CN101522559A - 含氢气体的制造方法 - Google Patents
含氢气体的制造方法 Download PDFInfo
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- CN101522559A CN101522559A CNA2007800374116A CN200780037411A CN101522559A CN 101522559 A CN101522559 A CN 101522559A CN A2007800374116 A CNA2007800374116 A CN A2007800374116A CN 200780037411 A CN200780037411 A CN 200780037411A CN 101522559 A CN101522559 A CN 101522559A
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- Prior art keywords
- hydrocarbon
- containing gas
- hydrogen
- manufacture method
- aforementioned
- Prior art date
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000007789 gas Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 85
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 85
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 83
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 239000000446 fuel Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 36
- 239000010970 precious metal Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- 239000003350 kerosene Substances 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000003225 biodiesel Substances 0.000 claims description 3
- 150000002148 esters Chemical group 0.000 claims description 3
- 239000000295 fuel oil Substances 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 41
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 238000002407 reforming Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- 239000011777 magnesium Substances 0.000 description 26
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 229910001701 hydrotalcite Inorganic materials 0.000 description 17
- 229960001545 hydrotalcite Drugs 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 15
- 239000010948 rhodium Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 230000023556 desulfurization Effects 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910003023 Mg-Al Inorganic materials 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- -1 aluminum compound Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910052599 brucite Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910003275 NiMgAl Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 150000001457 metallic cations Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- RTZYCRSRNSTRGC-LNTINUHCSA-K (z)-4-oxopent-2-en-2-olate;ruthenium(3+) Chemical compound [Ru+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O RTZYCRSRNSTRGC-LNTINUHCSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 229910002645 Ni-Rh Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910002787 Ru-Ni Inorganic materials 0.000 description 1
- 229910002793 Ru–Ni Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- MLIYPCQSOXNTLJ-UHFFFAOYSA-N carbon monoxide;ruthenium dihydride;triphenylphosphane Chemical compound [RuH2].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MLIYPCQSOXNTLJ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- 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
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Abstract
本发明提供对C5以上且在常温常压下为液态的烃或含氧的烃进行改性,从而制造含氢气体、特别是燃料电池用氢的方法。本发明的含氢气体的制造方法,其特征在于,使用含有Ni、Mg和Al同时还含有选自Pt、Pd、Ir、Rh和Ru中的至少一种贵金属元素的催化剂,对碳原子数5以上、且常温常压下为液态的烃或含氧的烃进行改性处理。
Description
技术领域
本发明涉及含氢气体的制造方法。更加详细地说,本发明涉及使用特定的催化剂,从碳原子数5以上(以下有时简写成C5以上)且在常温常压下为液态的烃或含氧的烃来制造含氢气体的方法,特别涉及燃料电池用的含氢气体的制造方法。
背景技术
近年来,新能源技术因为环境问题而备受瞩目,作为该新能源技术之一的燃料电池受到了人们的关注。该燃料电池通过使氢和氧发生电化学反应来使化学能转变为电能,具有能源的利用效率高的特征,人们正积极地开展将其作为民用、产业用或汽车用等的实用化研究。
根据使用的电解质的种类,已知该燃料电池中有磷酸型、溶融碳酸盐型、固体氧化物型和固体高分子型等类型。另一方面,作为氢源,正在开展以甲醇和甲烷为主体的液化天然气、以该天然气为主要成份的城市煤气、以天然气为原料的合成液体燃料、以及石油类的LPG、石脑油和煤油等石油类烃的使用的研究。
在使用这些石油类烃来制造氢时,通常,对于该烃,是在催化剂的存在下进行水蒸汽改性(改質)处理、自热改性处理、部分氧化改性处理等。
作为这样的烃的改性催化剂,以往已知有钌类催化剂和镍类催化剂,还已知在水滑石(多孔性复合氢氧化物的水合物)的基础上制备的催化剂的活性较高。
公开了使用在水滑石的基础上制备的烃改性催化剂,以低级烃为原料来制造氢的方法,作为在水滑石的基础上制备的烃改性催化剂,例如:(1)以水滑石作为前体,将其一部分组成元素(Mg、Al)用作为活性金属的贵金属(Rh或Ru)或过渡金属元素取代、烧结,使活性金属种从内部浸染到表面并高分散化的金属微粒载持烃改性催化剂(例如,参照专利文献1);(2)含有镁、铝和镍,在水滑石的基础上制造的改性催化剂(例如,参照专利文献2和3);(3)通过离子交换在水滑石的层间导入Ru,将其烧结后通过还原使之活化而制备的改性催化剂(例如,参照专利文献4);(4)含有镁、铝、镍和铁,在水滑石的基础上制备而成的、抑制了副产物氨的生成的自热改性催化剂(例如,参照专利文献5);(5)通过将水滑石状层状化合物烧结而制备的、含有选自Ru、Pt、Pd、Rh和Ir中的至少1种金属的含甲烷的气体改性催化剂(例如,参照专利文献6);(6)在水滑石的基础上制备的、以镁、铝、镍和钌为组成元素的烃分解用催化剂(例如,参照专利文献7);(7)在水滑石的基础上制备的、以镁、铝、镍为组成元素、含有选自碱性金属(除钠之外)、碱土类金属(除镁之外)、Zn、Co、Ce、Cr、Fe和La中的至少1种元素、而且含有铂、铑、钌、铱或钯等贵金属元素的催化剂(例如,参照专利文献8)。
进而,(8)在非专利文献1中,公开了使用以水滑石为前体制备的载持型催化剂(co-Ni-Rh/Mg-Al和Ni→Rh/Mg-Al)进行的丙烷的水蒸汽改性反应;(9)在非专利文献2中,公开了使用以不含Mg的Ni-Al水滑石样物质为起始物质的催化剂的葵花子油的水蒸汽改性反应。
然而,关于前述(1)的改性催化剂,有将前体水滑石的组成元素用贵金属元素取代的记载,也有关于使用烃的记载,但没有以甲烷或甲醇的改性为目的而使用C5以上的液态的烃或含氧烃的记载。关于(2)的改性催化剂,不仅没有关于含有贵金属元素的记载,而且也没有关于使用C5以上的液态的烃或含氧烃的记载。关于(3)的自热改性催化剂,记载了通过离子交换在水滑石的层间导入Ru,将之烧结,通过还原而使之活化的改性催化剂,但使用的原料主要为含有甲烷或乙烷等的气态的烃,没有关于使用C5以上的液态的烃或含氧烃的例子的记载。
记载了前述(4)的改性催化剂在含有镁和铝的同时还含有金属镍微粒和/或金属铁微粒,载持有选自金、银、铂、钯、铑、铱、铼、铜、锰、铬、钒、钛中的1种或2种以上的元素作为贵金属元素,但使用的原料主要为含有甲烷~丁烷的气态的低级烃,没有关于使用C5以上的液态的烃或含氧烃的例子的记载。
在(5)中,使用后述的催化剂进行含甲烷的气体的改性反应,所述催化剂是通过在改变Mg2+和Al3+的比例而配制成的各种水滑石状层状化合物上载持Ru、Pt、Pd、Rh和Ir等后进行烧结而制备的。但是(5)中并没有关于使用C5以上的液态的烃或含氧烃的记载。(6)和(7)中也没有关于使用C5以上的液态的烃或含氧烃的实施例的记载。(8)中记载了与使用未载持Rh的Ni/Mg~Al时相比,丙烷的转化率更高但焦炭析出量较多,但是没有关于处理C5以上的液态的烃或含氧烃的记载,(9)中不仅没有关于含有贵金属元素的记载,而且也没有关于使用除葵花子油之外的C5以上的液态的烃或含氧烃的记载。
进而,关于这些现有的烃改性催化剂,其活性未必能充分满足要求。
专利文献1:日本特开平11-276893号公报
专利文献2:日本特开2003-135967号公报
专利文献3:日本特开2004-255245号公报
专利文献4:日本特开2003-290657号公报
专利文献5:日本特开2005-224722号公报
专利文献6:日本特开2005-288259号公报
专利文献7:日本特开2006-061759号公报
专利文献8:日本特开2006-061760号公报
非专利文献2:Maximiliano Marquevich et al[Cat.Lett.Vol.85.Nos.1-2,p41-48(2003)]
发明内容
在这样的状况下,本发明的目的在于提供使用耐久性获得提高的催化剂来高效率地制造含氢气体、特别是燃料电池用的含氢气体的方法。
本发明人等为了达到前述目标而不断深入研究,结果发现,在将烃改性来制造含氢气体、特别是燃料电池用的含氢气体时,通过将含有特定金属元素的催化剂、特别是在水滑石状层状化合物的基础上获得的特定催化剂与C5以上的液态的烃或含氧烃组合使用,能够达成目标。本发明就是基于该见解而完成的。
即,本发明提供下述(1)~(9)
(1)含氢气体的制造方法,其特征在于,使用含有Ni、Mg和Al同时还含有选自Pt、Pd、Ir、Rh和Ru中的至少一种贵金属元素的催化剂,对碳原子数5以上、且常温常压下为液态的烃或含氧的烃进行改性处理;
(2)上述(1)中记载的含氢气体的制造方法,其中,对前述催化剂重复进行还原-氧化处理之后使用;
(3)上述(1)或(2)中记载的含氢气体的制造方法,其中,前述催化剂是在水滑石状层状化合物的基础上得到的;
(4)上述(1)~(3)中的任意一项记载的含氢气体的制造方法,其中,前述催化剂是通过对水滑石状层状化合物进行烧结后,再使之载持贵金属成分而得到的;,
(5)上述(1)~(3)中的任意一项记载的含氢气体的制造方法,其中,前述贵金属元素为Rh和/或Ru;
(6)上述(1)~(3)中的任意一项记载的含氢气体的制造方法,其中,前述烃的改性为水蒸汽改性、自热改性或部分氧化改性;
(7)上述(1)~(3)中的任意一项记载的含氢气体的制造方法,其中,前述烃为直链状或支链状的饱和烃、脂环式饱和烃、单环或多环芳香族烃、或该等烃的混合物;
(8)上述(1)~(3)中的任意一项记载的含氢气体的制造方法,其中,前述烃为选自轻石脑油、重石脑油、石脑油、汽油、煤油、轻油、A重油、生物柴油燃料或植物油中的至少一种;以及
(9)上述(1)~(3)中的任意一项记载的含氢气体的制造方法,其中,前述含氢气体为燃料电池用的含氢气体。
根据本发明,通过将含有特定金属元素的烃改性催化剂、特别是在水滑石状层状化合物的基础上获得的催化剂与C5以上的液态的烃或含氧烃组合使用,从而可以高效率地制造含氢气体、特别是燃料电池用的含氢气体。
具体实施方式
本发明中使用的催化剂为,在含有Ni、Mg和Al的同时还含有选自Pt、Pd、Ir、Rh和Ru中的至少1种贵金属元素,对烃进行改性从而制造含氢气体的催化剂(以下有时称为烃改性催化剂),被改性的烃为C5以上且在常温常压下为液态的烃或含氧的烃。
从催化剂活性和耐久性的方面出发,该烃改性催化剂特别优选在水滑石状层状化合物的基础上获得的催化剂。
现有的水滑石为下述式(1)表示的粘土矿物。
Mg6Al2(OH)16CO3·4H2O……(1)
近年来,含有2价的金属阳离子[M(II)2+]、3价的金属阳离子[M(III)3+]和n价的层间阴离子(An-)的下述式(2)表示的物质,被称作水滑石状物质、水滑石样化合物、水滑石结构体或者直接被称为水滑石。
[(M(II)2+)1-X(M(III)3+)x(OH-)2]X+(An- x-n)·mH2O
……式(2)
式(1)表示的水滑石具有如下结构:“OH-(0.75Mg2+、0.25Al3+)OH-”形成平面状的骨架作为水镁石(ブルサイト)层,在其层间夹着带负电荷的0.125CO3 2-和0.5H2O的结构。水镁石层内的Mg2+和Al3+的比例可以在广泛的范围内变化,可以由此来控制水镁石层内正电荷的密度。
关于上述催化剂中贵金属成分的含量,从对氧化的耐性、催化剂活性和经济性的平衡等观点出发,作为金属元素,优选为0.05~3质量%,更加优选为0.1~2.0质量%,进一步优选为0.2~1.0质量%。从催化剂活性的观点出发,作为贵金属元素,特别优选Rh和/或Ru。
Ni成分的含量,从催化剂活性和经济性平衡等观点出发,作为金属元素,优选为5~25质量%,更加优选为8~20质量%,进一步优选为10~20质量%。
另外,关于Mg元素和Al元素的含量,若以Mg元素和Al元素的总摩尔数为1,则Mg元素优选为0.5~0.85,更加优选为0.6~0.8。Mg元素的摩尔数为0.5以上时,可以发挥作为多孔质载体的特性,另外,为0.85以下时可以获得充分的强度。
作为构成上述催化剂的各个元素的来源,可以列举以下所示的化合物。
作为贵金属元素(Ru)来源的钌化合物,例如,可以列举:RuCl3·nH2O、Ru(NO3)3、Ru2(OH)2Cl4·7NH3·3H2O、K2(RuCl5(H2O))、(NH4)2(RuCl5(H2O))、K(RuCl5(NO))、RuBr3·nH2O、Na2RuO4、Ru(NO)(NO3)3、(Ru3O(OAc)6(H2O)3)OAc·nH2O、K4(Ru(CN)6)·nH2O、K2(Ru(NO2)4(OH)(NO))、(Ru(NH3)6)Cl3、(Ru(NH3)6)Br3、(Ru(NH3)6)Cl2、(Ru(NH3)6)Br2、(Ru3O2(NH3)14)Cl6·H2O、(Ru(NO)(NH3)5)Cl3、(Ru(OH)(NO)(NH3)4)(NO3)2、RuCl2(PPh3)3、RuCl2(PPh3)4、RuClH(PPh3)3·C7H8、RuH2(PPh3)4、RuClH(CO)(PPh3)3、RuH2(CO)(PPh3)3、(RuCl2(cod))n、Ru(CO)12、Ru(acac)3、(Ru(HCOO)(CO)2)n、Ru2I4(p-cymene)2、[Ru(NO)(edta)]-等钌盐。
这些成分可以单独使用1种,也可以将2种以上合并使用。
从操作上的观点出发,优选使用RuCl3·nH2O、Ru(NO3)3、Ru2(OH)2Cl4·7NH3·3H2O。
作为贵金属元素(Rh)来源的铑化合物,例如,可以列举Na3RhCl6、(NH4)2RhCl6、Rh(NH3)5Cl3、Rh(NO3)3、RhCl3等。
作为贵金属元素(Pt)来源的铂化合物,例如,可以列举PtCl4、H2PtCl6、Pt(NH3)4Cl2、(MH4)2PtCl2、H2PtBr6、NH4[Pt(C2H4)Cl3]、Pt(NH3)4(OH)2、Pt(NH3)2(NO2)2等。
作为贵金属元素(Pd)来源的钯化合物,例如,可以列举(NH4)2PdCl6、(NH4)2PdCl4、Pd(NH3)4Cl2、PdCl2、Pd(NO3)2等。
作为贵金属元素(Ir)来源的铱化合物,例如,可以列举(NH4)2IrCl6、IrCl3、H2IrCl6等。
作为Ni元素来源的镍化合物,例如,可以列举Ni(NO3)2·6H2O、NiO、Ni(OH)2、NiSO4·6H2O、NiCO3、NiCO3·2Ni(OH)2·nH2O、NiCl6·6H2O、(HCOO)2Ni·2H2O、(CH3COO)2Ni·4H2O等。
作为Mg元素来源的镁化合物,例如,可以列举Mg(NO3)2·6H2O、MgO、Mg(OH)2、MgC2H4·2H2O、MgSO4·7H2O、MgSO4·6H2O、MgCl2·6H2O、Mg3(C6H5O7)2·nH2O、3MgCO3·Mg(OH)2、Mg(C6H5COO)2·4H2O等。
作为Al元素来源的铝化合物,例如,可以列举Al(NO3)3·9H2O、Al2O3、Al(OH)3、AlCl3·6H2O、AlO(COOCH3)·nH2O、Al2(C2O4)3·nH2O等。
上述催化剂优选在对水滑石状层状化合物进行烧结后再使之载持贵金属成分而获得。
这样的催化剂,例如可以用以下所示的方法来制备。
向碳酸钠水溶液中缓慢地同时滴加水中溶解有硝酸镍等Ni源、硝酸镁等Mg源、硝酸铝等Al源的水溶液和氢氧化钠水溶液,在滴加的过程中时常调节pH使之保持稳定。pH可以为约9~13。之后,将生成的沉淀物在约40~100℃进行约30分钟至80小时、优选约1~24小时的成熟(ripen)后,过滤,再在约80~150℃进行干燥处理。
之后,将如此获得的水滑石状层状化合物在约400~1500℃的温度下进行烧结处理,由此可以获得NiMgAl的复合氧化物。之后,在该复合氧化物中浸渍含有Ru源Ru(NO3)3之类的贵金属化合物的水溶液,使之载持规定量的贵金属元素。此时,在贵金属元素存在于阴离子络合物中的情况下,还可以通过离子交换来载持贵金属元素。进行离子交换时,一旦将NiMgAl的复合氧化物放入水溶液中,就可以通过记忆效应(memory effect)而恢复成水滑石结构,而且在层间可以形成阴离子位点(anion site)。载持贵金属元素之后,再在约400~1500℃的温度下进行烧结处理。
另外,贵金属元素还可以在最初的沉淀生成反应中,例如与镍源、镁源和铝源一起将作为贵金属源的贵金属化合物以水溶液的形式导入。
如上所述,在水滑石状层状化合物的基础上制备的催化剂的比表面积通常为5~250m2/g,优选为7~200m2/g。比表面积不足5m2/g时,由于单个粒子的视盘直径(板面)和厚度都很大,催化剂难以成形。超过250m2/g时,由于每个粒子都很微细,在水洗工序和过滤工序上存在问题。
本发明的特征在于,将这样制备的改性催化剂和C5以上且在常温常压下为液态的烃或含氧的烃组合使用。
作为C5以上且在常温常压下为液态的烃,可以列举:戊烷、己烷、庚烷、辛烷、壬烷、癸烷等直链状或支链状的饱和脂肪烃,环己烷、甲基环己烷、环辛烷等脂环式饱和烃,单环或多环芳香族烃等。作为产品名称,相当于轻石脑油、重石脑油、石脑油、汽油、煤油、轻油、A重油等。作为含氧烃,可以列举从生物资源制造的生物柴油燃料、植物油等。
另外,通常这些C5以上且在常温常压下为液态的烃或含氧烃中存在硫时,通过脱硫工序,通常优选进行脱硫直至硫达到0.1质量ppm以下。当原料烃中的硫多于约0.1质量ppm时,有时会成为改性催化剂失活的原因。脱硫方法没有特别的限定,可以适当采用加氢脱硫、吸附脱硫等。
以下,说明C5以上且在常温常压下为液态的烃或含氧烃的各改性反应。
[水蒸汽改性反应]
作为反应条件,通常,可以决定烃量和水蒸汽量使满足水蒸汽/碳之比(摩尔比)为1.5~10,优选为1.5~5,更加优选为2~4。通过像这样调节水蒸汽/碳之比(摩尔比),可以高效率地获得氢含量高的产品气体。
反应温度通常为200~900℃,优选为250~900℃,更加优选为300~800℃。反应压力通常为0~3MPa·G,优选为0~1MPa·G。
可以使改性催化剂层的入口温度保持在630℃以下、优选600℃以下进行水蒸汽改性。入口温度超过630℃时,有时会促进烃的热分解,经由生成的自由基在催化剂或反应管壁上析出碳,使运转变得困难。
催化剂层的出口温度没有特别的限制,优选在650~800℃的范围内。出口温度为650℃以上时,氢的生成量充分;另外,在800℃以下时,反应装置也可以不使用耐热材料,在经济上是优选的。
此外,作为水蒸汽改性反应中使用的水蒸汽,没有特别的限制。
[自热改性反应]
自热改性反应是指,烃的氧化反应和烃与水蒸汽的反应在同一反应器或连续的反应器内发生,通常反应温度为200~1300℃,优选为400~1200℃,更加优选为500~900℃。
水蒸汽/碳之比(摩尔比)通常为0.1~10,优选为0.4~4。氧/碳之比(摩尔比)通常为0.1~1,优选为0.2~0.8。
反应压力通常为0~10MPa·G,优选为0~5MPa·G,更加优选为0~3MPa·G。
[部分氧化改性反应]
部分氧化改性反应是指,进行烃的部分氧化反应,通常反应温度为350~1200℃,优选为450~900℃。氧/碳之比(摩尔比)通常为0.4~0.8,优选为0.45~0.65。
反应压力通常为0~30MPa·G,优选为0~5MPa·G,更加优选为0~3MPa·G。
在开始上述的各反应之前,作为催化剂的活化前处理可以重复实施还原-氧化处理。通过重复实施还原-氧化处理,可以使催化剂高度活化同时使之高耐久化。
在还原-氧化的重复处理中,还原处理通常在含氢气体氛围下,在约600~1100℃、优选在700~1000℃范围的温度下进行。若该温度为600℃以上,则Ni成分的还原能充分进行,可以获得高活性的催化剂;另外,若为1100℃以下,则可以抑制因Ni成分、Ru成分等贵金属成分的烧结而导致的活性降低。
虽然还原处理的时间取决于处理温度,但从Ni成分的充分还原和经济性的平衡等观点出发,优选处理约30分钟至10小时,更加优选处理1~5小时。
另一方面,在还原-氧化的重复处理中,氧化处理通常在含氧气体氛围下,在约400~1200℃、优选500~1000℃范围的温度下进行。作为前述含氧气体,通常可以使用空气,还可以使用将空气用氮气、氩气等惰性气体稀释后的气体或水蒸汽等。
氧化处理温度若为400℃以上,则可以充分地进行Ni元素、Ru等贵金属元素的氧化,能够良好地发挥本发明的效果;另外,若为1200℃以下,则Ru等贵金属成分难以挥发、且难以降低表面积。
虽然氧化处理时间取决于处理温度,但从Ni元素、Ru等贵金属元素的充分氧化和经济性的平衡等观点出发,优选处理约30分钟至10小时,更加优选处理1~5小时。
本发明中,从提高催化剂活性的观点出发,优选对烧结的催化剂进行还原处理后,重复实施1~20次“氧化-还原”的处理,更加优选实施1~10次,进一步优选实施1~3次。
如此,对于烃改性催化剂,作为活化前处理通过重复实施还原-氧化的处理,能够提高该烃改性催化剂的活性和耐久性,认为其理由如下。
可以认为,作为活性金属元素的Ni与Ru、Rh等贵金属元素相互作用,通过重复进行使活性金属元素高分散化的还原/氧化处理,从而进一步增强所述相互作用,最终带来高度活化和高耐久化。但是,若重复至某种规定以上的次数,则会产生活性金属元素的凝集,导致活性降低。
作为以上改性反应的反应方式,可以是连续流通式、分批式中的任一种方式,但优选连续流通式。
采用连续流通式时,烃的液时空速(LHSV)通常为0.1~10h-1,优选为0.25~5h-1。
作为反应形式,没有特别的限制,可以采用固定床式、动床式(mobile bed)、流化床式的任意一种,优选采用固定床式。
作为反应器的形式也没有特别的限制,例如,可以使用管型反应器等。
在上述的条件下,通过使用改性催化剂,进行烃的水蒸汽改性反应、自热改性反应、部分氧化改性反应,可以获得含氢的混合物,特别是适合用作燃料电池的氢制造过程用的含氢气体。
实施例
以下,通过实施例更加详细地说明本发明,但本发明并不被这些例子限定。
[比较制备例1]
将Ni(NO3)2·6H2O 16.414g、Mg(NO3)2·6H2O 70.813g以及Al(NO3)3·9H2O 41.492g溶于150ml水中,配制A液;将Na2CO3·10H2O15.816g溶于100ml水中,配制B液。
之后,向前述B液中滴加A液。此时,适当地滴加1mol/L浓度的NaOH水溶液,使液体的pH为10。A溶液滴加结束之后,在90℃下搅拌40分钟,之后在90℃下静置20小时后,放冷,用抽滤提取沉淀物。
接着,用2L的水洗净沉淀物后,在105℃下进行9小时的干燥处理,然后以0.83℃/分钟的速度升温至850℃,在该温度下进行5小时的烧结处理,由此获得催化剂X-1(spc-Ni/Mg-Al)。
催化剂X-1中的Ni含量为14质量%、Mg含量为28质量%、Al含量为13质量%。
spc为solid phase crystallization(固相析晶法)的缩写。
[制备例1]
将50g/L浓度的Ru(NO3)3水溶液0.5ml用水200ml稀释,配制C液。在该C液中加入比较制备例1中获得的催化剂X-1 5.0g,在室温下搅拌12小时后,一边搅拌一边加热至90℃,将沉淀物蒸发干固。
之后,将干固物以0.83℃/分钟的速度升温至850℃,然后在该温度下进行5小时的烧结处理,由此获得催化剂Y-1(spc-Ru-Ni/Mg-Al)。
催化剂Y-1中的Ru含量为0.5质量%。
[比较制备例2]
(1)载体的配制
将Mn(CH3COO)2·4H2O 5.45g溶于水11.5ml,配制含浸液A。接着,用孔隙充填法使事先充分干燥的γ-氧化铝载体30g浸透前述含浸液A后,在120℃下干燥处理3小时,然后在800℃下进行3小时的烧结处理,由此获得Mn载持载体。
(2)催化剂的配制
将RuCI3 0.39g溶于水1.8ml中,配制含浸液B。之后,用孔隙充填法使事先充分干燥的前述(1)的Mn载持载体5.0g浸透前述含浸液B,之后用5mol/L浓度的NaOH水溶液100ml进行1小时的碱分解。之后,进行一昼夜水洗后,在120℃下干燥处理5小时,获得催化剂X-2(Ru/Mn/Al2O3)。
催化剂X-2中的Ru含量为3.0质量%,Mn含量为3.7质量%。
[实施例1和比较例1~2]
使用在制备例1中获得的催化剂Y-1、在比较制备例1~2中获得的催化剂X-1和X-2,进行初期还原处理之后,进行水蒸汽改性反应和自热改性反应。
<初期还原反应>
将如上所述制备的各个催化剂成型为16~32目(mesh)的大小,分别取200mg填充至反应管中,在氢气流下于850℃进行1小时的初期还原处理。
<水蒸汽改性反应>
将催化剂200mg填充在反应管中,作为催化剂层,在氢气流下进行1小时、850℃的初期还原处理。之后,使反应温度保持在500℃附近,同时向催化剂层中供应脱硫煤油(S:不足0.02质量ppm)和水,使该脱硫煤油的液时空速(LHSV)为16.5h-1、水蒸汽/碳(摩尔比)为3.0,从而开始水蒸汽改性反应,采集反应开始1小时后、7小时后、13小时后、19小时后和25小时后获得的气体作为样品,计算该脱硫煤油的C1转化率的经时变化。在反应过程中,控制温度以使催化剂层的平均温度保持在500℃。结果如表1所示。
<自热改性反应>
将催化剂200mg填充在反应管中,作为催化剂层,在氢气流下进行1小时、850℃的初期还原处理。之后,使反应温度保持在700℃附近,向催化剂层中供应脱硫煤油(S:不足0.02质量ppm)、水和空气,使水蒸汽/碳(摩尔比)为1.8、氧/碳(摩尔比)为0.45,从而开始自热改性反应,采集反应开始1小时后、7小时后、13小时后、19小时后和25小时后获得的气体作为样品,计算该脱硫煤油的C1转化率的经时变化。在反应过程中,控制温度以使催化剂层的平均温度保持在700℃。结果如表1所示。
脱硫煤油的C1转化率按照下式计算。
C1转化率(%)=(A/B)×100
[在上式中,A=CO摩尔流量+CO2摩尔流量+CH4摩尔流量(均为反应器出口的流量),B=反应器入口侧的脱硫煤油的碳摩尔流量]
[表1]
如表1所示,实施例与比较例相比,C1转化率随时间降低较少,从而可知,本发明的催化剂在使用煤油之类的C5以上且常温常压下为液态的烃或含氧烃时,能够发挥非常优异的效果。
产业上的可利用性
本发明的制造方法可以适用于从烃制造含氢气体、特别是燃料电池用氢。
Claims (9)
1.含氢气体的制造方法,其特征在于,使用含有Ni、Mg和Al同时还含有选自Pt、Pd、Ir、Rh和Ru中的至少一种贵金属元素的催化剂,对碳原子数5以上、且常温常压下为液态的烃或含氧的烃进行改性处理。
2.权利要求1所述的含氢气体的制造方法,其中,对前述催化剂重复进行还原-氧化处理之后使用。
3.权利要求1或2所述的含氢气体的制造方法,其中,前述催化剂是在水滑石状层状化合物的基础上得到的。
4.权利要求1~3中任一项所述的含氢气体的制造方法,其中,前述催化剂是通过对水滑石状层状化合物进行烧结后,再使之载持贵金属成分而得到的。
5.权利要求1~3中任一项所述的含氢气体的制造方法,其中,前述贵金属元素为Rh和/或Ru。
6.权利要求1~3中任一项所述的含氢气体的制造方法,其中,前述烃的改性为水蒸汽改性、自热改性或部分氧化改性。
7.权利要求1~3中任一项所述的含氢气体的制造方法,其中,前述烃为直链状或支链状的饱和烃、脂环式饱和烃、单环或多环芳香族烃、或该等烃的混合物。
8.权利要求1~3中任一项所述的含氢气体的制造方法,其中,前述烃为选自轻石脑油、重石脑油、石脑油、汽油、煤油、轻油、A重油、生物柴油燃料或植物油中的至少一种。
9.权利要求1~3中任一项所述的含氢气体的制造方法,其中,前述含氢气体为燃料电池用的含氢气体。
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US (1) | US20100166647A1 (zh) |
EP (1) | EP2075227A4 (zh) |
JP (1) | JP2008094665A (zh) |
KR (1) | KR20090066273A (zh) |
CN (1) | CN101522559A (zh) |
CA (1) | CA2665388A1 (zh) |
WO (1) | WO2008047676A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102451696A (zh) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | 用于烃类蒸汽转化制取氢气或羰基合成气反应的催化剂 |
CN116393124A (zh) * | 2023-03-23 | 2023-07-07 | 中国石油大学(北京) | 一种Pt基催化剂及其制备方法和应用 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2342814B1 (es) * | 2009-01-13 | 2011-05-23 | Hynergreen Technologies, S.A | Catalizador para un proceso para la obtencion de hidrogeno mediante reformado de hidrocarburos con vapor de agua, proceso de preparacion del catalizador y uso del mismo en el proceso. |
KR101207181B1 (ko) | 2009-02-06 | 2012-11-30 | 에스케이이노베이션 주식회사 | 유사 하이드로탈사이트를 이용하여 제조된 로듐으로 개질된니켈계 촉매, 이 촉매의 제조방법, 그리고 이 촉매를 이용한 수소가스 제조방법 |
EP2424960A1 (en) * | 2009-04-28 | 2012-03-07 | University Of Southern California | Efficient and environmentally friendly processing of heavy oils to methanol and derived products |
KR101227447B1 (ko) * | 2010-10-12 | 2013-01-29 | 한국과학기술연구원 | 귀금속이 유사 하이드로탈사이트에 담지된 알콜류의 개질 반응용 촉매 및 이를 이용한 수소 제조 방법 |
KR101372871B1 (ko) * | 2012-04-13 | 2014-03-10 | 한국화학연구원 | 하이드로탈사이트 구조의 8b족 전이금속-마그네슘-알루미늄 산화물을 담체로 사용한 백금함침 촉매 및 이의 제조방법 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19801373A1 (de) * | 1998-01-16 | 1999-07-29 | Daimler Chrysler Ag | Verfahren zur Vorbehandlung eines Katalysatormaterials |
JP4211900B2 (ja) | 1998-03-31 | 2009-01-21 | 三菱重工業株式会社 | 金属微粒子担持炭化水素改質用触媒及びその製造方法 |
US6409940B1 (en) * | 1999-10-18 | 2002-06-25 | Conoco Inc. | Nickel-rhodium based catalysts and process for preparing synthesis gas |
JP2001212460A (ja) * | 2000-02-02 | 2001-08-07 | Mitsubishi Heavy Ind Ltd | メタノール改質触媒及びメタノール改質触媒の安定化処理方法 |
JP4098508B2 (ja) | 2001-08-20 | 2008-06-11 | 財団法人 ひろしま産業振興機構 | 炭化水素と水蒸気とを反応させるための触媒の製造方法および当該触媒を使用した炭化水素から水素を製造する方法 |
JP2003290657A (ja) | 2002-01-31 | 2003-10-14 | National Institute Of Advanced Industrial & Technology | 炭化水素改質用触媒、その製造方法、合成ガスの製造方法及び該触媒前駆体 |
JP2004057869A (ja) * | 2002-07-25 | 2004-02-26 | Nissan Motor Co Ltd | 燃料改質触媒ならびに水素リッチガス製造方法 |
JP2004066170A (ja) * | 2002-08-08 | 2004-03-04 | Nissan Motor Co Ltd | モノリス型燃料改質触媒とその製法 |
JP4870900B2 (ja) | 2003-02-24 | 2012-02-08 | 戸田工業株式会社 | 炭化水素分解用触媒及びその製造方法、並びに該炭化水素分解用触媒を用いた水素製造方法 |
JP2005169236A (ja) * | 2003-12-10 | 2005-06-30 | Nissan Motor Co Ltd | 燃料改質触媒 |
JP4332724B2 (ja) * | 2004-02-13 | 2009-09-16 | 戸田工業株式会社 | オートサーマルリフォーミング触媒及びその製造方法、並びに該オートサーマルリフォーミング触媒を用いた水素の製造方法 |
JP2005288259A (ja) | 2004-03-31 | 2005-10-20 | Teikoku Oil Co Ltd | メタン含有ガス改質用触媒及び合成ガス製造方法 |
JP4332733B2 (ja) | 2004-08-24 | 2009-09-16 | 戸田工業株式会社 | 炭化水素分解用触媒及び該炭化水素分解用触媒を用いた水素の製造方法 |
JP4340892B2 (ja) | 2004-08-24 | 2009-10-07 | 戸田工業株式会社 | 炭化水素分解用触媒及びその製造法、該炭化水素分解用触媒を用いた水素の製造方法 |
JP4684639B2 (ja) * | 2004-12-09 | 2011-05-18 | 日揮ユニバーサル株式会社 | 炭化水素改質触媒、該触媒の製造方法、及び該触媒による改質方法 |
KR101319137B1 (ko) * | 2005-08-11 | 2013-10-17 | 도다 고교 가부시끼가이샤 | 탄화수소를 분해하는 촉매, 상기 촉매를 이용한 탄화수소의분해 방법 및 수소의 제조 방법, 및 발전 시스템 |
-
2006
- 2006-10-12 JP JP2006278638A patent/JP2008094665A/ja not_active Withdrawn
-
2007
- 2007-10-11 CA CA002665388A patent/CA2665388A1/en not_active Abandoned
- 2007-10-11 KR KR1020097005366A patent/KR20090066273A/ko not_active Application Discontinuation
- 2007-10-11 CN CNA2007800374116A patent/CN101522559A/zh active Pending
- 2007-10-11 WO PCT/JP2007/069852 patent/WO2008047676A1/ja active Application Filing
- 2007-10-11 EP EP07829590A patent/EP2075227A4/en not_active Withdrawn
- 2007-10-11 US US12/444,173 patent/US20100166647A1/en not_active Abandoned
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102451696A (zh) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | 用于烃类蒸汽转化制取氢气或羰基合成气反应的催化剂 |
CN102451696B (zh) * | 2010-10-22 | 2014-03-05 | 中国石油化工股份有限公司 | 用于烃类蒸汽转化制取氢气或羰基合成气反应的催化剂 |
CN116393124A (zh) * | 2023-03-23 | 2023-07-07 | 中国石油大学(北京) | 一种Pt基催化剂及其制备方法和应用 |
Also Published As
Publication number | Publication date |
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EP2075227A4 (en) | 2011-11-09 |
CA2665388A1 (en) | 2008-04-24 |
EP2075227A1 (en) | 2009-07-01 |
JP2008094665A (ja) | 2008-04-24 |
WO2008047676A1 (fr) | 2008-04-24 |
US20100166647A1 (en) | 2010-07-01 |
KR20090066273A (ko) | 2009-06-23 |
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