範囲の温度において、１ないし数時間程度、好ましくは攪拌しながらイオン交換処理する。次いで、固形物をろ過などの手段で分離し、水などで洗浄したのち、５００℃以下（好ましくは５０〜２００℃程度）の温度で乾燥処理する。このイオン交換処理は繰り返し行うことができる。次に、５００℃以下（好ましくは２００〜５００℃程度）の温度で数時間程度焼成処理することにより、目的の金属イオン交換ゼオライトが得られる。
このようにして得られた金属イオン交換ゼオライト中の金属担持量は、金属として５〜３０質量％の範囲が好ましく、特に１０〜２５質量％の範囲が好適である。また、アルカリ金属の含有量が２質量％以下であることが好ましい。
In order to prepare a metal ion exchange zeolite, first, the above zeolite is added to a solution containing the above metal ammine complex ions, and usually at a temperature in the range of 0 to 90 ° C., preferably 20 to 70 ° C., for 1 to several hours. The ion exchange treatment is carried out to an extent, preferably with stirring. Next, the solid is separated by a means such as filtration, washed with water, and then dried at a temperature of 500 ° C. or less (preferably about 50 to 200 ° C.). This ion exchange treatment can be repeated. Next, the target metal ion-exchanged zeolite is obtained by firing for several hours at a temperature of 500 ° C. or less (preferably about 200 to 500 ° C.).
The metal loading in the metal ion exchanged zeolite thus obtained is preferably in the range of 5 to 30% by mass, particularly preferably in the range of 10 to 25% by mass as the metal. Moreover, it is preferable that content of an alkali metal is 2 mass% or less.
以上のようにして調製された脱硫剤は、適当なバインダーを用いて押出成形、打錠成形、転動造粒、スプレードライなどの通常の方法で成形して使用する。また、予め成形した担体に活性金属を担持させてもよい。 The desulfurizing agent prepared as described above is used after being molded by an ordinary method such as extrusion molding, tableting molding, rolling granulation, spray drying and the like using an appropriate binder. Further, the active metal may be supported on a preformed carrier.
本発明においては、上記脱硫剤成形体を破砕して、平均粒径を０．０３〜１．０ｍｍにしてガス状炭化水素化合物の脱硫に供する。平均粒径が０．０３ｍｍ未満であると、使用する際の差圧が大きくなり使用できない。平均粒径が１．０ｍｍを超えると、所望の脱硫性能が得られない。好ましい平均粒径は０．０３〜０．５ｍｍである。さらに、該脱硫剤成形体を１００リットル未満の小型脱硫器に充填して用いると有効である。
前記のようにして得られた脱硫剤成形体は、天然ガス、都市ガス、ＬＰＧ、エタン、プロパン、プロピレン、ブタン、ブチレン、ブタジエン及びジメチルエーテルから選ばれるガス状炭化水素化合物燃料に適用される。
本発明の脱硫体成形体が適用されるガス状炭化水素化合物燃料中の硫黄化合物の濃度としては、０．００１〜１０,０００容量ｐｐｍが好ましく、特に０．１〜１００容量ｐｐｍが好ましい。また、脱硫条件としては、通常温度は−５０〜３００℃の範囲で選ばれ、ＧＨＳＶは１００〜１０,０００ｈ-1の範囲で選ばれる。
In this invention, the said desulfurization agent molded object is crushed and it uses for desulfurization of a gaseous hydrocarbon compound by making an average particle diameter 0.03-1.0 mm. If the average particle size is less than 0.03 mm, the differential pressure at the time of use becomes large and cannot be used. If the average particle size exceeds 1.0 mm, the desired desulfurization performance cannot be obtained. A preferred average particle size is 0.03 to 0.5 mm. Furthermore, it is effective to use the desulfurization agent compact after filling it in a small desulfurizer of less than 100 liters.
The desulfurization agent molded body obtained as described above is applied to a gaseous hydrocarbon compound fuel selected from natural gas, city gas, LPG, ethane, propane, propylene, butane, butylene, butadiene and dimethyl ether.
As a density | concentration of the sulfur compound in the gaseous hydrocarbon compound fuel to which the desulfurization molded object of this invention is applied, 0.001-10,000 volume ppm is preferable, and 0.1-100 volume ppm is especially preferable. As desulfurization conditions, the normal temperature is selected in the range of −50 to 300 ° C., and the GHSV is selected in the range of 100 to 10,000 h −1 .
次に、本発明の主に燃料電池に使用される水素の製造方法においては、前述の本発明の脱硫剤成形体を用いて、ガス状炭化水素化合物燃料中の硫黄化合物を脱硫処理したのち、この脱硫処理燃料を改質することにより、水素を製造する。 Next, in the method for producing hydrogen mainly used in the fuel cell of the present invention, after desulfurizing the sulfur compound in the gaseous hydrocarbon compound fuel using the above-described desulfurizing agent molded body of the present invention, Hydrogen is produced by reforming the desulfurized fuel.
この際、改質方法として、部分酸化改質、オートサーマル改質、水蒸気改質などの方法を用いることができる。この改質方法においては、脱硫処理炭化水素燃料又はジメチルエーテル燃料中の硫黄化合物の濃度は、各改質触媒の寿命の点から、０．１容量ｐｐｍ以下が好ましく、特に０．００５容量ｐｐｍ以下が好ましい。
前記部分酸化改質は、炭化水素の部分酸化反応により、水素を製造する方法であって、部分酸化改質触媒の存在下、通常、反応圧力常圧〜５ＭＰａ、反応温度４００〜１，１００℃、ＧＨＳＶ１，０００〜１００，０００ｈ-1、酸素（Ｏ2）／炭素比０．２〜０．８の条件で改質反応が行われる。
また、オートサーマル改質は、部分酸化改質と水蒸気改質とを組み合わせた方法であって、オートサーマル改質触媒の存在下、通常、反応圧力常圧〜５ＭＰａ、反応温度４００〜１，１００℃、酸素（Ｏ2）／炭素比０．１〜１、スチーム／炭素比０．１〜１０、ＧＨＳＶ１，０００〜１００，０００ｈ-1の条件で改質反応が行われる。
さらに、水蒸気改質は、炭化水素に水蒸気を接触させて、水素を製造する方法であって、水蒸気改質触媒の存在下、通常、反応圧力常圧〜３ＭＰａ、反応温度２００〜９００℃、スチーム／炭素比１．５〜１０、ＧＨＳＶ１，０００〜１００，０００ｈ-1の条件で改質反応が行われる。
At this time, methods such as partial oxidation reforming, autothermal reforming, and steam reforming can be used as reforming methods. In this reforming method, the concentration of the sulfur compound in the desulfurized hydrocarbon fuel or dimethyl ether fuel is preferably 0.1 ppm by volume or less, particularly preferably 0.005 ppm by volume or less, from the viewpoint of the life of each reforming catalyst. preferable.
The partial oxidation reforming is a method for producing hydrogen by a partial oxidation reaction of hydrocarbons, and in the presence of a partial oxidation reforming catalyst, usually a reaction pressure of normal pressure to 5 MPa, a reaction temperature of 400 to 1,100 ° C. The reforming reaction is carried out under the conditions of GHSV 1,000 to 100,000 h −1 and oxygen (O 2 ) / carbon ratio 0.2 to 0.8.
Autothermal reforming is a method in which partial oxidation reforming and steam reforming are combined. In the presence of an autothermal reforming catalyst, the reaction pressure is usually from normal pressure to 5 MPa, and the reaction temperature is from 400 to 1,100. The reforming reaction is carried out under the conditions of ° C., oxygen (O 2 ) / carbon ratio of 0.1 to 1, steam / carbon ratio of 0.1 to 10, and GHSV of 1,000 to 100,000 h −1 .
Furthermore, steam reforming is a method for producing hydrogen by bringing steam into contact with a hydrocarbon, usually in the presence of a steam reforming catalyst, at a reaction pressure of normal pressure to 3 MPa, a reaction temperature of 200 to 900 ° C., steam. The reforming reaction is performed under the conditions of / carbon ratio of 1.5 to 10 and GHSV of 1,000 to 100,000 h −1 .
本発明においては、前記の部分酸化改質触媒、オートサーマル改質触媒、水蒸気改質触媒としては、従来公知の各触媒の中から適宜選択して用いることができるが、特にルテニウム系及びニッケル系触媒が好適である。また、これらの触媒の担体としては、酸化マンガン、酸化セリウム及びジルコニアの中から選ばれる少なくとも一種を含む担体を好ましく挙げることができる。該担体は、これらの金属酸化物のみからなる担体であってもよく、アルミナなどの他の耐火性多孔質無機酸化物に、上記金属酸化物を含有させてなる担体であってもよい。 In the present invention, the partial oxidation reforming catalyst, autothermal reforming catalyst, and steam reforming catalyst can be appropriately selected from conventionally known catalysts, but are particularly ruthenium-based and nickel-based. A catalyst is preferred. Moreover, as a support | carrier of these catalysts, the support | carrier containing at least 1 type chosen from manganese oxide, a cerium oxide, and a zirconia can be mentioned preferably. The carrier may be a carrier composed of only these metal oxides, or may be a carrier obtained by adding the above metal oxide to another refractory porous inorganic oxide such as alumina.
本発明はまた、前記製造方法で得られた水素を用いる燃料電池システムを提供する。以下に本発明の燃料電池システムについて添付図１に従い説明する。
図１は本発明の燃料電池システムの一例を示す概略フロー図である。図１によれば、燃料タンク２１内の燃料は、必要に応じて、レギュレータ２２で減圧され、脱硫器２３に流入する。脱硫器内には本発明の吸着剤を充填することができる。脱硫器２３で脱硫された燃料は水タンクから水ポンプ２４を経た水と混合されて、水を気化させ改質器３１に送り込まれる。
改質器３１の内部には前述の改質触媒が充填されており、改質器３１に送り込まれた燃料混合物（水蒸気、酸素及び炭化水素燃料若しくは酸素含有炭化水素燃料を含む混合気体）から、前述した改質反応のいずれかによって水素又は合成ガスが製造される。
The present invention also provides a fuel cell system using hydrogen obtained by the production method. The fuel cell system of the present invention will be described below with reference to FIG.
FIG. 1 is a schematic flowchart showing an example of the fuel cell system of the present invention. According to FIG. 1, the fuel in the
The
このようにして製造された水素又は合成ガスはＣＯ変成器３２、ＣＯ選択酸化器３３を通じてそのＣＯ濃度が燃料電池の特性に影響を及ぼさない程度まで低減される。これらの反応器に用いる触媒の例としては、ＣＯ変成器３２では、鉄―クロム系触媒、銅―亜鉛系触媒あるいは貴金属系触媒が、ＣＯ選択酸化炉３３では、ルテニウム系触媒、白金系触媒あるいはそれらの混合物等を挙げることができる。
燃料電池３４は負極３４Ａと正極３４Ｂとの間に高分子電解質３４Ｃを備えた固体高分子型燃料電池である。負極側には上記の方法で得られた水素リッチガスが、正極側には空気ブロワー３５から送られる空気が、それぞれ必要に応じて適当な加湿処理を行った後（加湿装置は図示せず）導入される。
このとき負極側では水素ガスがプロトンとなり電子を放出する反応が進行し、正極側では酸素ガスが電子とプロトンを得て水となる反応が進行し、両極３４Ａ、３４Ｂ間に直流電流が発生する。負極には、白金黒、活性炭担持のＰｔ触媒あるいはＰｔ−Ｒｕ合金触媒などが、正極には白金黒、活性炭担持のＰｔ触媒などが用いられる。
The hydrogen or synthesis gas thus produced is reduced through the
The
At this time, a reaction in which hydrogen gas becomes protons and emits electrons proceeds on the negative electrode side, and a reaction in which oxygen gas obtains electrons and protons to become water proceeds on the positive electrode side, and a direct current is generated between both
負極３４Ａ側に改質器３１のバーナ３１Ａを接続して余った水素を燃料とすることができる。また、正極３４Ｂ側に接続された気水分離器３６において、正極３４Ｂ側に供給された空気中の酸素と水素との結合により生じた水と排気ガスとを分離し、水は水蒸気の生成に利用することができる。
なお、燃料電池３４では、発電に伴って熱が発生するため、排熱回収装置３７を付設してこの熱を回収して有効利用することができる。排熱回収装置３７は、反応時に生じた熱を奪う熱交換機３７Ａと、この熱交換器３７Ａで奪った熱を水と熱交換するための熱交換器３７Ｂと、冷却器３７Ｃと、これら熱交換器３７Ａ、３７Ｂ及び冷却器３７Ｃへ冷媒を循環させるポンプ３７Ｄとを備え、熱交換器３７Ｂにおいて得られた温水は、他の設備などで有効利用することができる。
The surplus hydrogen can be used as fuel by connecting the
In the
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
実施例１
硝酸銀３５ｇを水１，０００ｍＬに溶解し、これに攪拌しながら、３０質量％のアンモニア水５０ｇを加え銀アンミン錯イオンを含む溶液を得た。次いで、β型ゼオライト［東ソー社製「ＨＳＺ−９３０ＮＨＡ」、］の５００℃焼成物２００ｇを、上記銀アンミン錯イオンを含む溶液に投入し、スラリーの温度を５０℃に保ち、攪拌しながら４時間イオン交換処理を行った。その後、固形物をろ過し、水洗したのち、１２０℃で乾燥させ、Ａｇ交換β型ゼオライトを得た。次いで、このＡｇ交換β型ゼオライトにプソイドベーマイトゲル（アルミナ含量：７０質量％）を２９ｇ加え混合した。これに適量の水を加えて捏和し、捏和物を孔径１．７ｍｍの金型を用いて押出成形物を得、さらに１２０℃で乾燥させ、４００℃で３時間焼成した。こうして得られた成形物を成形体母体Ａと称する。この成形体母体Ａを乳鉢で破砕し、０．５〜０．７ｍｍに篩い分けし、平均粒径０．６ｍｍの成形体を得た。
Example 1
35 g of silver nitrate was dissolved in 1,000 mL of water, and 50 g of 30% by mass of ammonia water was added thereto while stirring to obtain a solution containing silver ammine complex ions. Next, 200 g of a 500 ° C. calcined product of β-type zeolite [“HSZ-930NHA” manufactured by Tosoh Corporation] is added to the solution containing the silver ammine complex ion, and the temperature of the slurry is kept at 50 ° C. for 4 hours while stirring. Ion exchange treatment was performed. Thereafter, the solid was filtered, washed with water, and then dried at 120 ° C. to obtain an Ag-exchanged β-type zeolite. Next, 29 g of pseudoboehmite gel (alumina content: 70% by mass) was added to and mixed with the Ag-exchanged β-type zeolite. An appropriate amount of water was added to this and kneaded, and the kneaded product was obtained by using a mold having a pore diameter of 1.7 mm, further dried at 120 ° C., and calcined at 400 ° C. for 3 hours. The molded product thus obtained is referred to as a molded body matrix A. This molded body matrix A was crushed with a mortar and sieved to 0.5 to 0.7 mm to obtain a molded body having an average particle size of 0.6 mm.
実施例２
成形体母体Ａを乳鉢で破砕し、０．２１〜０．３ｍｍに篩い分けし、平均粒径０．２５ｍｍの成形体を得た。
Example 2
The molded body matrix A was crushed with a mortar and sieved to 0.21 to 0.3 mm to obtain a molded body having an average particle size of 0.25 mm.
実施例３
成形体母体Ａを乳鉢で破砕し、０．０５３〜０．０７５ｍｍに篩い分けし、平均粒径０．０６ｍｍの成形体を得た。
Example 3
The molded body base A was crushed with a mortar and sieved to 0.053 to 0.075 mm to obtain a molded body having an average particle size of 0.06 mm.
比較例１
成形体母体Ａを乳鉢で破砕し、１．０〜１．４ｍｍに篩い分けし、平均粒径１．２ｍｍの成形体を得た。
Comparative Example 1
The molded body base A was crushed with a mortar and sieved to 1.0 to 1.4 mm to obtain a molded body having an average particle diameter of 1.2 mm.
実施例４
硝酸セリウム３０質量％水溶液を、約５０℃に保持した１モル／Ｌ濃度の水酸化ナトリウム水溶液に攪拌しながら滴下し、沈殿を生成させた。次いで、生成した沈殿をろ過し、十分洗浄したのち、１２０℃で乾燥後、４００℃で焼成することにより、酸化セリウムを得た。次いで、この酸化セリウムに４２質量％濃度の硝酸銀水溶液を含浸させ、乾燥させたのち、４００℃で焼成した。得られた粉末を圧縮成形機により固形化した。こうして得られた固形物を成形体母体Ｂと称する。この成形体母体Ｂを乳鉢で破砕し、０．５〜０．７ｍｍに篩い分けし、平均粒径０．６ｍｍの成形体を得た。
Example 4
A 30% by mass aqueous solution of cerium nitrate was added dropwise with stirring to a 1 mol / L aqueous sodium hydroxide solution maintained at about 50 ° C. to form a precipitate. Next, the produced precipitate was filtered, washed sufficiently, dried at 120 ° C., and then baked at 400 ° C. to obtain cerium oxide. Next, the cerium oxide was impregnated with an aqueous silver nitrate solution having a concentration of 42% by mass, dried, and then fired at 400 ° C. The obtained powder was solidified by a compression molding machine. The solid material thus obtained is referred to as a molded body base B. This molded body matrix B was crushed with a mortar and sieved to 0.5 to 0.7 mm to obtain a molded body having an average particle size of 0.6 mm.
実施例５
成形体母体Ｂを乳鉢で破砕し、０．２１〜０．３ｍｍに篩い分けし、平均粒径０．２５ｍｍの成形体を得た。
Example 5
The molded body matrix B was crushed with a mortar and sieved to 0.21 to 0.3 mm to obtain a molded body having an average particle size of 0.25 mm.
比較例２
成形体母体Ｂを乳鉢で破砕し、１．０〜１．４ｍｍに篩い分けし、平均粒径１．２ｍｍの成形体を得た。
Comparative Example 2
The molded body matrix B was crushed with a mortar and sieved to 1.0 to 1.4 mm to obtain a molded body having an average particle diameter of 1.2 mm.
なお、本願発明において、脱硫剤成形体の平均粒径の求め方は下記のとおりである。
成形体の平均粒径は、成形体の形状に基づいて以下のように測定する。
（１）成形体が球状の場合；２０個以上の成形体を無作為に選び、それぞれの直径を計測し、その平均値を平均粒径とする。
（２）成形体が円柱形の場合；２０個以上の成形体を無作為に選び、それぞれの底辺の直径と高さを測定し、（底辺の面積の平均値）×（高さの平均値）＝（成形体の体積）とし、（成形体の体積）＝（４／３）πｒ3として得られる直径（＝２ｒ）を平均粒径の値とする。
（３）上記（１）（２）以外の形状の成形体（破砕物など）を篩い分けて用いる場合；Ｘ1〜Ｘ2（Ｘ2＞Ｘ1）に篩い分けられたものの（Ｘ2−Ｘ1）／２を平均粒径とする。
（４）上記（１）（２）以外の形状の成形体（破砕物など）を篩い分けずに用いる場合；用いた成形体の一部を篩い分け、Ｘ1〜Ｘ2（Ｘ2＞Ｘ1）に篩い分けられたものの（Ｘ2−Ｘ1）／２を粒径とし、加重平均値を平均粒径とする。
In the present invention, the method for obtaining the average particle size of the desulfurizing agent molded body is as follows.
The average particle diameter of the molded body is measured as follows based on the shape of the molded body.
(1) When the compact is spherical: 20 or more compacts are randomly selected, the diameters of each are measured, and the average value is taken as the average particle diameter.
(2) When the compact is cylindrical: 20 or more compacts are randomly selected, the diameter and height of each base are measured, and (average value of base area) x (average height) ) = (Volume of compact), and the diameter (= 2r) obtained as (volume of compact) = (4/3) πr 3 is the value of the average particle diameter.
(3) above (1) (2) When used in sieving molded body having a shape other than (such as crushed); X 1 to X 2 though (X 2> X 1) were sieved to (X 2 - X 1) / 2 and the average particle size.
(4) above (1) (2) (such as crushed) other than the molded body shape when used without sieving a; moldings sieving a part of which was used, X 1 ~X 2 (X 2 > X although was sieved to 1) (X 2 -X 1) / 2 and a particle size, the average particle diameter weighted average.
試験例１
実施例１〜３及び比較例１の各脱硫剤成形体７ｃｍ3を内径１５．８ｍｍの脱硫管に充填した。脱硫温度を２０℃とし、市販ＬＰガスを、常圧、ＧＨＳＶ（ガス時空間速度）２５，０００ｈ-1の条件で流通させた。
脱硫管出口ガスの各硫黄化合物濃度をＳＣＤ（Ｓｕｌｆｕｒ Ｃｈｅｍｉｌｕｍｉｎｅｓｃｅｎｃｅ Ｄｅｔｅｃｔｏｒ）ガスクロマトグラフィーにより、１時間毎に測定した。硫黄化合物のうち、硫化カルボニルを除く硫黄化合物の総濃度が０．５質量ｐｐｍを超える時間（破過時間１）を第１表に示す。
Test example 1
7 cm 3 of each desulfurizing agent molded body of Examples 1 to 3 and Comparative Example 1 was filled in a desulfurization pipe having an inner diameter of 15.8 mm. The desulfurization temperature was 20 ° C., and commercially available LP gas was circulated under the conditions of normal pressure and GHSV (gas hourly space velocity) 25,000 h −1 .
The concentration of each sulfur compound in the desulfurization pipe outlet gas was measured every hour by SCD (Sulfur Chemiluminescence Detector) gas chromatography. Table 1 shows the time during which the total concentration of sulfur compounds excluding carbonyl sulfide exceeds 0.5 mass ppm among the sulfur compounds (breakthrough time 1).
試験例２
実施例４，５及び比較例２の各脱硫剤成形体７ｃｍ3を内径１５．８ｍｍの脱硫管に充填した。試験例１と同様の試験方法で試験し、硫黄化合物のうち、硫黄化合物の総濃度が０．５質量ｐｐｍを超える時間（破過時間２）を第２表に示す。
Test example 2
7 cm 3 of each desulfurizing agent molded body of Examples 4 and 5 and Comparative Example 2 was filled in a desulfurization pipe having an inner diameter of 15.8 mm. Table 2 shows the time when the total concentration of the sulfur compounds exceeds 0.5 mass ppm (breakthrough time 2) in the same test method as in Test Example 1.
試験例３
内径５０ｍｍの脱硫管に実施例２記載の平均粒径が０．２５ｍｍである脱硫剤成形体を３００ｃｍ3充填し、市販ＬＰガスを、常圧下、２０℃で、２リットル／分で流通させ、脱硫管前後で差圧を測定した。差圧は０．００１ＭＰａ以下であった。
Test example 3
A desulfurization tube having an inner diameter of 50 mm was filled with 300 cm 3 of a desulfurization agent molded body having an average particle diameter of 0.25 mm described in Example 2, and a commercially available LP gas was allowed to flow at 20 ℃ under normal pressure at 2 liters / minute. The differential pressure was measured before and after the desulfurization pipe. The differential pressure was 0.001 MPa or less.
試験例４
内径５０ｍｍの脱硫管に実施例３記載の平均粒径が０．０６ｍｍである脱硫剤成形体を３００ｃｍ3充填し、市販ＬＰガスを、常圧下、２０℃で、２リットル／分で流通させ、脱硫管前後で差圧を測定した。差圧は０．００２ＭＰａであった。
Test example 4
A desulfurization tube having an inner diameter of 50 mm was filled with 300 cm 3 of a desulfurization agent molded body having an average particle size of 0.06 mm described in Example 3, and a commercially available LP gas was allowed to flow at 20 ° C. and 2 liters / minute under normal pressure. The differential pressure was measured before and after the desulfurization pipe. The differential pressure was 0.002 MPa.
試験例５
内径５０ｍｍの脱硫管に、成形体母体Ａを乳鉢で粉砕し、０．０２２〜０．０３２ｍｍに篩い分けし、平均粒径が０．０２７ｍｍである脱硫剤成形体を３００ｃｍ3充填し、市販ＬＰガスを、常圧下、２０℃で、２リットル／分で流通させ、脱硫管前後で差圧を測定した。差圧は０．００７ＭＰａであった。
Test Example 5
The molded body base A was pulverized in a mortar into a 50 mm inner diameter desulfurization tube, sieved to 0.022 to 0.032 mm, and filled with 300 cm 3 of a desulfurization agent molded body having an average particle size of 0.027 mm. The gas was circulated at 2 liters / minute at 20 ° C. under normal pressure, and the differential pressure was measured before and after the desulfurization pipe. The differential pressure was 0.007 MPa.
１： 燃料電池システム
１１： 水供給管
１２： 燃料導入管
２０： 水素製造システム
２１： 燃料タンク
２２： レギュレータ
２３： 脱硫器
３１： 改質器
３１Ａ：ボイラー
３２： ＣＯ変成器
３３： ＣＯ選択酸化器
３４： 燃料電池
３４Ａ：負極
３４Ｂ：正極
３４Ｃ：高分子電解質
３６： 気水分離器
３７： 排熱回収装置
３７Ａ：熱交換機
３７Ｂ：熱交換器
３７Ｃ：冷却器
1: Fuel cell system 11: Water supply pipe 12: Fuel introduction pipe 20: Hydrogen production system 21: Fuel tank 22: Regulator 23: Desulfurizer 31:
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| JP4840907B2 (en) * | 2005-11-11 | 2011-12-21 | 独立行政法人産業技術総合研究所 | Method for producing organic sulfur compound adsorbent |
| JP4969090B2 (en) * | 2005-11-29 | 2012-07-04 | Ｊｘ日鉱日石エネルギー株式会社 | Desulfurization method for hydrocarbon fuel |
| JP4969091B2 (en) * | 2005-11-29 | 2012-07-04 | Ｊｘ日鉱日石エネルギー株式会社 | Desulfurization method for hydrocarbon fuel |
| JP2008031306A (en) * | 2006-07-28 | 2008-02-14 | Nippon Oil Corp | Desulfurization process for hydrocarbon fuel |
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