JP4722429B2 - Method for producing metal-supported zeolite molding and adsorbent for removing sulfur compound containing the zeolite - Google Patents
Method for producing metal-supported zeolite molding and adsorbent for removing sulfur compound containing the zeolite Download PDFInfo
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- JP4722429B2 JP4722429B2 JP2004241133A JP2004241133A JP4722429B2 JP 4722429 B2 JP4722429 B2 JP 4722429B2 JP 2004241133 A JP2004241133 A JP 2004241133A JP 2004241133 A JP2004241133 A JP 2004241133A JP 4722429 B2 JP4722429 B2 JP 4722429B2
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- zeolite
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- 239000010457 zeolite Substances 0.000 title claims description 155
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 153
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 152
- 150000003464 sulfur compounds Chemical class 0.000 title claims description 39
- 239000003463 adsorbent Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 238000000465 moulding Methods 0.000 title claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 73
- 239000002184 metal Substances 0.000 claims description 71
- 239000000446 fuel Substances 0.000 claims description 67
- 239000013078 crystal Substances 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 26
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 26
- 150000002736 metal compounds Chemical class 0.000 claims description 25
- 238000005342 ion exchange Methods 0.000 claims description 24
- 229930195733 hydrocarbon Natural products 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 21
- 229910021645 metal ion Inorganic materials 0.000 claims description 21
- 238000002407 reforming Methods 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 238000000629 steam reforming Methods 0.000 claims description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002453 autothermal reforming Methods 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 239000003350 kerosene Substances 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 239000003345 natural gas Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000001294 propane Substances 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
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000001273 butane Substances 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
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 238000006477 desulfuration reaction Methods 0.000 description 17
- 230000023556 desulfurization Effects 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- 150000003573 thiols Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003009 desulfurizing effect Effects 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- -1 LPG Chemical class 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000011049 filling 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
- 238000007654 immersion Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002739 metals 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
- 229920000642 polymer Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FTVZOQPUAHMAIA-UHFFFAOYSA-N O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FTVZOQPUAHMAIA-UHFFFAOYSA-N 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development 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
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WXEHBUMAEPOYKP-UHFFFAOYSA-N methylsulfanylethane Chemical compound CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Images
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
- 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
Landscapes
- Separation Of Gases By Adsorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Fuel Cell (AREA)
Description
本発明は、金属担持ゼオライト成型体、その製造方法及び該ゼオライト成型体からなる硫黄化合物除去用吸着剤に関するものであり、さらに詳しくはゼオライト結晶の内部と外部の両方に金属成分を有する金属担持ゼオライト成型体、その製造方法、該金属担持ゼオライト成型体を用いた硫黄化合物除去用吸着剤、該吸着剤を用いて硫黄化合物を除去した気体燃料又は液体燃料からの水素の製造、及び該水素を用いた燃料電池システムに関するものである。 The present invention relates to a metal-supported zeolite molded body, a method for producing the same, and a sulfur compound removing adsorbent comprising the zeolite molded body, and more specifically, a metal-supported zeolite having a metal component both inside and outside the zeolite crystal. Molded body, method for producing the same, adsorbent for removing sulfur compounds using the metal-supported zeolite molded body, production of hydrogen from gaseous fuel or liquid fuel from which sulfur compounds have been removed using the adsorbent, and use of 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、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 natural gas, synthetic liquid fuel using natural gas as a raw material, and petroleum-based systems such as LPG, naphtha and kerosene The use of hydrocarbons has been studied.
ＬＰＧ、都市ガス、灯油、軽油など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。
改質触媒の被毒を抑制するためには、硫黄分を長期間にわたり０．１ｐｐｍ以下に低減させる必要がある。また、プロピレン、ブテン等は石油化学製品の原料として使用する場合にも、やはり触媒の被毒を防ぐため、硫黄分を０．１ｐｐｍ以下に低減させる必要がある。この様に、燃料電池用水素を製造するためには高度な脱硫が必要とされている。
When hydrogen is produced using gaseous or liquid hydrocarbons such as LPG, city gas, kerosene, and light oil, generally, the hydrocarbon is partially oxidized reformed, autothermal reformed or steamed in the presence of a reforming catalyst. A method of processing by reforming or the like is used.
In order to suppress poisoning of the reforming catalyst, it is necessary to reduce the sulfur content to 0.1 ppm or less over a long period of time. Further, when propylene, butene, etc. are used as a raw material for petrochemical products, it is necessary to reduce the sulfur content to 0.1 ppm or less in order to prevent poisoning of the catalyst. Thus, advanced desulfurization is required to produce hydrogen for fuel cells.
前記ＬＰＧ中には、硫黄化合物として、一般にメタンチオールや硫化カルボニル（以下ＣＯＳと表すことがある）、ジメチルジスルフィド（以下ＤＭＤＳと略すことがある）等に加えて、ガス着臭剤としてジメチルスルフィド（以下ＤＭＳと略すことがある）、２−メチル−２−プロパンチオール（以下ＭＰＴと略すことがある）、メチルエチルスルフィド等の硫黄化合物が添加されている。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ないが、漏洩対策から意図的にガス着臭剤の添加が検討されている。 In the LPG, in addition to methanethiol, carbonyl sulfide (hereinafter sometimes referred to as COS), dimethyl disulfide (hereinafter sometimes abbreviated as DMDS), etc., as a sulfur compound, dimethyl sulfide (as a gas odorant) A sulfur compound such as 2-methyl-2-propanethiol (hereinafter abbreviated as MPT), methyl ethyl sulfide, or the like is added. 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 a gas odorant has been studied intentionally to prevent leakage.
ＬＰＧや都市ガス等の気体炭化水素中の硫黄分を吸着除去する各種吸着剤が知られているが、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った。
例えば、硫黄化合物除去用吸着剤として、アルカリ土類金属以外の多価金属イオン（Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｓｎ及びＺｎ）を交換したゼオライト系脱硫剤（例えば、特許文献１参照）、疎水性ゼオライトにＡｇ、Ｃｕ、Ｚｎ、Ｆｅ、Ｃｏ、Ｎｉなどをイオン交換により担持させた脱硫剤（例えば、特許文献２参照）や、Ｙ型ゼオライト、β型ゼオライト又はＸ型ゼオライトにＡｇ又はＣｕを担持した脱硫剤（例えば、特許文献３参照）などが開示されている。
これらの脱硫剤は、いずれも硝酸塩、酢酸塩、塩化物を用いてイオン交換を行い製造することが記載されている。しかしながら、このような方法でイオン交換を行う場合、実際には１回のイオン交換では、担持量を十分に多くすることが困難である。したがって、担持量を増大させるには、繰り返しイオン交換を行う必要がある。
さらに、後述のように、本発明の開発過程において、こうした従来の脱硫剤は、チオール類やスルフィド類を室温で効率的に吸着除去できるものの、硫化カルボニルに対しては不十分であることが明らかになった。
Various adsorbents that adsorb and remove sulfur in gas hydrocarbons such as LPG and city gas are known, but conventional adsorbents do not have sufficient adsorption capacity and need to be replaced frequently for long-term use. there were.
For example, as a sulfur compound removing adsorbent, a zeolite-based desulfurization agent in which polyvalent metal ions other than alkaline earth metals (Mn, Fe, Co, Ni, Cu, Sn, and Zn) are exchanged (see, for example, Patent Document 1) , A desulfurization agent in which Ag, Cu, Zn, Fe, Co, Ni, etc. are supported on a hydrophobic zeolite by ion exchange (for example, see Patent Document 2), Y-type zeolite, β-type zeolite or X-type zeolite with Ag or A desulfurization agent supporting Cu (see, for example, Patent Document 3) is disclosed.
It is described that these desulfurization agents are produced by ion exchange using nitrate, acetate, and chloride. However, when ion exchange is performed by such a method, it is actually difficult to sufficiently increase the loading amount by one ion exchange. Therefore, it is necessary to repeatedly perform ion exchange in order to increase the loading amount.
Further, as will be described later, in the development process of the present invention, such a conventional desulfurizing agent can adsorb and remove thiols and sulfides efficiently at room temperature, but is insufficient for carbonyl sulfide. Became.
本発明は、金属担持ゼオライト成型体、その製造方法及び該ゼオライト成型体からなる硫黄化合物除去用吸着剤を提供することを主な目的とするものである。
さらに詳しくは本発明は、チオール類やスルフィド類ばかりでなく硫化カルボニルをも効率よく除去できる金属担持ゼオライト成型体、その製造方法、該金属担持ゼオライト成型体の硫黄化合物除去用吸着剤としての応用方法、該硫黄化合物除去用吸着剤によって脱硫した気体燃料又は液体燃料からの水素の製造、及び該水素を用いた燃料電池システムを提供することを目的とする。
The main object of the present invention is to provide a metal-supported zeolite molding, a method for producing the same, and an adsorbent for removing sulfur compounds comprising the zeolite molding.
More specifically, the present invention relates to a metal-supported zeolite molding that can efficiently remove not only thiols and sulfides but also carbonyl sulfide, a method for producing the same, and an application method of the metal-supporting zeolite molding as an adsorbent for removing sulfur compounds. Another object of the present invention is to provide hydrogen from gaseous fuel or liquid fuel desulfurized by the sulfur compound removing adsorbent 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、ゼオライト結晶の内部と外部の両方に金属成分を有する金属担持ゼオライト成型体がチオール類やスルフィド類ばかりでなく硫化カルボニルをも効率よく除去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 present inventors have found that a metal-supported zeolite molded body having a metal component both inside and outside the zeolite crystal contains not only thiols and sulfides but also carbonyl sulfide. Also found that it can be removed efficiently.
The present invention has been completed based on such findings.
すなわち、本発明は、
（１）ゼオライト成型体と、それに担持された金属成分とを有する金属担持ゼオライト成型体であって、前記金属成分が、Ａｇ、Ｃｕ、Ｚｎ、Ｎｉ、Ｆｅ、Ｃｅ、Ｌａ、Ｚｒ及びＴｉ金属元素の中から選ばれる少なくとも１種であり、ゼオライト結晶中に金属イオンとして担持されたものと、ゼオライト結晶外部に金属または金属化合物の状態で担持されたものからなり、かつ、前記のゼオライト結晶外部における金属成分の担持量が、金属担持ゼオライト成形体全量に対して０．５〜２０質量％であることを特徴とする金属担持ゼオライト成型体、
（２）ゼオライトが、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１種である上記（１）の金属担持ゼオライト成型体、
（３）金属担持量が、金属担持ゼオライト成型体全量に基づき、金属として５〜５０質量％である上記（１）又は（２）の金属担持ゼオライト成型体、
（４）ゼオライト成型体を用い、ゼオライト結晶中に金属イオン交換により金属イオンを担持し、次いでゼオライト結晶外部に金属または金属化合物を担持する上記（１）〜（３）のいずれかの金属担持ゼオライト成型体の製造方法、
（５）ゼオライト結晶外部への金属または金属化合物の担持を、溶解状態の金属化合物の溶解度を低下させ、該金属化合物を沈着させることにより行う上記（４）の金属担持ゼオライト成型体の製造方法、
（６）ゼオライト成型体を用い、ゼオライト結晶の少なくとも外部に１族または２族に属する金属元素を担持させ、次いでゼオライト結晶の内部に、金属イオン交換により、Ａｇ、Ｃｕ、Ｚｎ、Ｎｉ、Ｆｅ、Ｃｅ、Ｌａ、Ｚｒ及びＴｉ金属元素の中から選ばれる少なくとも１種の金属成分の金属イオンを担持させると共に、ゼオライト結晶の外部に担持された１族又は２族に属する金属元素を、前記金属成分を含む化合物と反応させて、ゼオライト結晶の外部に前記金属成分の水酸化物又は酸化物として金属化合物を担持させることを特徴とする上記（１）〜（３）のいずれかの金属担持ゼオライト成型体の製造方法、
（７）上記（１）〜（３）のいずれかの金属担持ゼオライト成型体を含むことを特徴とする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除去用吸着剤、
（８）炭化水素燃料がＬＰＧ、都市ガス、天然ガス、ナフサ、灯油、軽油、あるいはエタン、エチレン、プロパン、プロピレン、ブタン、ブテンの中から選ばれる少なくとも一種の炭化水素である上記（７）の硫黄化合物除去用吸着剤、
（９）前記の炭化水素燃料又はジメチルエーテル燃料に含有される硫化カルボニルを吸着除去する、上記（７）又は（８）に記載の硫黄化合物除去用吸着剤、
（１０）上記（７）〜（９）のいずれかの硫黄化合物除去用吸着剤を用いて、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を脱硫した後、この脱硫処理燃料を部分酸化改質触媒、オートサーマル改質触媒また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、
（１１）部分酸化改質触媒、オートサーマル改質触媒または水蒸気改質触媒が、ルテニウム系触媒またはニッケル系触媒である上記（１０）の水素の製造方法、及び
（１２）上記（１０）又は（１１）の製造方法で得ら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) and the molded zeolite, it a metal loaded zeolite molded to have a the supported metal component, the metal component, Ag, Cu, Zn, Ni , Fe, Ce, La, Zr and Ti metal is at least one selected from the elements, to those carried as metal ions in the zeolite crystal, Ri Do from those supported on zeolite crystals outside in the form of metal or metal compound, and said zeolite crystals The metal-supported zeolite molded body, wherein the supported amount of the metal component on the outside is 0.5 to 20% by mass with respect to the total amount of the metal-supported zeolite molded body,
( 2 ) The above (1 ), wherein the zeolite is at least one selected from zeolites having FAU, BEA, LTL, MOR, MTW, GME, OFF, MFI, MEL, FER, TON, MTT and LTA structures . Metal-supported zeolite moldings,
( 3 ) The metal-supported zeolite molded body according to the above (1) or (2) , wherein the metal-supported amount is 5 to 50% by mass as a metal based on the total amount of the metal-supported zeolite molded body.
( 4 ) The metal-supported zeolite according to any one of (1) to ( 3 ), wherein a zeolite molded body is used, metal ions are supported in the zeolite crystals by metal ion exchange, and then the metal or metal compound is supported outside the zeolite crystals. Manufacturing method of molded body,
( 5 ) The method for producing a metal-supported zeolite molded article according to ( 4 ), wherein the metal or metal compound is supported outside the zeolite crystal by reducing the solubility of the metal compound in a dissolved state and depositing the metal compound.
(6) using a shaped zeolite, by supporting a metal element belonging to Group 1 or 2 at least to the outside of the zeolite crystals, and then the interior of the zeolite crystal, a metal ion exchange, Ag, Cu, Zn, Ni, Fe, A metal element belonging to Group 1 or Group 2 supported on the outside of the zeolite crystal is supported while supporting a metal ion of at least one metal component selected from Ce, La, Zr and Ti metal elements. The metal-supported zeolite molding according to any one of (1) to ( 3 ), wherein the metal compound is supported as a hydroxide or oxide of the metal component outside the zeolite crystal by reacting with a compound containing Body manufacturing method,
( 7 ) An adsorbent for removing sulfur compounds in hydrocarbon fuel or dimethyl ether fuel, comprising the metal-supported zeolite molded body according to any one of (1) to ( 3 ) above,
(8) hydrocarbon fuel is LPG, city gas, natural gas, naphtha, kerosene, light oil or ethane, ethylene, propane, propylene, butane, the above (7) at least one hydrocarbon selected from among butene Adsorbent for removing sulfur compounds,
(9) The adsorbent for sulfur compound removal according to (7) or (8) above, which adsorbs and removes carbonyl sulfide contained in the hydrocarbon fuel or dimethyl ether fuel.
(10) The sulfur compound in the hydrocarbon fuel or dimethyl ether fuel is desulfurized using the sulfur compound removing adsorbent according to any one of ( 7 ) to (9) above, and the desulfurized fuel is used as a partial oxidation reforming catalyst. , A method for producing hydrogen, characterized by contacting with an autothermal reforming catalyst or a steam reforming catalyst,
(11) The method for producing hydrogen of (10) above, wherein the partial oxidation reforming catalyst, autothermal reforming catalyst or steam reforming catalyst is a ruthenium catalyst or nickel catalyst, and (12) (10) or ( The present invention provides a fuel cell system using hydrogen obtained by the production method of 11).
本発明によれば、チオール類やスルフィド類ばかりでなく、従来の金属含有ゼオライトでは除去できなかった硫化カルボニルをも効率よく除去できる金属担持ゼオライト成型体、その製造方法及び該ゼオライト成型体から成る硫黄化合物除去用吸着剤を提供することができる。
さらに詳しくは、本発明によれば、ゼオライト結晶の内部と外部の両方に金属成分を有する金属担持ゼオライト成型体、その製造方法、該成型体を用いた硫黄化合物除去用吸着剤、該硫黄化合物除去用吸着剤を用いて脱硫した気体及び液体燃料からの水素の製造、及び該水素を用いた燃料電池システムを提供することができる。
According to the present invention, not only thiols and sulfides, but also a metal-supported zeolite molded body that can efficiently remove carbonyl sulfide that could not be removed by conventional metal-containing zeolite, a method for producing the same, and sulfur comprising the zeolite molded body An adsorbent for compound removal can be provided.
More specifically, according to the present invention, a metal-supported zeolite molded body having a metal component both inside and outside of the zeolite crystal, a production method thereof, a sulfur compound removing adsorbent using the molded body, and the sulfur compound removal Production of hydrogen from gas and liquid fuel desulfurized using the adsorbent for fuel, and a fuel cell system using the hydrogen can be provided.
本発明の金属担持ゼオライト成型体は、ゼオライト結晶の内部と外部の両方に金属成分を有する。
金属交換するゼオライトの種類は、特に限定はされないが、ゼオライト構造が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１種を用いることができる。これらの中で、１２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い。
The metal-supported zeolite molding of the present invention has a metal component both inside and outside the zeolite crystal.
The type of zeolite for the metal exchange is not particularly limited, but the zeolite structure is selected from those having FAU, BEA, LTL, MOR, MTW, GME, OFF, MFI, MEL, FER, TON, MTT and LTA structures. At least one kind can be used. Among these, FAU, BEA, LTL, MOR, MTW, GME having 12-membered ring pores and zeolite having an OFF structure are preferable.
本発明で用いるゼオライト成型体は、ゼオライトに該成型体全量に基づきバインダー成分を好ましくは５〜５０質量％、より好ましくは１０〜３０質量％の割合で、添加して成型したものが望ましい。この際用いるバインダー成分としてはアルミナ、シリカなどが好ましい。成型を容易にするためにさらにベントナイト、バーミキュライト等の粘土鉱物やセルロースなどの有機添加剤を加えて成型したものを用いてもよい。ゼオライトに上記のバインダーを加えて、押出成型、打錠成型、転動造粒、スプレードライなどの通常の方法で成型してゼオライト成型体にしたものを用いる。このゼオライト成型体の粒径は小さいほど好ましい。 The zeolite molded body used in the present invention is preferably formed by adding a binder component to zeolite based on the total amount of the molded body, preferably in a proportion of 5 to 50 mass%, more preferably 10 to 30 mass%. As the binder component used in this case, alumina, silica and the like are preferable. In order to facilitate molding, a clay mineral such as bentonite and vermiculite, and an organic additive such as cellulose may be used. A zeolite molded product obtained by adding the above binder to zeolite and molding it by an ordinary method such as extrusion molding, tableting molding, rolling granulation, spray drying or the like is used. The smaller the particle size of this zeolite molding, the better.
本発明では、上記ゼオライト成型体に、イオン交換によってゼオライト結晶の内部に金属イオンを担持させ、結晶外部に金属または金属化合物を沈着担持させることによって、結晶内部と外部の両方に金属成分を有する金属担持ゼオライト成型体を製造する。ここで、金属とは金属元素が還元された状態を言い、金属化合物とは、イオン交換していない金属塩や金属酸化物を言う。イオン交換する金属元素としては特に限定されないが、硫黄化合物の吸着除去に用いる場合はＡｇ、Ｃｕ、Ｚｎ及びＮｉが好ましい。 In the present invention, a metal having a metal component both inside and outside the crystal is obtained by supporting metal ions inside the zeolite crystal by ion exchange and depositing or supporting a metal or metal compound on the outside of the crystal. A supported zeolite molding is produced. Here, the metal means a state in which a metal element is reduced, and the metal compound means a metal salt or metal oxide that is not ion-exchanged. Although it does not specifically limit as a metal element to ion-exchange, When using for adsorption removal of a sulfur compound, Ag, Cu, Zn, and Ni are preferable.
ゼオライト結晶中のイオンを金属イオンで交換する方法は、金属イオンを含有する溶液中に上記ゼオライト成型体を入れ、常温から８０℃程度の温度で１〜数時間、接触させる方法で処理する。この時、金属イオン源としては、硝酸塩や塩化物など水溶性の金属塩が使用できる。アンモニア水に溶解させて、金属アンミン錯イオンを形成させた溶液を使用してもよい。イオン交換後、水で洗浄してもよい。更にイオン交換処理を繰り返してもよい。 The method of exchanging the ions in the zeolite crystal with metal ions is performed by placing the zeolite molded body in a solution containing metal ions and bringing them into contact at a temperature of from room temperature to about 80 ° C. for 1 to several hours. At this time, a water-soluble metal salt such as nitrate or chloride can be used as the metal ion source. A solution in which metal ammine complex ions are formed by dissolving in ammonia water may be used. You may wash | clean with water after ion exchange. Further, the ion exchange process may be repeated.
上述の方法でゼオライト結晶内部にイオン交換担持した後、乾燥または焼成を加えても構わないし、乾燥、焼成を行わずに次の沈着担持に移行しても構わない。
次いで、ゼオライト結晶外部へ金属又は金属化合物を沈着担持させる。
沈着担持の方法としては、下記の１）金属成分を含浸させる方法、及び２）金属交換時に溶液の溶解度を低下させて金属化合物を析出させる方法の２種類が挙げられる。
After carrying out ion exchange support inside the zeolite crystal by the above-mentioned method, drying or firing may be added, or the next deposition support may be carried out without performing drying and firing.
Next, a metal or a metal compound is deposited and supported on the outside of the zeolite crystal.
Examples of the deposition supporting method include the following two methods: 1) a method of impregnating a metal component, and 2) a method of precipitating a metal compound by lowering the solubility of a solution during metal exchange.
１）金属成分を含浸させる方法：通常の方法で金属成分を含浸担持すればよい。この場合には、金属成分はゼオライト結晶粒子の間隙やバインダー上に担持される。金属成分の種類は特に限定されないが、Ａｇ、Ｃｕ、Ｎｉ、Ｚｎ、Ｍｎ、Ｆｅ、Ｃｅ、Ｌａ、Ｚｒ及びＴｉが特に好ましい。イオン交換に用いた金属種と同じでもよいし、異なる金属種でもよい。この場合の含浸による金属担持量は、金属担持ゼオライト成型体全量に基づいて、金属成分として、通常０．５〜２０質量％、好ましくは１〜１０質量％である。担持量が多過ぎるとゼオライトの細孔が閉鎖されたり、ゼオライトの構造が崩壊することがある。含浸方法としては、ポアフィリング法、インシピエントウェットネス法、浸漬法及び蒸発乾固法等がある。含浸後、通常の方法で乾燥、焼成を行う。 1) Method of impregnating a metal component: The metal component may be impregnated and supported by an ordinary method. In this case, the metal component is supported on the gap between the zeolite crystal particles or on the binder. The type of the metal component is not particularly limited, but Ag, Cu, Ni, Zn, Mn, Fe, Ce, La, Zr and Ti are particularly preferable. The metal species used for ion exchange may be the same or different metal species. The amount of metal supported by impregnation in this case is usually 0.5 to 20% by mass, preferably 1 to 10% by mass, as a metal component, based on the total amount of the metal-supported zeolite molding. If the amount is too large, the zeolite pores may be closed or the structure of the zeolite may collapse. Examples of the impregnation method include a pore filling method, an incipient wetness method, an immersion method, and an evaporation to dryness method. After impregnation, drying and firing are performed by a usual method.
２）金属交換時に溶液の溶解度を低下させて金属化合物を析出させる方法：金属イオン交換を行い、ゼオライト結晶中に金属イオンを担持させた後に、溶液中の溶解残存している金属化合物を析出させてゼオライト結晶外部やバインダー上に沈着させる。金属化合物を沈着させる方法としては、金属元素の硝酸塩、酢酸塩、塩化物などで金属交換を行っていた場合には、塩基を加えてｐＨを６〜１０．５程度まで上昇させ、金属元素の水酸化物または酸化物としてゼオライト結晶外部に沈着させる。金属アンミン錯イオンで交換する場合には、酸を加えてｐＨを７〜４程度の範囲にして、溶解度を低下させ沈着させる。また水溶性有機化合物を添加して、金属化合物の溶解度を低下させて金属化合物を沈着担持させてもよいし、金属化合物と不溶性の化合物を形成させて、析出させてもよい。例えば，Ａｇ交換の場合には塩化水素、塩化ナトリウムなどの塩化物を加えると、塩化銀が生成し析出させることができる。 2) Method of precipitating a metal compound by lowering the solubility of the solution at the time of metal exchange: After carrying out metal ion exchange and supporting metal ions in zeolite crystals, the metal compound remaining in solution is precipitated. To deposit on the outside of the zeolite crystal or on the binder. As a method for depositing a metal compound, when metal exchange is performed with a nitrate, acetate, chloride, etc. of a metal element, a base is added to raise the pH to about 6 to 10.5, Deposited outside the zeolite crystal as hydroxide or oxide. When exchanging with a metal ammine complex ion, acid is added to bring the pH to a range of about 7 to 4, and the solubility is lowered and deposited. Further, a water-soluble organic compound may be added to reduce the solubility of the metal compound to deposit and carry the metal compound, or an insoluble compound and the metal compound may be formed and precipitated. For example, in the case of Ag exchange, silver chloride can be produced and precipitated by adding chlorides such as hydrogen chloride and sodium chloride.
本発明の別の方法は、ゼオライト結晶に１族または２族元素を担持した後金属交換する方法である。すなわち、ゼオライト成型体を用い、ゼオライト結晶の少なくとも外部に１族または２族に属する金属元素を担持させ、次いでゼオライト結晶内部に金属イオン交換により金属イオンを担持させる際に、ゼオライト結晶の外部に金属又は金属化合物を担持させる方法である。１族または２族元素をゼオライト結晶外部に担持する方法としては、ゼオライト成型体に１族または２族元素をポアフィリング法、インシピエントウェットネス法、浸漬法、蒸発乾固法等の方法でゼオライト結晶外部に担持する。１族または２族元素の一部はゼオライト結晶内部に担持されてもよい。次いで、ゼオライト結晶内部に金属イオン交換により金属イオンを担持させるがこの時、ゼオライト細孔外部に担持された１族または２族元素は交換する金属元素と反応し、交換金属は水酸化物または酸化物としてゼオライト結晶外部に沈着担持させることができる。 Another method of the present invention is a method of exchanging metals after supporting a group 1 or group 2 element on a zeolite crystal. That is, when a zeolite molded body is used, a metal element belonging to Group 1 or Group 2 is supported at least outside the zeolite crystal, and then metal ions are supported inside the zeolite crystal by metal ion exchange. Or it is the method of carrying | supporting a metal compound. As a method of supporting the group 1 or group 2 element outside the zeolite crystal, the group 1 or group 2 element can be supported on the zeolite molding by a pore filling method, an incipient wetness method, an immersion method, an evaporation to dryness method, or the like. It is supported outside the zeolite crystal. A part of the group 1 or group 2 element may be supported inside the zeolite crystal. Next, metal ions are supported inside the zeolite crystal by metal ion exchange. At this time, the group 1 or group 2 element supported outside the zeolite pores reacts with the metal element to be exchanged, and the exchange metal is hydroxide or oxidized. It can be deposited and supported outside the zeolite crystal as a product.
以上のようにして得られた金属担持ゼオライト成型体は、水などで洗浄したのち、通常５００℃以下、好ましくは５０〜２００℃程度の温度で乾燥処理する。乾燥後、通常５００℃以下、好ましくは２００〜５００℃程度の温度、で数時間焼成する。イオン交換担持および沈着担持の合計である金属元素の総担持量は、金属担持ゼオライト成型体全量に基づいて、通常５〜５０質量％、好ましくは１０〜３０質量％である。本発明の金属担持ゼオライト成型体は、従来の金属イオン交換ゼオライトに比べて、金属担持量が多く、また、同じ金属担持量の場合でも、従来の金属イオン交換ゼオライトよりも、脱硫性能にはるかに優れている。 The metal-supported zeolite molding obtained as described above is washed with water or the like, and then dried at a temperature of usually 500 ° C. or lower, preferably about 50 to 200 ° C. After drying, it is fired for several hours at a temperature of usually 500 ° C. or lower, preferably about 200 to 500 ° C. The total supported amount of the metal element, which is the sum of the ion exchange support and the deposition support, is usually 5 to 50% by mass, preferably 10 to 30% by mass, based on the total amount of the metal-supported zeolite compact. The metal-supported zeolite molded body of the present invention has a larger amount of metal supported than conventional metal ion-exchanged zeolite, and even in the case of the same metal supported amount, the desulfurization performance is much higher than that of conventional metal ion-exchanged zeolite. Are better.
本発明の金属担持ゼオライト成型体を硫黄化合物除去用吸着剤として利用することによって、天然ガス、都市ガス、ＬＰＧ、石油化学製品、ナフサ、ガソリン、灯油、軽油などの炭化水素燃料又はジメチルエーテルに含有される硫黄分を吸着除去する。ゼオライト結晶内部にイオン交換された金属イオンは硫化カルボニルを除く硫黄化合物の吸着に優れ、ゼオライト結晶外部に沈着担持された電荷を有しない金属成分（金属又は金属化合物）は硫化カルボニルの吸着に優れる。 By using the metal-supported zeolite molding of the present invention as an adsorbent for removing sulfur compounds, it is contained in hydrocarbon fuel or dimethyl ether such as natural gas, city gas, LPG, petrochemical products, naphtha, gasoline, kerosene, and light oil. To remove the sulfur content. Metal ions ion-exchanged inside the zeolite crystal are excellent in adsorption of sulfur compounds excluding carbonyl sulfide, and a non-charged metal component (metal or metal compound) deposited and supported outside the zeolite crystal is excellent in adsorption of carbonyl sulfide.
硫黄化合物の除去方法は、下記のように気体燃料と液体燃料で異なる。
気体燃料の場合には、供給原料燃料中の硫黄化合物の濃度は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。脱硫条件は、通常温度が−５０℃〜１５０℃の範囲、ＧＨＳＶは１００〜１，０００，０００ｈ-1の範囲の中から選ばれる。脱硫温度が高過ぎると、硫黄化合物の吸着が起こりにくくなる。
The method for removing sulfur compounds differs between gaseous fuel and liquid fuel as described below.
In the case of gaseous fuel, the concentration of the sulfur compound in the feedstock fuel is preferably 0.001 to 10,000 ppm by volume, particularly preferably 0.1 to 100 ppm by volume. The desulfurization conditions are usually selected from a range of -50 ° C to 150 ° C and a range of GHSV of 100 to 1,000,000 h -1 . If the desulfurization temperature is too high, adsorption of sulfur compounds is difficult to occur.
液状燃料の場合には、供給原料燃料中の硫黄化合物の濃度は０．００１〜１０，０００質量ｐｐｍが好ましく、特に０．１〜１００質量ｐｐｍが好ましい。脱硫条件は、通常温度が−５０℃〜１５０℃の範囲、ＷＨＳＶが０．１〜１０００ｈ-1の範囲の中から選ばれる。液体燃料の場合にも、脱硫温度が１５０℃を超えると硫黄化合物の吸着が起こりにくくなる。 In the case of a liquid fuel, the concentration of the sulfur compound in the feedstock fuel is preferably 0.001 to 10,000 mass ppm, particularly preferably 0.1 to 100 mass ppm. The desulfurization conditions are usually selected from the range of -50 ° C. to 150 ° C. and the range of WHSV of 0.1 to 1000 h −1 . Also in the case of liquid fuel, if the desulfurization temperature exceeds 150 ° C., the adsorption of sulfur compounds is difficult to occur.
次に、本発明の燃料電池用水素の製造方法においては、前述の本発明の金属担持ゼオライト成型体からなる硫黄化合物除去用吸着剤を用いて、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 for a fuel cell of the present invention, the sulfur compound in the hydrocarbon fuel or dimethyl ether fuel is desulfurized using the sulfur compound-removing adsorbent comprising the metal-supported zeolite molded body of the present invention. After the treatment, hydrogen is produced by reforming the desulfurized fuel.
この改質方法として、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。この時それぞれの改質で触媒として用いる部分酸化改質触媒、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。各改質触媒の寿命の点から、改質の供給原料の脱硫処理済の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、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。 As this reforming method, methods such as partial oxidation reforming, autothermal reforming, and steam reforming can be used. At this time, the partial oxidation reforming catalyst, autothermal reforming catalyst, and steam reforming catalyst used as the catalyst in each reforming can be appropriately selected and used from the conventionally known catalysts. Nickel-based catalysts are 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. From the viewpoint of the life of each reforming catalyst, the concentration of the sulfur compound in the desulfurized hydrocarbon fuel or dimethyl ether fuel of the reforming feedstock is preferably 0.1 ppm by volume or less, particularly preferably 0.005 ppm by volume or less. Is preferred.
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。 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.
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。 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 .
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。 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、燃料ポンプ２２を経て脱硫器２３に流入する。脱硫器内には本発明の硫黄化合物除去用吸着剤が充填されている。脱硫器２３で脱硫された燃料は水タンクから水ポンプ２４を経た水と混合した後、気化器１に導入されて気化され、次いで空気ブロアー３５から送り出された空気と混合され改質器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ジメチルエーテル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 inside of 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を、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、実施例を用いて本発明を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ない。 EXAMPLES Next, although this invention is demonstrated further in detail using an Example, this invention is not limited at all by these examples.
実施例１
市販のＮａＹ型ゼオライト成型体（東ソー株式会社製ＨＳＺ−３２０ＮＡＤ１Ａ）を砕いて０．５〜１ｍｍの粒径とした。本ゼオライト成型体１ｋｇに、硫酸ナトリウム１１０ｇを水４５０ｇに溶解させた溶液を注いで硫酸ナトリウムの含浸を行った。１２０℃で乾燥した後、５００℃で３時間焼成した。硝酸銀３９４ｇを水２．５Ｌに溶解した。これに、上記Ｎａを含浸したゼオライトを投入し、液を４時間撹拌してＡｇイオン交換を行った。溶液のｐＨは８．８であった。その後、水洗した後、１２０℃で乾燥した。次いで、４００℃で焼成し、イオン交換されたＡｇと沈着されたＡｇを含有するＹ型ゼオライトを得た。Ａｇの含有量は１８．１質量％、Ｎａ含量２．４質量％であった。
Example 1
A commercially available NaY-type zeolite molding (HSZ-320NAD1A manufactured by Tosoh Corporation) was crushed to a particle size of 0.5 to 1 mm. A solution prepared by dissolving 110 g of sodium sulfate in 450 g of water was poured into 1 kg of the zeolite compact, and impregnation with sodium sulfate was performed. After drying at 120 ° C., it was calcined at 500 ° C. for 3 hours. 394 g of silver nitrate was dissolved in 2.5 L of water. The zeolite impregnated with Na was added thereto, and the solution was stirred for 4 hours to perform Ag ion exchange. The pH of the solution was 8.8. Then, after washing with water, it dried at 120 degreeC. Subsequently, it was calcined at 400 ° C. to obtain a Y-type zeolite containing ion-exchanged Ag and deposited Ag. The Ag content was 18.1% by mass and the Na content was 2.4% by mass.
実施例２
市販のＨＹ型ゼオライト成型体（東ソー株式会社製、ＨＳＺ−３２０ＨＯＤ１Ａ）を砕いて０．５〜１ｍｍの粒径とした。硝酸銀３９４ｇを水２．５Ｌに溶解した。これに３０質量％のアンモニア水４００ｇを加え、銀アンミン錯体の溶液を得た。この銀アンミン錯体溶液に上記ゼオライト１ｋｇを投入した。液を４時間撹拌しＡｇイオン交換を行った。溶液のｐＨは８．５であった。次いで３０質量％硝酸溶液を加えて、ｐＨを５に調整した。その後、水洗した後、１２０℃で乾燥した。次いで、４００℃で焼成し、イオン交換されたＡｇと沈着されたＡｇを含有するＹ型ゼオライトを得た。Ａｇの含有量は１５．５質量％、Ｎａ含量０．１質量％であった。
Example 2
A commercially available HY-type zeolite molding (manufactured by Tosoh Corporation, HSZ-320HOD1A) was crushed to a particle size of 0.5 to 1 mm. 394 g of silver nitrate was dissolved in 2.5 L of water. To this, 400 g of 30% by mass aqueous ammonia was added to obtain a silver ammine complex solution. 1 kg of the zeolite was charged into the silver ammine complex solution. The solution was stirred for 4 hours to perform Ag ion exchange. The pH of the solution was 8.5. Subsequently, 30 mass% nitric acid solution was added to adjust the pH to 5. Then, after washing with water, it dried at 120 degreeC. Subsequently, it was calcined at 400 ° C. to obtain a Y-type zeolite containing ion-exchanged Ag and deposited Ag. The Ag content was 15.5% by mass and the Na content was 0.1% by mass.
実施例３
市販のＨＹ型ゼオライト成型体（東ソー株式会社製、ＨＳＺ−３２０ＨＯＤ１Ａ）を砕いて０．５〜１ｍｍの粒径とした。硝酸銀３９４ｇを水２．５Ｌに溶解した。これに上記ゼオライト１ｋｇを投入した。液を４時間撹拌しＡｇイオン交換を行った。溶液のｐＨは３．５であった。次いで、３０質量％アンモニア水を加えて、ｐＨを８に調整した。その後、水洗した後、１２０℃で乾燥した。次いで、４００℃で焼成し、イオン交換されたＡｇと沈着担持されたＡｇを含有するＹ型ゼオライトを得た。Ａｇの含有量は１５．１質量％、Ｎａ含量０．１質量％であった。
Example 3
A commercially available HY-type zeolite molding (manufactured by Tosoh Corporation, HSZ-320HOD1A) was crushed to a particle size of 0.5 to 1 mm. 394 g of silver nitrate was dissolved in 2.5 L of water. 1 kg of the above zeolite was added thereto. The solution was stirred for 4 hours to perform Ag ion exchange. The pH of the solution was 3.5. Subsequently, 30 mass% ammonia water was added and pH was adjusted to 8. Then, after washing with water, it dried at 120 degreeC. Subsequently, it was calcined at 400 ° C. to obtain Y-type zeolite containing ion-exchanged Ag and deposition-supported Ag. The Ag content was 15.1% by mass and the Na content was 0.1% by mass.
実施例４
市販のβ型ゼオライト成型体（東ソー株式会社製、ＨＳＺ−９３０ＨＯＤＡ）を砕いて０．５〜１ｍｍの粒径とした。硝酸銀３９４ｇを水２．５Ｌに溶解した。これに上記ゼオライト１ｋｇを投入した。液を４時間撹拌しＡｇイオン交換を行った。溶液のｐＨは２．７であった。次いで、３０質量％アンモニア水を加えて、ｐＨを７に調整した。その後、水洗した後、１２０℃で乾燥した。次いで、４００℃で焼成し、イオン交換されたＡｇと沈着担持されたＡｇを含有するβ型ゼオライトを得た。Ａｇの含有量は１４．８質量％、Ｎａ含量０．１質量％であった。
Example 4
A commercially available β-type zeolite molded product (manufactured by Tosoh Corporation, HSZ-930HODA) was crushed to a particle size of 0.5 to 1 mm. 394 g of silver nitrate was dissolved in 2.5 L of water. 1 kg of the above zeolite was added thereto. The solution was stirred for 4 hours to perform Ag ion exchange. The pH of the solution was 2.7. Subsequently, 30 mass% ammonia water was added and pH was adjusted to 7. Then, after washing with water, it dried at 120 degreeC. Subsequently, it was calcined at 400 ° C. to obtain β-type zeolite containing ion-exchanged Ag and deposition-supported Ag. The Ag content was 14.8% by mass and the Na content was 0.1% by mass.
実施例５
市販のＮａＹ型ゼオライト成型体（東ソー株式会社製、ＨＳＺ−３２０ＮＡＤ１Ａ）を砕いて０．５〜１ｍｍの粒径とした。硝酸銀３９４ｇを水２．５Ｌに溶解した。これに、上記ゼオライト１ｋｇを投入し、液を４時間撹拌してＡｇイオン交換を行った。溶液のｐＨは６．２であった。水洗、乾燥後、硝酸銀５．９ｇを水５５０ｇに溶解させた溶液を含浸し、次いで、乾燥、焼成を行い、イオン交換されたＡｇと沈着担持されたＡｇを含有するＹ型ゼオライトを得た。Ａｇの含有量は１７．８質量％、Ｎａ含量２．６質量％であった。
Example 5
A commercially available NaY-type zeolite molding (manufactured by Tosoh Corporation, HSZ-320NAD1A) was crushed to a particle size of 0.5 to 1 mm. 394 g of silver nitrate was dissolved in 2.5 L of water. To this, 1 kg of the zeolite was added, and the solution was stirred for 4 hours to perform Ag ion exchange. The pH of the solution was 6.2. After washing with water and drying, impregnation with a solution in which 5.9 g of silver nitrate was dissolved in 550 g of water was performed, followed by drying and calcination to obtain a Y-type zeolite containing ion-exchanged Ag and deposition-supported Ag. The Ag content was 17.8% by mass and the Na content was 2.6% by mass.
比較例１
硝酸ナトリウムを含浸しなかったこと以外は実施例１と同様にＡｇ交換を４時間行った。ついで、乾燥、焼成を行い、イオン交換されたＡｇを含有するＹ型ゼオライトを得た。Ａｇの含有量は１４．５質量％，Ｎａ含量２．７質量％であった。
Comparative Example 1
Ag exchange was carried out for 4 hours in the same manner as in Example 1 except that sodium nitrate was not impregnated. Subsequently, drying and baking were performed to obtain a Y-type zeolite containing ion-exchanged Ag. The Ag content was 14.5% by mass and the Na content was 2.7% by mass.
比較例２
３０質量％硝酸溶液を加なかったこと以外は実施例２と同様にＡｇ交換を４時間行った。ついで、乾燥、焼成を行い、イオン交換されたＡｇを含有するＹ型ゼオライトを得た。Ａｇの含有量は１１．２質量％，Ｎａ含量０．１質量％であった。
Comparative Example 2
Ag exchange was performed for 4 hours in the same manner as in Example 2 except that the 30% by mass nitric acid solution was not added. Subsequently, drying and baking were performed to obtain a Y-type zeolite containing ion-exchanged Ag. The Ag content was 11.2% by mass and the Na content was 0.1% by mass.
実施例６
市販の１３Ｘゼオライト成型体（ユニオン昭和製１３Ｘペレット）を砕いて０．５〜１ｍｍの粒径としたもの１ｋｇを使用したこと以外は実施例５と同様に実施し、イオン交換されたＡｇと含浸担持されたＡｇを含有するＸ型ゼオライトを得た。Ａｇの含有量は１９．８質量％，Ｎａ含量５．７質量％であった。
Example 6
The same procedure as in Example 5 was used, except that 1 kg of a commercially available 13X zeolite molded product (Union Showa 13X pellets) was crushed to a particle size of 0.5 to 1 mm was used, and impregnated with ion-exchanged Ag. An X-type zeolite containing supported Ag was obtained. The Ag content was 19.8% by mass and the Na content was 5.7% by mass.
実施例７
市販のモルデナイト型ゼオライト成型体（東ソー製ＨＳＺ−６４０ＮＡＤ１Ａ）を砕いて０．５〜１ｍｍの粒径としたもの１ｋｇを使用したこと以外は実施例５と同様に実施し、イオン交換されたＡｇと含浸担持されたＡｇを含有するモルデナイト型ゼオライトを得た。Ａｇの含有量は１６．４質量％，Ｎａ含量２．３質量％であった。
Example 7
Except for using 1 kg of a commercially available mordenite-type zeolite molded product (HSZ-640NAD1A manufactured by Tosoh Corp.) to give a particle size of 0.5 to 1 mm, this was carried out in the same manner as in Example 5, and ion-exchanged Ag and A mordenite-type zeolite containing Ag impregnated and supported was obtained. The Ag content was 16.4% by mass and the Na content was 2.3% by mass.
実施例８
市販のＬ型ゼオライト成型体（東ソー製ＨＳＺ−５００Ｋ０Ｄ１Ａ）を砕いて０．５〜１ｍｍの粒径としたもの１ｋｇを使用したこと以外は実施例５と同様に実施し、イオン交換されたＡｇと含浸担持されたＡｇを含有するＬ型ゼオライトを得た。Ａｇの含有量は１５．３質量％，Ｎａ含量２．１質量％であった。
Example 8
Except for using 1 kg of a commercially available L-type zeolite molded product (HSZ-500K0D1A manufactured by Tosoh Corp.) to give a particle size of 0.5 to 1 mm, this was carried out in the same manner as in Example 5, and ion-exchanged Ag and An L-type zeolite containing Ag impregnated and supported was obtained. The Ag content was 15.3% by mass and the Na content was 2.1% by mass.
実施例９
市販のＵＳＹ型ゼオライト成型体（東ソー製ＨＳＺ−３４１ＮＨＤ１Ａ）を砕いて０．５〜１ｍｍの粒径としたもの１ｋｇを使用したこと以外は実施例４と同様に実施し、イオン交換されたＡｇと沈着担持されたＡｇを含有するＵＳＹ型ゼオライトを得た。Ａｇの含有量は１５．１質量％，Ｎａ含量０．１質量％以下であった。
Example 9
Except for using 1 kg of a commercially available USY-type zeolite molded product (HSZ-341NHD1A manufactured by Tosoh Corp.) to obtain a particle size of 0.5 to 1 mm, the same procedure as in Example 4 was carried out. A USY-type zeolite containing Ag deposited and supported was obtained. The Ag content was 15.1% by mass, and the Na content was 0.1% by mass or less.
実施例１０
比較例２のＡｇ交換されたＹ型ゼオライト１００ｇを用いて水５０ｇに硝酸ランタン６水和物１５．６ｇを溶解した溶液を含浸し、乾燥、焼成を行い、イオン交換されたＡｇと含浸担持されたＬａを含有するＹ型ゼオライトを得た。Ａｇの含有量は１０．３質量％，Ｌａ含量４．９質量％であった。
Example 10
100 g of Ag-exchanged Y-type zeolite of Comparative Example 2 was impregnated with a solution of 15.6 g of lanthanum nitrate hexahydrate dissolved in 50 g of water, dried and calcined, and impregnated and supported with ion-exchanged Ag. Y-type zeolite containing La was obtained. The content of Ag was 10.3 mass%, and the La content was 4.9 mass%.
実施例１１
比較例２のＡｇ交換されたＹ型ゼオライト１００ｇを用いて水２００ｇに硝酸セリウム６水和物５６．８ｇを溶解した溶液に浸漬し蒸発乾固させ含浸した。乾燥、焼成を行い、イオン交換されたＡｇと含浸担持されたＣｅを含有するＹ型ゼオライトを得た。Ａｇの含有量は９．１質量％，Ｃｅ含量１４．９質量％であった。
Example 11
Using 100 g of Ag-exchanged Y-type zeolite of Comparative Example 2, it was immersed in a solution prepared by dissolving 56.8 g of cerium nitrate hexahydrate in 200 g of water, evaporated to dryness, and impregnated. Drying and firing were performed to obtain a Y-type zeolite containing ion-exchanged Ag and impregnated Ce. The Ag content was 9.1% by mass, and the Ce content was 14.9% by mass.
実施例１２
比較例２の脱硫剤１００ｇを用いて水５０ｇに硝酸ニッケル６水和物４０．０ｇを溶解した溶液を含浸し、乾燥、焼成を行い、イオン交換されたＡｇと含浸担持されたＮｉを含有するＹ型ゼオライトを得た。Ａｇの含有量は１０．１質量％，Ｎｉ含量７．２質量％であった。
Example 12
100 g of the desulfurizing agent of Comparative Example 2 is used to impregnate a solution of 40.0 g of nickel nitrate hexahydrate in 50 g of water, dried and fired, and contains ion-exchanged Ag and impregnated Ni. Y-type zeolite was obtained. The content of Ag was 10.1% by mass, and the Ni content was 7.2% by mass.
実施例１３
比較例２の脱硫剤１００ｇを用いて水５０ｇに硝酸亜鉛６水和物２４．７ｇを溶解した溶液を含浸し、乾燥、焼成を行い、イオン交換されたＡｇと含浸担持されたＺｎを含有するＹ型ゼオライトを得た。Ａｇの含有量は１０．５質量％，Ｚｎ含量４．４質量％であった。
Example 13
100 g of the desulfurizing agent of Comparative Example 2 is used to impregnate a solution of 24.7 g of zinc nitrate hexahydrate in 50 g of water, dried and fired, and contains ion-exchanged Ag and impregnated Zn. Y-type zeolite was obtained. The content of Ag was 10.5% by mass, and the Zn content was 4.4% by mass.
実施例１４
比較例２の脱硫剤１００ｇを用いて水２００ｇに硝酸ジルコニウム２水和物４５．４ｇを溶解した溶液に浸漬し、蒸発乾固させ含浸した。乾燥、焼成を行い、イオン交換されたＡｇと含浸担持されたＺｒを含有するＹ型ゼオライトを得た。Ａｇの含有量は９．３質量％，Ｚｒ含量１３．７質量％であった。
Example 14
Using 100 g of the desulfurizing agent of Comparative Example 2, it was immersed in a solution of 45.4 g of zirconium nitrate dihydrate in 200 g of water, evaporated to dryness and impregnated. Drying and firing were performed to obtain a Y-type zeolite containing ion-exchanged Ag and impregnated Zr. The Ag content was 9.3% by mass, and the Zr content was 13.7% by mass.
〔金属担持ゼオライトの硫黄化合物吸着性能テスト〕
実施例１〜１４及び比較例１〜２で得られたそれぞれの金属担持ゼオライト３ｃｍ3を内径９ｍｍの脱硫管に充填した。常圧下、温度２０℃で、硫化カルボニル、ジメチルスルフィド、２‐メチル‐２‐プロパンチオール、ジメチルジスルフィドを各１０容量ｐｐｍ（合計４０容量ｐｐｍ）含むプロパンガスを、常圧下、ＧＨＳＶ＝３０００ｈ-1で脱硫管中を流通させた。１０時間後の脱硫管出口ガスの各硫黄化合物濃度をそれぞれＳＣＤ（Ｓｕｌｆｕｒ Ｃｈｅｍｉｌｕｍｉｎｅｓｃｅｎｃｅ Ｄｅｔｅｃｔｏｒ＝硫黄化学発光検出器）ガスクロマトグラフィーにより測定した。表１に各硫黄化合物の脱硫率を示す。
[Sulfur compound adsorption performance test of metal-supported zeolite]
3 cm 3 of each metal-supported zeolite obtained in Examples 1 to 14 and Comparative Examples 1 and 2 was filled in a desulfurization tube having an inner diameter of 9 mm. Propane gas containing carbonyl sulfide, dimethyl sulfide, 2-methyl-2-propanethiol, and dimethyl disulfide 10 ppm by volume (total 40 ppm by volume) under normal pressure at a temperature of 20 ° C. under normal pressure and GHSV = 3000 h −1 . The desulfurization pipe was circulated. The concentration of each sulfur compound in the desulfurization pipe outlet gas after 10 hours was measured by SCD (Sulfur Chemiluminescence Detector = sulfur chemiluminescence detector) gas chromatography. Table 1 shows the desulfurization rate of each sulfur compound.
比較例１及び２では、３０質量％硝酸によるｐＨ調整を行わなかったため、イオン交換だけであり、金属成分がゼオライト結晶内部には存在するが、結晶外部には無い。
この場合には、ジメチルスルフィド、２−メチル−２−プロパンチオール及びジメチルジスルフィドについては十分な脱硫効果を示すものの、硫化カルボニルに対する脱硫効果は不十分である。
これに対して、実施例１〜１４で得られた結晶内部と外部の両方に金属が担持している金属担持ゼオライトはいずれも、ジメチルスルフィド、２−メチル−２−プロパンチオール及びジメチルジスルフィドばかりではなく、硫化カルボニルに対しても十分な脱硫効果があることが分かる。
In Comparative Examples 1 and 2, since pH adjustment with 30% by mass nitric acid was not performed, only ion exchange was performed, and the metal component was present inside the zeolite crystal but not outside the crystal.
In this case, although dimethyl sulfide, 2-methyl-2-propanethiol and dimethyl disulfide have a sufficient desulfurization effect, the desulfurization effect on carbonyl sulfide is insufficient.
On the other hand, all of the metal-supported zeolites in which metals are supported both inside and outside the crystals obtained in Examples 1 to 14 are not only dimethyl sulfide, 2-methyl-2-propanethiol and dimethyl disulfide. It can be seen that there is a sufficient desulfurization effect for carbonyl sulfide.
以上詳細に説明したように、ゼオライト結晶の内部と外部の両方に金属成分を担持させることによって、チオール類やスルフィド類ばかりでなく、従来の銀ゼオライトでは除去できなかった硫化カルボニルまでも効率よく除去できる。ＬＰＧ、都市ガス、ナフサ、灯油、軽油又はエタン、エチレン、プロパン、プロピレン、ブタン、ブテン等の炭化水素燃料及びジメチルエーテル燃料中に含まれる硫黄化合物の効率的な除去が可能になり、この硫黄除去燃料を原料として用いることによって、触媒被毒が極めて少なく部分酸化改質、オートサーマル改質又は水蒸気改質を行うことができ、燃料電池用の水素を効果的に製造できるようになる。 As explained in detail above, by loading metal components both inside and outside the zeolite crystal, not only thiols and sulfides but also carbonyl sulfide that could not be removed by conventional silver zeolite can be removed efficiently. it can. Sulfur compounds contained in hydrocarbon fuels such as LPG, city gas, naphtha, kerosene, light oil or ethane, ethylene, propane, propylene, butane, butene, and dimethyl ether fuel can be efficiently removed. As a raw material, partial poisoning reforming, autothermal reforming or steam reforming can be carried out with very little catalyst poisoning, and hydrogen for fuel cells can be produced effectively.
１： 気化器
２： 燃料電池システム
２０： 水素製造システム
２１： 燃料タンク
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: Vaporizer 2: Fuel cell system 20: Hydrogen production system 21: Fuel tank 23: Desulfurizer 31:
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| JPH04292412A (en) * | 1990-11-02 | 1992-10-16 | Kanebo Ltd | Modified synthetic zeolite and its production |
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| JP4676690B2 (en) * | 2002-11-05 | 2011-04-27 | 出光興産株式会社 | METAL ION EXCHANGE ZEOLITE, PROCESS FOR PRODUCING THE SAME, AND SOLUTION COMPOUND ADSORBENT CONTAINING THE METAL ION EXCHANGE ZEOLITE |
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| KR101394343B1 (en) * | 2012-07-05 | 2014-05-13 | 경북대학교 산학협력단 | Organosulfur adsorbent, its manufacturing method, organosulfur compound adsorption method from petroleum oily, and recycle method of organosulfur adsorbent |
| RU2743434C1 (en) * | 2020-08-10 | 2021-02-18 | Акционерное общество "Волжский научно-исследовательский институт углеводородного сырья" (АО "ВНИИУС") | Method for fine purification of hydrocarbon fractions from dimethyl sulfide |
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