CN1678390A - 脱除硫化合物的吸附剂、生产氢的方法和燃料电池体系 - Google Patents
脱除硫化合物的吸附剂、生产氢的方法和燃料电池体系 Download PDFInfo
- Publication number
- CN1678390A CN1678390A CNA038210339A CN03821033A CN1678390A CN 1678390 A CN1678390 A CN 1678390A CN A038210339 A CNA038210339 A CN A038210339A CN 03821033 A CN03821033 A CN 03821033A CN 1678390 A CN1678390 A CN 1678390A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- sulfur compounds
- hydrogen
- removing sulfur
- cerium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000446 fuel Substances 0.000 title claims abstract description 79
- 239000003463 adsorbent Substances 0.000 title claims abstract description 76
- 150000003464 sulfur compounds Chemical class 0.000 title claims abstract description 65
- 239000001257 hydrogen Substances 0.000 title claims abstract description 61
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 54
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 38
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 36
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000002407 reforming Methods 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000002453 autothermal reforming Methods 0.000 claims abstract description 10
- 238000000629 steam reforming Methods 0.000 claims abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 claims description 33
- 230000023556 desulfurization Effects 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000011164 primary particle Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 5
- 239000003345 natural gas Substances 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 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
- 150000003568 thioethers Chemical class 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 239000001273 butane Substances 0.000 claims description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- 229910000037 hydrogen sulfide 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
- 229910052696 pnictogen Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000002594 sorbent Substances 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 150000003577 thiophenes Chemical class 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 2
- 239000002245 particle Substances 0.000 description 33
- 239000003795 chemical substances by application Substances 0.000 description 30
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 25
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 241000894007 species Species 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 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 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000010944 silver (metal) Substances 0.000 description 4
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission 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
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 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
- 238000002309 gasification Methods 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
- 238000005470 impregnation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
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- 238000011084 recovery Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910004625 Ce—Zr Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 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
- 240000007594 Oryza sativa Species 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
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- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
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- 229910008341 Si-Zr Inorganic materials 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 239000002826 coolant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction 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
- -1 dimethyl ether Chemical class 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
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- WXEHBUMAEPOYKP-UHFFFAOYSA-N methylsulfanylethane Chemical compound CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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Abstract
一种用于脱除硫化合物的吸附剂,它甚至在室温下也能从烃类燃料中有效地脱除各种硫化合物到低浓度;一种有效地生产可用于燃料电池的氢的方法和一种利用所述方法制得的氢的燃料电池体系。具体地说,一种含有氧化铈的用于从烃类燃料脱除硫化合物的吸附剂;一种生产用于燃料电池的氢的方法,所述的方法包含用上述吸附剂使烃类燃料脱硫,以便脱除硫化合物,然后将如此脱硫的燃料与部分氧化重整催化剂、自热重整催化剂或蒸汽重整催化剂接触,从而生产用于燃料电池的氢;以及一种利用所述方法制得的氢的燃料电池体系。
Description
技术领域
本发明涉及一种用于脱除硫化合物的吸附剂,涉及一种生产氢的方法以及涉及一种燃料电池体系。更具体地说,本发明涉及这样一种用于脱除硫化合物的吸附剂,所述的吸附剂甚至在室温下也能有效地将烃类燃料中所含的各种硫化合物脱除到低浓度;涉及一种从已用所述的吸附剂脱硫的烃类燃料有效地生产可用于燃料电池的氢的方法;以及涉及一种使用通过所述的方法生产的氢的燃料电池体系。
背景技术
近年来,从环境问题的观点出发,各种新型的能源生产技术已受到注意,在这些技术中,燃料电池已引起特别的兴趣。燃料电池通过氢和氧的电化学反应将化学能转化成电能,得到高的能源利用效率。所以,已对燃料电池在民用、工业应用、汽车等方面应用的实现进行了广泛研究。
燃料电池根据使用电解质的类型分类,已知有磷酸盐类型、熔融碳酸盐类型、固体氧化物类型和固体聚合物类型。就氢源来说,已对甲醇;主要含甲烷的液化天然气;主要含天然气的城市煤气;天然气作为原料生产的合成液体燃料以及石油生产的烃类例如液化石油气、石脑油和煤油进行了研究。
当由这些气体或液体烃类生产氢时,烃类通常在转化催化剂存在下进行部分氧化转化、自热转化或水蒸汽转化。
当烃类燃料例如液化石油气、城市煤气或煤油进行转化以便生产用作燃料的氢时,必需将烃类燃料的硫含量下降到0.1ppm或更低,以便防止转化催化剂中毒。当烃类例如丙烯或丁烯用作生产石油化工产品的原料时,必需将烃类燃料的硫含量下降到0.1ppm或更低,以便防止转化催化剂中毒。
上述液化石油气通常含有硫化合物例如甲基硫醇和羰基硫化物(COS)以及恶臭物质例如二甲基硫醚(DMS)、叔丁基硫醇(TBM)或有意加入其中的甲基乙基硫醚。最近,各种研究努力集中到含氧的烃类化合物例如二甲基醚作为燃料的利用上。虽然在含氧的烃类化合物中不含有硫化合物,但对上述恶臭物质有意加到烃类化合物中进行了研究,因为所述的恶臭物质可有效地警告气体的泄漏。
已经知道各种吸附剂,它们可吸附烃类燃料例如液化石油气或城市煤气中所含的硫化合物的,以致从所述的燃料中脱除这些化合物。虽然某些已知的吸附剂在约150℃至约300℃下有极好的脱硫性能,但目前在室温下得到的脱硫性能是不能令人满意的。
已公开了一些脱硫剂;例如含有憎水沸石和通过离子交换负载其上的金属元素例如Ag、Cu、Zn、Fe、Co或Ni的脱硫剂(例如参见日本专利申请公开(kokai)2001-286753)和含有Y型沸石、β型沸石或X型沸石和负载其上的Ag或Cu的脱硫剂(例如参见日本专利申请公开(kokai)2001-305123)。这些吸附剂在室温下有效地吸附燃料中所含的硫醇类和硫醚类,以致从所述的燃料中脱除硫化合物,但它们实际上不吸附羰基硫化物。
还公开了铜-锌脱硫剂(例如参见日本专利申请公开(kokai)2-302496)。虽然所述的脱硫剂在150℃或更高的温度下吸附各种硫化合物,以致脱除这些化合物,但是在100℃或更低的温度下硫化合物的吸附性能不能令人满意。还公开了含多孔载体(例如氧化铝)和负载其上的铜的脱硫剂(例如参见日本专利延迟公开申请书(kokai)2001-123188)。所述的脱硫剂也可在100℃或更低的温度下使用,但是它的吸附性能仍不够好。
发明内容
在这样的情况下,本发明的一个目的是要提供这样一种用于脱除硫化合物的吸附剂,所述的吸附剂甚至在室温下也可有效地将烃类燃料中所含的各种硫化合物脱除到低浓度。本发明的另一目的是要提供一种从使用所述吸附剂脱硫的烃类燃料有效生产可用于燃料电池的氢的方法。本发明的另一目的是要提供一种使用通过所述方法生产的氢的燃料电池体系。
为了达到上述这些目的,本发明人进行了广泛的研究,并已发现氧化铈特别是平均晶体粒度为10纳米或更小的氧化铈甚至在室温下仍有极好的吸附各种硫化合物的性能,以及可通过已用所述的吸附剂脱硫的烃类燃料的转化有效地生产用于燃料电池的氢。本发明已在这些发现的基础上实现。
因此,本发明提供以下内容。
(1)一种脱除烃类燃料中硫化合物的吸附剂,其特征是所述的吸附剂含有氧化铈。
(2)一种如上述(1)中所述的脱除硫化合物的吸附剂,其中所述吸附剂的比表面积为20米2/克或更大。
(3)一种如上述(1)中所述的脱除硫化合物的吸附剂,其中所述吸附剂的比表面积为50米2/克或更大。
(4)一种如上述(1)中所述的脱除硫化合物的吸附剂,其中氧化铈主颗粒的平均晶体粒度为10纳米或更小。
(5)一种如上述(1)中所述的脱除硫化合物的吸附剂,其中氧化铈的累积氢消耗量为200微摩尔/克或更大,在程序升温还原试验中直到600℃的计算得到的。
(6)一种如上述(1)中所述的脱除硫化合物的吸附剂,其中氧化铈的累积氢消耗量为300微摩尔/克或更大,在程序升温还原试验中直到600℃的计算得到的。
(7)一种如上述(1)中所述的脱除硫化合物的吸附剂,其中吸附剂含有氧化铈和至少一种选自Al2O3、SiO2、TiO2、ZrO2和MgO的氧化物的混合物。
(8)一种如上述(1)中所述的脱除硫化合物的吸附剂,其中吸附剂还含有至少一种选自周期表的第1至第15族元素的元素,所述的至少一种元素负载在氧化铈上。
(9)一种如上述(8)中所述的脱除硫化合物的吸附剂,其中至少一种选自周期表第1至第15族元素的元素负载其上的氧化铈在400℃或更低的温度下焙烧。
(10)一种如上述(8)中所述的脱除硫化合物的吸附剂,其中按吸附剂的总量计,至少一种选自周期表第1至第15族元素的元素的负载化合物(还原成对应的金属元素)的数量为1-90%(质量)。
(11)一种如上述(1)中所述的脱除硫化合物的吸附剂,其中氧化铈为含有铈和至少一种选自周期表第2至第16族元素的不同于铈的金属元素的复杂氧化物。
(12)一种如上述(1)中所述的脱除硫化合物的吸附剂,其中烃类燃料为液化石油气、城市煤气、天然气、石脑油、煤油、瓦斯油或至少一种选自乙烷、乙烯、丙烷、丙烯、丁烷、丁烯、甲醇和二甲醚的烃类化合物或含氧的烃类化合物。
(13)一种生产氢的方法,其特征是所述的方法包含通过使用上述(1)的吸附剂脱除烃类燃料中所含的含硫化合使烃类燃料脱硫,随后将脱硫的燃料与部分氧化重整催化剂、自热重整催化剂或蒸汽重整催化剂接触。
(14)一种如上述(13)中所述的生产氢的方法,其中部分氧化重整催化剂、自热重整催化剂或蒸汽重整催化剂含有钌或镍。
(15)一种如上述(13)中所述的生产氢的方法,其中在不加入氢或氧的条件下进行脱硫。
(16)一种如上述(13)中所述的生产氢的方法,其中硫化合物为至少一种选自羰基硫化物、二硫化碳、硫化氢、硫醇类、硫醚类和噻吩类的化合物。
(17)一种如上述(13)中所述的生产氢的方法,其中脱硫在200℃或更低的温度下进行。
(18)一种如上述(13)中所述的生产氢的方法,其中脱硫在100℃或更低的温度下进行。
(19)一种燃料电池体系,其特征是使用通过上述(13)-(18)中任一项的生产氢的方法生产的氢。
附图简介
图1为本发明例证性燃料电池体系的示图。
实施本发明的最好方式
本发明用于脱除硫化合物的吸附剂含有氧化铈,用于脱除烃类燃料中所含的各种硫化合物。
硫化合物的例子包括羰基硫化物、二硫化碳、硫化氢、硫醇类、硫醚类和噻吩类。
对本发明吸附剂中所含的氧化铈的类型没有特殊的限制,吸附剂的例子包括如下:
(a)一种仅包含氧化铈或含有铈和一种不同于铈的元素的复杂氧化物(下文称为Ce-M复杂氧化物)的吸附剂;
(b)一种包含氧化铈或Ce-M复杂氧化物与其他金属氧化物的混合物的吸附剂;
(c)一种包含氧化铈或Ce-M复杂氧化物制成的载体与负载其上的活性金属物种的混合物的吸附剂;
(d)一种包含氧化铈或Ce-M复杂氧化物制成的载体和另外一种金属氧化物以及负载其上的活性金属物种的混合物的吸附剂;
(e)一种包含难熔的多孔载体和负载其上的氧化铈或Ce-M复杂氧化物的吸附剂;以及
(f)一种包含难熔的多孔载体和氧化铈或Ce-M复杂氧化物以及负载其上的活性金属物种的吸附剂。
用于形成上述Ce-M复杂氧化物的不同于铈的元素为至少一种选自周期表第2至第16族元素的金属元素。Ce-M复杂氧化物的具体例子包括Ce-Si复杂氧化物、Ce-Zr复杂氧化物和Ce-Si-Zr复杂氧化物。
在上述(b)或(d)中,优选用于与氧化铈或Ce-M复杂氧化物组合的金属氧化物的例子包括选自La、Sc、Y、Nd、Pr、Sm、Gd和Yb的金属的氧化物。这些金属氧化物可单独使用或两种或两种以上物种组合使用。
负载在上述(c)或(d)中的载体上的活性金属物种可选自周期表第1至第15族元素。具体的例子包括Cs、Ba、Yb、Ti、Zr、Hf、Nb、Mo、W、Mn、Re、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Ga、In、Sn和Bi。这些元素可单独使用或两种或两种以上组合使用。对这些元素的形式没有特殊的限制,氧化物、金属和其他物种都可使用。对于烃类燃料中所含的某种类型和数量的硫化合物来说,在这些元素中,Ag、Cu、Ni、Fe、Mn等是优选的。
通过将上述活性物种结合到氧化铈或Ce-M复杂氧化物制成的载体或氧化铈或Ce-M复杂氧化物和其他金属氧化物制成的载体中,可提高生产的吸附剂的脱硫性能。
对上述负载的活性金属物种的数量(按还原成金属元素计)没有特殊的限制,按活性金属物种数量和载体数量的总和计,所述的数量通常为1-90%(质量)、优选3-80%(质量)。
用于上述(e)或(f)的难熔多孔载体的例子包括氧化硅、氧化铝、氧化硅-氧化铝、氧化钛、氧化锆、沸石、氧化镁、硅藻土、石膏粉和白土。这些物种可单独使用或两种或组合使用。
上述难熔多孔载体和负载其上的氧化铈或Ce-M复杂氧化物制成的吸附剂也优选用于本发明。
从脱硫性能的观点出发,本发明的吸附剂优选含有其数量为3%(质量)或更多、更优选10%(质量)或更多的氧化铈。
从脱硫性能的观点出发,吸附剂中所含的氧化铈的平均晶体粒度优选为10纳米或更小、更优选1-10纳米。氧化铈的平均晶体粒度可在吸附剂的制备过程中控制。
本文使用的术语吸附剂中所含的氧化铈的“平均晶体粒度”指在透射电子显微镜下测量的粒度。颗粒不必是结晶的,粒度指一次粒度,不管颗粒是结晶的或是无定形的。术语“一次颗粒”指未团聚的颗粒或作为团聚物的单位碎片的颗粒。甚至当一次颗粒团聚形成二次颗粒、三次颗粒或更高的团聚颗粒时,也应将氧化铈的平均晶体粒度理解为是指氧化铈的一次粒度。在所观测的颗粒有不均匀尺寸的情况下,选择10个或更多的任意一次颗粒,将粒度平均,从而得到平均晶体粒度。在包含棒状或针状颗粒的情况下,由颗粒的宽度(较短的尺寸)而不是由长度(较长的尺寸)得到每一个粒度。当氧化铈负载在载体例如氧化铝上时,CeO2的平均晶体粒度指负载氧化铈的一次粒度。当氧化铈与其他氧化物形成固体溶液时,平均晶体粒度指含铈的固体溶液颗粒的一次粒度。在透射电子显微镜下观测的上述粒度测定中,当颗粒与其他的明显不同时,可使用自动计数器来测定粒度。
从脱硫性能的观点出发,上述氧化铈的累积氢消耗量优选为200微摩尔/克或更大、更优选300微摩尔/克或更大,在程序升温还原试验(TPR)中直到600℃计算的。在氧化铈的程序升温还原试验中,将样品(100毫克)在升温速率10℃/分下加热到827℃,同时将氢(氩中10%(体积))以20毫升/分的速率送入,并计算直到600℃的累积氢消耗量。
在氧化铈的TPR中,在低温区(约300至550℃)和高温区(827℃或更高)分别观测到两个属于还原(H2消耗)的峰。当氧化铈被氢还原时,CeO2按以下反应图示转化成Ce2O3。
在两个TPR峰中,在低温区观测到的峰可能属于构成CeO2颗粒表面氧的还原,而在高温区观测到的峰可能属于整体CeO2的还原。本发明人的研究揭示,低温区内的峰(即氢消耗)越大,所述的氧化铈在室温下的脱硫性能就越好。虽然原因还未完全清楚,但是一个可能的原因是,在约300至550℃(即还原)下与H2反应的氧化铈的氧原子在室温下与硫化合物反应,从而化学吸附硫化合物。
从脱硫性能的观点出发,本发明的吸附剂的比表面积优选为20米2/克或更大、更优选50米2/克或更大。吸附剂的比表面积例如可用比表面积测量仪(Yuasa Ionics Inc.的产品)通过以下步骤来测定。
具体地说,将样品(约100毫克)装入样品管;作为预处理,在氮气流中在200℃下加热20分钟进行脱水。随后,将脱水的样品与气体混合物(氮(30%)/氦(70%))流在液氮温度下接触,以便使样品吸附氮。然后将吸附的氮脱附,用TCD检测器测定脱附氮的数量,从而测定样品的比表面积。
本发明的吸附剂可通过以下步骤来生产。在吸附剂仅由氧化铈制成的情况下,将含有铈源(例如硝酸铈)的水溶液与碱性水溶液接触,从而生成沉积物。通过过滤分离沉积的固体,用水洗涤,然后在约50至200℃下干燥。将干燥的产品在约250至500℃下焙烧,随后模化(例如造粒或挤条)和粉碎成所需的粒度。
可通过传统的已知方法将氧化铈负载在难熔的多孔载体上,例如孔填充、浸渍或蒸发至干。在这种情况下,干燥温度通常为约50至200℃,而焙烧温度通常为约250至500℃。
同样,也可通过上述传统的已知方法将上述活性金属物种负载在氧化铈或类似的化合物制成的载体上,例如孔填充、浸渍或蒸发至干。在这种情况下,干燥温度通常为约50至200℃,而焙烧温度优选为400℃或更低、更优选100-400℃。
本发明如此制备的用于脱除硫化合物的吸附剂用于烃类燃料脱硫。烃类燃料的例子包括液化石油气、城市煤气、天然气、石脑油、煤油、瓦斯油、选自乙烷、乙烯、丙烷、丙烯、丁烷和丁烯的烃类化合物以及含氧的烃类化合物。含氧的烃类化合物可为选自醇类例如甲醇、乙醇和异丙醇以及醚类例如二甲基醚和甲基乙基醚中的至少一种物种。其中,二甲基醚是特别优选的。
要用本发明吸附剂处理的含烃类燃料的气体的硫化合物浓度优选为0.001至10000ppmv、特别优选0.1-100ppmv。脱硫通常在50-200℃的温度和100-1000000小时-1的GHSV(气时空速)下进行。
当脱硫温度高于200℃时,硫化合物不易吸附。因此,脱硫温度优选为-50至120℃、更优选-20至100℃,而GHSV优选为100-100000小时-1、更优选100-50000小时-1。
当脱硫在氢存在下进行时,某些负载的金属物种可提高脱硫性能。但是,在本发明催化剂存在下的脱硫过程中,氢的加入不是必不可少的。氧的加入应当避免,以便防止可能的烃类燃料的燃烧(氧化)。
根据本发明生产可用于燃料电池的氢的方法,使用本发明上述的吸附剂使烃类燃料进行脱硫,以便脱除硫化合物,并将脱硫的燃料转化,从而生产氢气。
可用部分氧化转化、自热转化或水蒸汽转化来进行转化。从每种转化催化剂的使用寿命的观点出发,转化时,脱硫的烃类燃料的硫化合物浓度优选为0.1ppmv或更低、特别优选0.05ppmv或更低。
部分氧化转化为一种在部分氧化重整催化剂存在下通过烃类的部分氧化来生产氢的方法。通常使用的条件如下:反应压力为常压至5兆帕,反应温度为400-1100℃,GHSV为1000-100000小时-1和氧(O2)/碳比为0.2-0.8。
自热转化为一种在自热重整催化剂存在下的部分氧化转化和水蒸汽转化的组合方法。通常使用的条件如下:反应压力为常压至5兆帕,反应温度为400-1100℃,氧(O2)/碳比为0.1-1,水蒸汽/碳比为0.1-10和GHSV为1000-100000小时-1。
水蒸汽转化为一种在蒸汽重整催化剂存在下通过烃类与水蒸汽接触来生产氢的方法。通常使用的条件如下:反应压力为常压至3兆帕,反应温度为200-900℃,水蒸汽/碳比为1.5-10和GHSV为1000-100000小时-1。
在本发明中,上述的部分氧化重整催化剂、自热重整催化剂和蒸汽重整催化剂可从传统的已知催化剂中恰当地选择。其中,含钌的催化剂和含镍的催化剂是特别优选的。优选的催化剂载体的例子包括至少一种选自氧化锰、氧化铈和氧化锆的物种。载体可仅由金属氧化物制成。例如,上述金属氧化物中任何一种都可加到难熔的多孔无机氧化物例如氧化铝中,从而作为载体。
本发明还提供一种使用上述方法生产的氢的燃料电池体系。本发明的燃料电池体系随后参考附图1进行描述。
图1为本发明的一个例证性燃料电池体系的示图。如图1所示,将燃料罐21中所装的燃料通过燃料泵22送入脱硫反应器23。本发明的吸附剂可装入脱硫反应器。已通过脱硫反应器23脱硫的燃料与由水罐通过水泵24送入的水混合,然后将燃料混合物送入气化反应器1,以便使混合物气化。将燃料混合物气体与空气鼓风机35送入的空气混合,然后将气体送入转化设备31。
将上述转化催化剂装入转化设备31。通过上述转化反应中任何一个反应,由送入转化设备31的燃料混合物(含有水蒸汽、氧和烃类燃料或含氧的烃类燃料的气体混合物)生产氢或合成气。
将如此生产的氢或合成气送入CO转化反应器32和/或CO选择氧化反应器33使CO浓度下降,以致不会影响生产的燃料电池的特性。用于CO转化反应器32的催化剂例子包括铁-铬催化剂、铜-锌催化剂和贵金属催化剂。用于CO选择氧化反应器33的催化剂例子包括钌催化剂、铂催化剂及其混合物。
燃料电池34为一种聚合物电解质燃料电池,它包含一个负电极34A、一个正电极34B和在它们之间的聚合物电解质34C。将通过上述方法生产的富氢气体送入负电极,同时通过空气鼓风机35将空气送入正电极。如果需要,在送入电极以前,将这些气体进行适当增湿(借助加湿器,未示出)。
在负电极中,氢解离成质子和电子,而在正电极中,氧与电子和质子反应生成水,从而在电极34A和34B之间产生直流电流。负电极由铂黑、铂/活性炭催化剂、Pt-Ru合金催化剂等制成。正电极由铂黑、铂/活性炭催化剂等制成。
当转化设备31的燃烧器31A与负电极34A相连时,过量的氢可用作燃料。在与正电极34B相连的液/气分离器36中,排放气体与送入正电极34B的空气中所含的氧和氢生成的水分离。分离的水可用来制成水蒸汽。
值得注意的是,因为燃料电池34在产生电能的过程中产生热量,所以通过废热回收设备37来回收热量,以便有效地利用回收热。废热回收设备37包含一个用于吸收反应过程中产生的热量的换热器37A;一个用于将换热器37A中吸收的热量转移到水中的换热器37B;一个冷却器37C和一个用于将冷却介质循环到换热器37A和37B和冷却器37C的泵37D。可将换热器37B中得到的热水有效地用于其他设备。
实施例
下文通过实施例更详细地描述本发明,所述的实施例不应作为对本发明的限制。
用TPP试验(≤600℃)测定氧化铈的平均晶体粒度、累积氢消耗量,而根据本说明书所述的方法测定实施例中生产的脱硫剂的比表面积。
实施例1
在搅拌下,将NaOH水溶液(3摩尔/升)滴加到溶于加热到50℃的离子交换水(用离子交换树脂膜纯化的水,1升)中的六水合硝酸铈(特种试剂级,Wako Pure Chemical Industries,Ltd.产品)(470克)溶液中,以便将混合溶液的pH值调节到13。将混合溶液在恒定的50℃下继续搅拌1小时。
随后,过滤分离出生成的固体,用离子交换水(20升)洗涤,然后用带鼓风机的烤箱将洗涤的产品在110℃下干燥12小时。将干燥的产品在350℃下焙烧3小时。将焙烧的产品造粒和粉碎,从而生产由粒度为0.5-1.0毫米的CeO2(A)制成的用于脱除硫化合物的吸附剂(下文简称为脱硫剂)。所述脱硫剂的性质列入表1。
实施例2
在搅拌下,将氨溶液(30%(质量))滴加到溶于加热到50℃的离子交换水(1升)中的六水合硝酸铈(特种试剂级,Wako Pure ChemicalIndustries,Ltd.产品)(470克)溶液中,以便将混合溶液的pH值调节到12。将混合溶液在恒定的50℃下继续搅拌1小时。
随后,过滤分离出生成的固体,用离子交换水(20升)洗涤,然后用带鼓风机的烤箱将洗涤的产品在110℃下干燥12小时。将干燥的产品在350℃下焙烧3小时。将焙烧的产品造粒和粉碎,从而生产由粒度为0.5-1.0毫米的CeO2(B)制成的用于脱除硫化合物的吸附剂。所述脱硫剂的性质列入表1。
实施例3
将六水合硝酸铈(特种试剂级,Wako Pure Chemical Industries,Ltd.产品)(605克)和二水合硝酸锆(特种试剂级,Wako Pure ChemicalIndustries,Ltd.产品)(52.0克)溶于加热到50℃的离子交换水(1升)中,从而生产制剂液体A。单独制备3N NaOH溶液,作为制剂液体B。在搅拌下,将制剂液体B滴加到制剂液体A中,以便将混合溶液的pH值调节到13.9。将混合溶液在恒定的50℃下继续搅拌1小时。
随后,用离子交换水洗涤生成的固体,过滤分离,然后用带鼓风机的烤箱将分离的产品在110℃下干燥12小时。将干燥的产品在400℃下焙烧3小时。将焙烧的产品造粒和粉碎,从而生产由平均粒度为0.8毫米的CeO2和ZrO2的混合物(质量比50∶50,CeO2(50)-ZrO2(50))制成的吸附剂。所述脱硫剂的性质列入表1。
实施例4
将六水合硝酸铈(特种试剂级,Wako Pure Chemical Industries,Ltd.产品)(310克)溶于加热到50℃的离子交换水(60毫升)中。将氧化铝(KHD-24)(400克)加到溶液中,以便用所述的溶液浸渍氧化铝。用带鼓风机的烤箱将溶液浸渍的氧化铝在110℃下干燥12小时。将干燥的产品在400℃下焙烧3小时。将焙烧的产品造粒和粉碎,从而生产由平均粒度为0.5-1.0毫米的CeO2(20)/Al2O3(80)(Al2O3载体(80质量份)负载CeO2(20质量份))制成的脱硫剂。所述脱硫剂的性质列入表1。
对比例1
将实施例2生产的CeO2(B)放入马弗炉中,并在800℃下焙烧6小时,从而生产CeO2(C)制成的脱硫剂。所述脱硫剂的性质列入表1。
对比例2-6
将MnO2、ZnO、氧化铝、β型沸石和活性炭的商业产品分别用作对比例2-6的脱硫剂。这些脱硫剂的比表面积列入表1。
试验实施例1
将实施例1-4和对比例1-6生产的每种脱硫剂模化和造粒,使粒度为0.5-1毫米。将脱硫剂(1毫升)装入脱硫管(内径:9毫米)。将COS、甲硫醚(DMS)、叔丁基硫醇(TBM)和二甲基二硫醚(DMDS)(每种10ppmv,总计40ppmv)加到丙烷气体中,将所述的硫化合物的气体在以下条件下流过所述的脱硫管:脱硫剂的温度为20℃,常压,GHSV(气时空速)为30000小时-1。
每小时用装有SCD(硫化学发光检测器)的色谱仪测定脱硫管出口处的每种硫化合物的浓度。硫化合物浓度超过0.1ppmv的时间和吸附硫的总量列入表2。
表1
脱硫剂的组分 | 脱硫剂的比表面积(米2/克) | CeO2 | ||
平均晶体粒度(纳米) | 氢消耗量[≤600℃](微摩尔/克CeO2) | |||
实施例1 | CeO2(A) | 147 | 5 | 466 |
实施例2 | CeO2(B) | 121 | 3 | 326 |
对比例1 | CeO2(C) | 21 | 20-100 | 102 |
实施例3 | CeO2(50)-ZrO2(50) | 125 | 10 | 2,540 |
实施例4 | CeO2(20)/Al2O3(80) | 204 | 10 | 1,665 |
对比例2 | MnO2 | 301 | ||
对比例3 | ZnO | 18 | ||
对比例4 | 氧化铝 | 271 | (6)* | |
对比例5 | β型沸石 | 638 | ||
对比例6 | 活性炭 | 1,080 |
*():每克氧化铝的数值
表2
浓度超过0.1ppm的时间(小时) | 吸附硫的总量(硫克/毫升) | |
实施例1 | 5 | 1.42 |
实施例2 | 5 | 1.03 |
对比例1 | 2 | 0.70 |
实施例3 | 3 | 0.95 |
实施例4 | 2 | 0.62 |
对比例2 | 0 | 0.11 |
对比例3 | 0 | 0.19 |
对比例4 | 0 | 0.38 |
对比例5 | 0 | 0.53 |
正如从表1和2清楚看到的,对比例中多孔材料制成的脱硫剂难以使硫化合物的浓度下降到0.1ppm以下。但是,实施例中含有特定氧化铈的脱硫剂有显著的脱硫性能。
实施例5-10
氧化铈(A)用表3所示的每一种金属的盐浸渍,随后在120℃下干燥和在400℃下焙烧,从而生成含有负载金属元素的脱硫剂(表3所示),其数量相对于脱硫剂的总量为10%(质量)。
对比例7
由β型沸石生产脱硫剂,Ag负载其上,相对于脱硫剂的总量其数量为10%(质量)。
试验实施例2
将实施例5-10和对比例7生产的每种脱硫剂模化和造粒,使粒度为0.5-1毫米。将脱硫剂(1毫升)装入脱硫管(内径:9毫米)。将含有COS(40ppmv)的丙烷气在以下条件下流过所述的脱硫管:脱硫剂的温度为20℃,环境压力,GHSV为30000小时-1。
每小时用装有SCD(硫化学发光检测器)的色谱仪测定脱硫管出口处的每种硫化合物的浓度。硫化合物浓度超过0.1ppmv的时间和吸附硫的总量列入表3。
表3
载体类型 | 负载的金属 | COS浓度超过0.1ppmv的时间(小时) | ||
金属 | 数量(%(质量)) | |||
实施例5 | CeO2(A) | - | - | 9 |
实施例6 | CeO2(A) | Ag | 10 | 15 |
实施例7 | CeO2(A) | Cu | 10 | 11 |
实施例8 | CeO2(A) | Ni | 10 | 15< |
实施例9 | CeO2(A) | Fe | 10 | 15 |
实施例10 | CeO2(A) | Mn | 10 | 15< |
对比例7 | β沸石 | Ag | 10 | 0 |
正如从表3清楚看到的,Ni/CeO2和Mn/CeO2可有效地脱除羰基硫化物。
实施例11-15
氧化铈(A)用硝酸银溶液浸渍,以便将Ag负载在氧化铈上,相对于总量其数量为10%(质量)。将含Ag的氧化铈在120℃下干燥(焙烧),然后进一步在表4所示的每一温度下焙烧,从而生成脱硫剂。
试验实施例3
将实施例11-15生产的每种脱硫剂模化和造粒,使粒度为0.5-1毫米。将脱硫剂(1毫升)装入脱硫管(内径:9毫米)。将含有二甲基硫醚(DMS)(40ppmv)的丙烷气在以下条件下流过所述的脱硫管:脱硫剂的温度为20℃,环境压力,GHSV为30000小时-1。
每小时用装有SCD(硫化学发光检测器)的色谱仪测定脱硫管出口处的二甲基硫醚的浓度。硫化合物浓度超过0.1ppmv的时间和吸附硫的总量列入表4。
表4
载体类型 | 负载的金属 | 焙烧温度(℃) | DMS浓度超过0.1ppmv的时间(小时) | ||
金属 | 数量(%(质量)) | ||||
实施例11 | CeO2(A) | Ag | 10 | 500 | 6 |
实施例12 | CeO2(A) | Ag | 10 | 400 | 10 |
实施例13 | CeO2(A) | Ag | 10 | 300 | 12 |
实施例14 | CeO2(A) | Ag | 10 | 200 | 13 |
实施例15 | CeO2(A) | Ag | 10 | 120 | 14 |
正如从表4清楚看到的,在120-500℃的焙烧温度内,焙烧温度越低,使二甲基硫醚的浓度超过0.1ppmv的时间越长。这一趋势表明随着焙烧温度下降吸附硫的数量增加。
工业应用
本发明可提供一种用于脱除硫化合物的吸附剂,所述的吸附剂甚至在室温下也能有效地将烃类燃料中所含的硫化合物脱除到低浓度;提供一种从已用所述的吸附剂脱硫的烃类燃料有效地生产可用于燃料电池的氢的方法;以及提供一种使用由所述的方法生产的氢的燃料电池体系。
Claims (19)
1.一种用于脱除烃类燃料中硫化合物的吸附剂,其特征在于该吸附剂含有氧化铈。
2.根据权利要求1的用于脱除硫化合物的吸附剂,其中吸附剂的比表面积为20米2/克或更大。
3.根据权利要求1的用于脱除硫化合物的吸附剂,其中吸附剂的比表面积为50米2/克或更大。
4.根据权利要求1的用于脱除硫化合物的吸附剂,其中氧化铈的一次颗粒平均晶体粒度为10纳米或更小。
5.根据权利要求1的用于脱除硫化合物的吸附剂,其中在程序升温还原试验中直到600℃计算的氧化铈的累积氢消耗量为200微摩尔/克或更大。
6.根据权利要求1的用于脱除硫化合物的吸附剂,其中正如在程序升温试验中直到600℃计算的,氧化铈的累积氢消耗量为300微摩尔/克或更大。
7.根据权利要求1的用于脱除硫化合物的吸附剂,其中吸附剂含有氧化铈和至少一种选自Al2O3、SiO2、TiO2、ZrO2和MgO的氧化物的混合物。
8.根据权利要求1的用于脱除硫化合物的吸附剂,其中吸附剂还含有至少一种选自周期表第1至第15族元素的元素,所述的至少一种元素负载在氧化铈上。
9.根据权利要求8的用于脱除硫化合物的吸附剂,其中将至少一种选自周期表第1至第15族元素的元素负载其上的氧化铈在400℃或更低的温度下焙烧。
10.根据权利要求8的用于脱除硫化合物的吸附剂,其中按吸附剂的总量计,至少一种选自周期表第1至第15族元素的元素的负载化合物按所述的负载化合物还原成相应的金属元素计的量为1-90%(质量)。
11.根据权利要求1的用于脱除硫化合物的吸附剂,其中氧化铈为含有铈和至少一种不同于铈的金属元素的复杂氧化物,所述的金属元素选自周期表第2至第16族元素的元素。
12.根据权利要求1的用于脱除硫化合物的吸附剂,其中烃类燃料为液化石油气、城市煤气、天然气、石脑油、煤油、瓦斯油,或至少一种选自乙烷、乙烯、丙烷、丙烯、丁烷、丁烯、甲醇和二甲醚的烃类化合物或含氧的烃类化合物。
13.一种生产氢的方法,其特征在于所述的方法包括通过使用权利要求1的吸附剂脱除烃类燃料中的硫化合物使烃类燃料脱硫,随后将已脱硫的燃料与部分氧化重整催化剂、自热重整催化剂或蒸汽重整催化剂接触。
14.根据权利要求13的生产氢的方法,其中部分氧化重整催化剂、自热重整催化剂或蒸汽重整催化剂含钌或镍。
15.根据权利要求13的生产氢的方法,其中在既不加入氢又不加入氧的条件下进行脱硫。
16.根据权利要求13的生产氢的方法,其中硫化合物为至少一种选自羰基硫化物、二硫化碳、硫化氢、硫醇类、硫醚类和噻吩类的化合物。
17.根据权利要求13的生产氢的方法,其中脱硫在200℃或更低的温度下进行。
18.根据权利要求13的生产氢的方法,其中脱硫在100℃或更低的温度下进行。
19.一种燃料电池体系,其特征是使用权利要求13-18中任一项的生产氢的方法所生产的氢。
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US (1) | US7556872B2 (zh) |
EP (1) | EP1550505A4 (zh) |
KR (1) | KR100973876B1 (zh) |
CN (1) | CN100469434C (zh) |
AU (1) | AU2003261728A1 (zh) |
CA (1) | CA2497899C (zh) |
WO (1) | WO2004022224A1 (zh) |
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CN101811039A (zh) * | 2010-03-12 | 2010-08-25 | 浙江大学 | 一种硫改性二氧化铈催化剂的制备方法及制备的催化剂 |
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CN108404899A (zh) * | 2018-03-16 | 2018-08-17 | 浙江华昱科技有限公司 | 一种用于电化学氧化脱柴油硫的阳极催化剂的制备方法、阳极催化剂及应用 |
CN111019727A (zh) * | 2018-10-09 | 2020-04-17 | 南京雪郎化工科技有限公司 | 一种液化石油气氧化脱硫的方法 |
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KR101280200B1 (ko) * | 2004-02-19 | 2013-06-28 | 이데미쓰 고산 가부시키가이샤 | 탄화수소 개질 촉매, 이런 개질 촉매를 이용한 수소의 제조방법 및 연료 전지 시스템 |
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-
2003
- 2003-08-26 CA CA2497899A patent/CA2497899C/en not_active Expired - Fee Related
- 2003-08-26 AU AU2003261728A patent/AU2003261728A1/en not_active Abandoned
- 2003-08-26 EP EP03794097A patent/EP1550505A4/en not_active Withdrawn
- 2003-08-26 US US10/526,397 patent/US7556872B2/en not_active Expired - Fee Related
- 2003-08-26 CN CNB038210339A patent/CN100469434C/zh not_active Expired - Fee Related
- 2003-08-26 KR KR1020057003716A patent/KR100973876B1/ko not_active IP Right Cessation
- 2003-08-26 WO PCT/JP2003/010781 patent/WO2004022224A1/ja active Application Filing
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101479371B (zh) * | 2006-07-07 | 2013-04-17 | 宝洁公司 | 具有低硫含量的风味油及其在口腔护理组合物中的应用 |
CN101811039A (zh) * | 2010-03-12 | 2010-08-25 | 浙江大学 | 一种硫改性二氧化铈催化剂的制备方法及制备的催化剂 |
CN108404899A (zh) * | 2018-03-16 | 2018-08-17 | 浙江华昱科技有限公司 | 一种用于电化学氧化脱柴油硫的阳极催化剂的制备方法、阳极催化剂及应用 |
CN111019727A (zh) * | 2018-10-09 | 2020-04-17 | 南京雪郎化工科技有限公司 | 一种液化石油气氧化脱硫的方法 |
Also Published As
Publication number | Publication date |
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CA2497899C (en) | 2012-03-06 |
WO2004022224A1 (ja) | 2004-03-18 |
AU2003261728A1 (en) | 2004-03-29 |
KR20050057151A (ko) | 2005-06-16 |
EP1550505A1 (en) | 2005-07-06 |
KR100973876B1 (ko) | 2010-08-03 |
CN100469434C (zh) | 2009-03-18 |
CA2497899A1 (en) | 2004-03-18 |
US7556872B2 (en) | 2009-07-07 |
EP1550505A4 (en) | 2008-12-10 |
US20050271913A1 (en) | 2005-12-08 |
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