JP2005066525A - Catalyst for producing hydrogen and method for producing hydrogen using the same - Google Patents
Catalyst for producing hydrogen and method for producing hydrogen using the same Download PDFInfo
- Publication number
- JP2005066525A JP2005066525A JP2003302127A JP2003302127A JP2005066525A JP 2005066525 A JP2005066525 A JP 2005066525A JP 2003302127 A JP2003302127 A JP 2003302127A JP 2003302127 A JP2003302127 A JP 2003302127A JP 2005066525 A JP2005066525 A JP 2005066525A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- group
- hydrocarbon
- hydrogen
- nickel
- 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
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 71
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 71
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 78
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 35
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 21
- -1 lanthanoid group metals Chemical class 0.000 claims abstract description 17
- 230000000737 periodic effect Effects 0.000 claims abstract description 12
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 8
- 150000002602 lanthanoids Chemical group 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052799 carbon Inorganic materials 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 abstract description 17
- 239000011593 sulfur Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 35
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 17
- 239000000654 additive Substances 0.000 description 16
- 230000000996 additive effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000002816 nickel compounds Chemical class 0.000 description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052702 rhenium Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 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
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- JMWUYEFBFUCSAK-UHFFFAOYSA-L nickel(2+);octadecanoate Chemical compound [Ni+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JMWUYEFBFUCSAK-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、炭化水素の分解による水素製造用触媒及びそれを用いた水素の製造方法に関するものである。 The present invention relates to a catalyst for producing hydrogen by cracking hydrocarbons and a method for producing hydrogen using the same.
水素はアンモニアやメタノールの原料等として化学工業で広く使われており、今後は、燃料電池等のエネルギー源としても大量に使われる方向にある。
最近、炭化水素の分解反応により水素を製造する触媒として、ニッケル系触媒を用いることが報告されている(非特許文献1参照)。
Hydrogen is widely used in the chemical industry as a raw material for ammonia and methanol, and in the future, it will be used in large quantities as an energy source for fuel cells and the like.
Recently, it has been reported that a nickel-based catalyst is used as a catalyst for producing hydrogen by a hydrocarbon decomposition reaction (see Non-Patent Document 1).
しかしながら、このニッケル系触媒は、メタンなどの水素/炭素比が高い炭化水素の改質反応においては、優れた触媒効果を示すものの、ガソリンや灯油などのような水素/炭素比の低い炭化水素油に適用した場合には、反応時に生成する炭素がニッケル触媒上に多量に析出してしまい、水(スチーム)による炭素除去/水素変換反応が十分に進行しないため、所望とする水素が十分に得られないという欠点があった。またニッケルは極微量の硫黄の存在により著しく活性が低下するという問題点もあった。 However, although this nickel-based catalyst shows an excellent catalytic effect in the reforming reaction of hydrocarbons with a high hydrogen / carbon ratio such as methane, it has a low hydrogen / carbon ratio such as gasoline and kerosene. When this is applied, a large amount of carbon produced during the reaction is deposited on the nickel catalyst, and the carbon removal / hydrogen conversion reaction by water (steam) does not proceed sufficiently. There was a disadvantage that it was not possible. Nickel also has a problem that the activity is remarkably lowered due to the presence of a very small amount of sulfur.
したがって、ニッケル系触媒を、水素/炭素比の高い炭化水素の分解反応のみならず、極微量の硫黄をも含む水素/炭素比の低い炭化水素や炭化水素油の分解反応等にも活用していくためには、炭素析出量が少なく水素生成量を増加させる高活性で安定性と耐硫黄性に優れた改良型ニッケル系触媒の開発が重要となっている。 Therefore, nickel-based catalysts can be used not only for cracking of hydrocarbons with a high hydrogen / carbon ratio but also for cracking reactions of hydrocarbons and hydrocarbon oils with a low hydrogen / carbon ratio that contain trace amounts of sulfur. In order to achieve this goal, it is important to develop an improved nickel-based catalyst that has a low carbon deposition amount and an increased hydrogen production rate and that is highly active and excellent in stability and sulfur resistance.
本発明の目的は、高炭素析出性や低耐硫黄性のために、水素生成量が十分ではないという従来のニッケル系触媒の有する問題点を克服し、低炭素析出性と耐硫黄性に富み、水素/炭素比の高い炭化水素の分解反応のみならず、極微量の硫黄をも含む水素/炭素比の低い炭化水素や炭化水素油の分解反応等に対しても、優れた水素生成活性を示し高収量で水素を与え、かつ安定性に優れた改良型ニッケル系触媒を提供すること及び該触媒を用いて炭化水素から水素を工業的に有利に製造し得る方法を提供することにある。 The object of the present invention is to overcome the problems of conventional nickel-based catalysts that hydrogen production is not sufficient due to high carbon precipitation and low sulfur resistance, and is rich in low carbon precipitation and sulfur resistance. Excellent hydrogen generation activity not only for cracking of hydrocarbons with high hydrogen / carbon ratio but also for cracking of hydrocarbons and hydrocarbon oils with low hydrogen / carbon ratio including trace amounts of sulfur An object of the present invention is to provide an improved nickel-based catalyst which gives hydrogen in a high yield and is excellent in stability, and to provide a method capable of industrially advantageously producing hydrogen from hydrocarbons using the catalyst.
本発明者らは、上記課題を解決するために鋭意検討した結果、ジルコニア系またはアルミナ系担体に、ニッケル含有物質と周期律表第6B族、7B族、第8族又はランタノイド族金属から選ばれた少なくとも一種の金属を含む物質とを担持させた触媒が有効であることを知見し本発明を完成するに至った。
すなわち、本発明によれば、以下の発明が提供される。
(1) ジルコニア系またはアルミナ系担体に、(i)ニッケル含有物質及び、(ii)周期律表第6B族、7B族、第8族又はランタノイド族金属から選ばれた少なくとも一種の金属を含む物質、とを担持させたことを特徴とする炭化水素の分解反応による水素製造用触媒。
(2) 触媒成分として、さらに周期律表第Ia族金属又はIIa族金属から選ばれた少なくとも一種の金属を含有させたことを特徴とする上記(1)に記載の水素製造用触媒。
(3)炭化水素が、脂肪族炭化水素、脂環式炭化水素及び芳香族炭化水素から選ばれた少なくとも一種の炭化水素であることを特徴とする上記(1)又は(2)に記載の水素製造用触媒。
(4) 炭化水素が、脂肪族炭化水素、脂環式炭化水素及び芳香族炭化水素から選ばれた少なくとも2種の炭化水素からなる混合油であることを特徴とする上記(3)に記載の水素製造用触媒。
(5)炭化水素またはその混合油が、さらに有機硫黄化合物を含むものであることを特徴とする上記(1)乃至(4)何れかに記載の水素製造用触媒。
(6)炭化水素を、ジルコニア系またはアルミナ系担体に、(i)ニッケル含有物質及び(ii)周期律表第6B族、7B族、第8族又はランタノイド族金属から選ばれた少なくとも一種の金属を含む物質、を担持させた触媒と加熱条件下に接触させて水素を得ることを特徴とする炭化水素の分解反応による水素の製造方法。
As a result of intensive studies to solve the above problems, the present inventors have selected a zirconia-based or alumina-based support from a nickel-containing substance and a group 6B, 7B, 8 or lanthanoid group metal in the periodic table. In addition, the inventors have found that a catalyst supporting at least one kind of metal-containing substance is effective, and completed the present invention.
That is, according to the present invention, the following inventions are provided.
(1) A material containing (i) a nickel-containing material and (ii) at least one metal selected from Group 6B, Group 7B, Group 8 or a lanthanoid group metal in a zirconia-based or alumina-based carrier. , And a catalyst for hydrogen production by a hydrocarbon decomposition reaction.
(2) The catalyst for hydrogen production as described in (1) above, further comprising at least one metal selected from Group Ia metal or Group IIa metal of the Periodic Table as a catalyst component.
(3) The hydrogen as described in (1) or (2) above, wherein the hydrocarbon is at least one hydrocarbon selected from aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons. Catalyst for production.
(4) The hydrocarbon according to (3) above, wherein the hydrocarbon is a mixed oil composed of at least two types of hydrocarbons selected from aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons. Catalyst for hydrogen production.
(5) The hydrogen production catalyst according to any one of (1) to (4) above, wherein the hydrocarbon or a mixed oil thereof further contains an organic sulfur compound.
(6) At least one kind of metal selected from (i) a nickel-containing substance and (ii) Group 6B, Group 7B, Group 8 or Lanthanoid group metal in a zirconia-based or alumina-based carrier A method for producing hydrogen by a hydrocarbon decomposition reaction, wherein hydrogen is obtained by contacting a catalyst containing a substance containing hydrogen under heating conditions.
本発明の改良型ニッケル系触媒では、従来公知のニッケル系触媒とは異なり、(ii)の第6B、7B、8属またはランタノイド属元素と、アルミナやジルコニア担体との相乗効果により、(i)のニッケル含有物質上に堆積されている炭素がより効率的に水(スチーム)と反応して水素へと変換されるため、その水素生成活性や耐硫黄性に優れることから、原料炭化水素として水素/炭素比の低くかつ、硫黄分を含む10ppm程度含む炭化水素や炭化水素油たとえばガソリンや灯油などの混合油を用いたとしても、高選択率、高収率で水素を製造することができる。また、かかる触媒系に、さらに周期律表第Ia族金属又はIIa族金属から選ばれた少なくとも一種の金属を含有させると、更に高選択率、高収率で水素を製造することができる。 In the improved nickel-based catalyst of the present invention, unlike the conventionally known nickel-based catalysts, the synergistic effect of (ii) Group 6B, 7B, 8 or lanthanoid genus element and alumina or zirconia support, (i) Since carbon deposited on nickel-containing materials reacts more efficiently with water (steam) and is converted to hydrogen, it has excellent hydrogen generation activity and sulfur resistance. Even if a hydrocarbon or hydrocarbon oil having a low carbon ratio and containing about 10 ppm containing sulfur is used, hydrogen can be produced with high selectivity and high yield. Further, when such a catalyst system further contains at least one metal selected from Group Ia metal or Group IIa metal of the periodic table, hydrogen can be produced with higher selectivity and higher yield.
本発明の炭化水素の分解反応による水素製造用触媒は、ジルコニア系又はアルミナ系触媒担体に、(i)ニッケル含有物質と(ii)周期律表第6B族、7B族、第8族又はランタノイド族金属から選ばれた少なくとも一種の金属を含む物質(添加物I)とを活性成分として担持させたものである。 The catalyst for hydrogen production by the hydrocarbon decomposition reaction of the present invention comprises (i) a nickel-containing substance and (ii) a group 6B, 7B, 8 or lanthanoid group in a periodic table on a zirconia-based or alumina-based catalyst support. A substance (additive I) containing at least one metal selected from metals is supported as an active ingredient.
本発明の触媒担体として用いるジルコニア系又はアルミナ系物質としては、従来より触媒担体として公知の各種ジルコニア又はアルミナ構造体及びそれらの前駆体が挙げられ、それらの製造法や原材料によっては何ら限定されるものではない。
このようなジルコニア系担体としては、アモルファスジルコニア、単斜晶ジルコニア、四方晶ジルコニアなどの酸化物が例示される。また焼成してジルコニアになる前駆体として、ジルコニウムイソプロポキシド、ジルコニウムアセチルアセトナートなどの有機ジルコニウム化合物、塩化ジルコニウム、硝酸ジルコニルなどの無機ジルコニウム塩などを用いることもできる。これらはそのまま焼成することもできるが、水やアンモニア等により加水分解してジルコニア水酸化物としてから、焼成することもできる。他方アルミナ系担体としては、α-アルミナ、β-アルミナ、γ-アルミナなどの酸化物が例示される。また焼成してアルミナになる前駆体として、アルミニウムイソプロポキシド、アルミニウムアセチルアセトナートなどの有機アルミニウム化合物、硝酸アルミニウム、塩化アルミニウムなどの無機アルミニウム塩が挙げられる。これらはそのまま焼成することもできるが、水やアンモニア等により加水分解して水酸化アルミニウムとしてから、焼成することもできる。
Examples of the zirconia-based or alumina-based material used as the catalyst support of the present invention include conventionally known various zirconia or alumina structures and their precursors as catalyst supports, and are limited depending on the production method and raw materials. It is not a thing.
Examples of such zirconia-based carriers include oxides such as amorphous zirconia, monoclinic zirconia, and tetragonal zirconia. In addition, as a precursor that is calcined to become zirconia, organic zirconium compounds such as zirconium isopropoxide and zirconium acetylacetonate, inorganic zirconium salts such as zirconium chloride and zirconyl nitrate can be used. These can be calcined as they are, but can also be calcined after being hydrolyzed with water, ammonia or the like to form zirconia hydroxide. On the other hand, examples of the alumina carrier include oxides such as α-alumina, β-alumina, and γ-alumina. Examples of the precursor that is calcined into alumina include organic aluminum compounds such as aluminum isopropoxide and aluminum acetylacetonate, and inorganic aluminum salts such as aluminum nitrate and aluminum chloride. These can be calcined as they are, but can also be calcined after being hydrolyzed with water, ammonia or the like to form aluminum hydroxide.
本発明で触媒の活性金属として用いる、(i)のニッケル含有物質としては,いかなる形態のものも含まれるが、水や有機溶媒に可溶なものが推奨され、硝酸ニッケル、硫酸ニッケルなどの無機酸ニッケル塩類、塩化ニッケル、臭化ニッケルなどのハロゲン化ニッケル類、蓚酸ニッケル、ステアリン酸ニッケル、酢酸ニッケルなどの有機酸ニッケル類、ニッケロセン、ニッケルアセチルアセトネートなどの有機金属ニッケル類、などが例示される。ニッケル系物質の添加量は任意であるが、ジルコニア又はアルミナ系担体に対して、ニッケル0.01wt%〜100wt%、好ましくは1wt%〜70wt%である。 The nickel-containing material (i) used as the active metal of the catalyst in the present invention includes any form, but those soluble in water and organic solvents are recommended, and inorganic materials such as nickel nitrate and nickel sulfate are recommended. Illustrative examples include nickel acid salts, nickel halides such as nickel chloride and nickel bromide, organic acid nickels such as nickel oxalate, nickel stearate and nickel acetate, and organometallic nickels such as nickelocene and nickel acetylacetonate. The The addition amount of the nickel-based material is arbitrary, but it is 0.01 wt% to 100 wt% nickel, preferably 1 wt% to 70 wt% with respect to the zirconia or alumina support.
また、上記ニッケル含有物質と併用される、(ii)の他方の触媒の活性成分(添加物I)としては、周期律表第6B族、7B族、第8族又はランタノイド族金属から選ばれた少なくとも一種の金属を含む物質が用いられる。第6B族金属としては、クロム、モリブデン、タングステンが挙げられ、7B族金属としては、マンガン、テクネチウム、レニウムなどが挙げられる。また第8族としては、鉄、コバルト、ロジウムなどが例示される。これらの金属を含む物質としては、それらの硝酸塩、硫酸塩などの無機酸塩、塩化物、臭化物などのハロゲン化物、蓚酸塩、酢酸塩などの有機酸塩、クロム酸塩、過レニウム酸塩などの遷移金属酸塩、テトラカルボニル鉄酸塩などの有機金属酸塩、シクロペンタジエニル化合物などの有機配位化合物、などが例示される。 The active component (additive I) of the other catalyst of (ii) used in combination with the nickel-containing substance was selected from Group 6B, Group 7B, Group 8 or lanthanoid group metal of the periodic table A substance containing at least one metal is used. Examples of the Group 6B metal include chromium, molybdenum, and tungsten. Examples of the Group 7B metal include manganese, technetium, and rhenium. Examples of Group 8 include iron, cobalt, and rhodium. Substances containing these metals include inorganic acid salts such as nitrates and sulfates, halides such as chlorides and bromides, organic acid salts such as oxalates and acetates, chromates and perrhenates. Transition metal acid salts, organic metal acid salts such as tetracarbonyl ferrate, organic coordination compounds such as cyclopentadienyl compounds, and the like.
これらの添加量は任意であるが、ジルコニアまたはアルミナ系担体に対して金属元素0.01wt%〜80wt%、好ましくは1wt%〜20wt%である。これらの添加物(I)は、単独もしくは2種以上の混合物として用いることができる。とりわけ7B族のレニウム元素の場合には、レニウム−硫黄結合の選択的な生成により、水素生成能だけでなくニッケルの耐硫黄性が高められるので、特に好ましい。 Although these addition amounts are arbitrary, they are 0.01 wt%-80 wt%, Preferably they are 1 wt%-20 wt% with respect to a zirconia or an alumina type | system | group support | carrier. These additives (I) can be used alone or as a mixture of two or more. In particular, in the case of a rhenium element belonging to Group 7B, selective generation of a rhenium-sulfur bond is particularly preferable because not only hydrogen generation ability but also sulfur resistance of nickel is enhanced.
本発明の触媒は、上記したように、ジルコニア系またはアルミナ系担体に、(i)ニッケル含有物質及び、(ii)周期律表第6B族、7B族、第8族又はランタノイド族金属から選ばれた少なくとも一種の金属を含む物質を担時させることを必須要件とするものであるが、さらに他の活性成分としては、周期律表第Ia族金属又はIIa族金属(アルカリ又はアルカリ土類金属ともいう)を含む物質(添加物II)を併用するとことが好ましい。添加物(II)を併用すると、更に高選択率、高収率で水素を製造することができるからである。 As described above, the catalyst of the present invention is selected from (i) a nickel-containing substance and (ii) a group 6B, 7B, 8 or lanthanoid group metal in the periodic table as a zirconia-based or alumina-based support. In addition, it is an essential requirement that a substance containing at least one metal is supported, but as another active ingredient, a Group Ia metal or Group IIa metal (alkaline or alkaline earth metal) is also included. It is preferable that a substance (additive II) containing This is because when additive (II) is used in combination, hydrogen can be produced with higher selectivity and yield.
この場合、第Ia族金属としては、リチウム、ナトリウム、カリウムが挙げられ、IIa族金属としては、マグネシウム、ストロンチウム、カルシウム、バリウムなどが挙げられる。これらの金属を含む物質としては、それらの硝酸塩、硫酸塩などの無機酸塩、塩化物、臭化物などのハロゲン化物、蓚酸塩、酢酸塩などの有機酸塩、クロム酸塩、バナジン酸塩などの遷移金属酸塩、テトラカルボニル鉄酸塩などの有機金属酸塩、シクロペンタジエニル化合物などの有機配位化合物、メチラートやエチラートなどのアルコラート類、などが例示される。これらの添加量は任意であるが、ジルコニアやアルミナ系担体に対して金属元素0.01wt%〜80wt%、好ましくは1wt%〜20wt%である。これらの添加物(II)は、単独もしくは2種以上の混合物として用いることができる。 In this case, the Group Ia metal includes lithium, sodium, and potassium, and the Group IIa metal includes magnesium, strontium, calcium, barium, and the like. Substances containing these metals include inorganic acid salts such as nitrates and sulfates, halides such as chlorides and bromides, organic acid salts such as oxalates and acetates, chromates and vanadates. Examples include transition metal acid salts, organic metal acid salts such as tetracarbonyl ferrate, organic coordination compounds such as cyclopentadienyl compounds, alcoholates such as methylate and ethylate, and the like. Although these addition amounts are arbitrary, they are 0.01 wt%-80 wt%, preferably 1 wt%-20 wt% of a metal element with respect to a zirconia or an alumina type support | carrier. These additives (II) can be used alone or as a mixture of two or more.
本発明の触媒の調製方法としては,(イ)担体であるジルコニアまたはアルミナ系物質にニッケル化合物および添加物Iを含浸させる方法,(ロ)ジルコニアまたはアルミナ系担体に添加物Iを含浸させ、さらにニッケル化合物を沈澱させる方法,(ハ)ジルコニアまたはアルミナ系担体にニッケルおよび添加物Iの溶液を滴下する方法(incipient wetness法),(ニ)ジルコニアまたはアルミナ系担体,ニッケル化合物および添加物Iを混ねいする方法、(ホ)ゾルゲル法(ジルコニウムまたはアルミニウム化合物,ニッケル化合物、添加物Iの3者を水やアルコールなどの溶液にすべて溶かし、必要に応じて有機酸を添加して、蒸発乾固後、焼成する)、(ヘ)これまで示した(イ)〜(ホ)の方法において、さらに添加物IIを共存させる方法、などが例示される.(ロ)の場合,通常ニッケルの無機酸塩と,塩基性の沈澱剤の組み合わせが好ましく,沈澱剤としてはアンモニア水,炭酸カリウム,炭酸ナトリウムなどが例示される.また(ホ)の有機酸としては、クエン酸、アルギン酸などの生物由来の多価酸が好ましく用いられる。また(ヘ)では、添加物IとIIをニッケル含有物質と同時に共存させて行う方法だけでなく、逐次的に共存させることも可能である。(イ)〜(へ)のいずれの方法でも、最終的に焼成を行うが、この時の温度は、300〜1500℃、好ましくは500〜900℃である。 The catalyst preparation method of the present invention includes (a) a method of impregnating a carrier zirconia or alumina material with a nickel compound and additive I, (b) impregnating a zirconia or alumina carrier with additive I, Method of precipitating nickel compound, (c) Method of dropping nickel and additive I solution on zirconia or alumina carrier (incipient wetness method), (d) Mixing zirconia or alumina carrier, nickel compound and additive I Nebulization method, (e) sol-gel method (zirconium or aluminum compound, nickel compound, additive I are all dissolved in a solution such as water or alcohol, and if necessary, add an organic acid and evaporate to dryness. , Calcination), (f) Examples of methods (i) to (e) shown above, and a method in which additive II is further coexisted. It is done. In the case of (b), a combination of a nickel inorganic acid salt and a basic precipitating agent is usually preferred, and examples of the precipitating agent include ammonia water, potassium carbonate, and sodium carbonate. As the organic acid (e), polyvalent acids derived from organisms such as citric acid and alginic acid are preferably used. In (f), it is possible not only to add the additives I and II together with the nickel-containing substance, but also to coexist sequentially. Firing is finally performed by any of the methods (i) to (f), and the temperature at this time is 300 to 1500 ° C, preferably 500 to 900 ° C.
本発明で水素製造原料として使用する炭化水素としては、通常、常温で気体又は液体の炭化水素であって、具体的には、メタン、エタン、エチレン、プロパン等の脂肪族炭化水素;シクロヘキサン、メチルシクロヘキサン、シクロペンタン等の脂環式炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素等が挙げられ、これらは単独又は2種以上の混合物として使用される。また、パラフィンワックス等の常温で固体の炭化水素を使用することもできる。
特に、本発明においては、前記特有なニッケル系触媒を用いたことから、原料炭化水素として、水素/炭素比の高い炭化水素のみならず水素/炭素比の低い炭化水素や上記脂肪族炭化水素、脂環式炭化水素及び芳香族炭化水素の2種以上の組み合わせからなる炭化水素油たとえばガソリン、灯油などの混合油を用いることが可能である。さらに硫黄を含む有機物質を共存させることもできる。この時の有機物質として、チオフェン、ジベンゾチオフェンなどの芳香族チオフェン類、
チオフェノール、プロピルスルフィドなどの脂肪族硫黄化合物などが例示される。炭化水素混合物中に許容される硫黄濃度は、0〜1000ppm(硫黄の重量基準)、好ましくは0〜10ppmである。
The hydrocarbon used as a raw material for producing hydrogen in the present invention is usually a gas or liquid hydrocarbon at normal temperature, specifically, an aliphatic hydrocarbon such as methane, ethane, ethylene, propane, etc .; cyclohexane, methyl Examples thereof include alicyclic hydrocarbons such as cyclohexane and cyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene, and these are used alone or as a mixture of two or more. Also, hydrocarbons that are solid at room temperature, such as paraffin wax, can be used.
In particular, in the present invention, since the unique nickel-based catalyst is used, as a raw material hydrocarbon, not only hydrocarbons having a high hydrogen / carbon ratio but also hydrocarbons having a low hydrogen / carbon ratio and the above aliphatic hydrocarbons, It is possible to use hydrocarbon oils composed of a combination of two or more of alicyclic hydrocarbons and aromatic hydrocarbons, for example, mixed oils such as gasoline and kerosene. Furthermore, an organic substance containing sulfur can be allowed to coexist. As organic substances at this time, aromatic thiophenes such as thiophene and dibenzothiophene,
Examples thereof include aliphatic sulfur compounds such as thiophenol and propyl sulfide. The sulfur concentration allowed in the hydrocarbon mixture is 0 to 1000 ppm (based on the weight of sulfur), preferably 0 to 10 ppm.
炭化水素は、そのまま純品で用いることもできるが、熱力学的に有利に効率良く熱分解させるためにアルゴン、窒素、ヘリウム等の不活性ガスで希釈して使うことも可能である。このときの希釈率は任意である。反応温度は200〜1,200℃、好ましくは500〜800℃であり、また触媒表面と炭化水素ガスとの接触時間は0.01〜1000秒、好ましくは0.1〜10秒とするのが望ましい。
また本反応は通常水の共存下で行われ、水(スチーム)量は任意であるが、原料炭化水素中に含まれる炭素1モルに対し0.001〜100モル、好ましくは0.01〜10モルの割合である。さらに、水に加えて酸素や二酸化炭素を共存させることも可能であり、加える量は任意であるが、水と同程度の範囲で用いられる。
Hydrocarbons can be used pure as they are, but they can also be diluted with an inert gas such as argon, nitrogen, helium, etc. in order to thermally decompose efficiently and efficiently thermodynamically. The dilution rate at this time is arbitrary. The reaction temperature is 200 to 1,200 ° C, preferably 500 to 800 ° C, and the contact time between the catalyst surface and the hydrocarbon gas is 0.01 to 1000 seconds, preferably 0.1 to 10 seconds. desirable.
Further, this reaction is usually carried out in the presence of water, and the amount of water (steam) is arbitrary, but 0.001 to 100 mol, preferably 0.01 to 10 mol per mol of carbon contained in the raw material hydrocarbon. The molar ratio. Furthermore, it is possible to coexist oxygen and carbon dioxide in addition to water, and the amount to be added is arbitrary, but it is used in the same range as water.
本発明の熱分解方法は、バッチ方式或いは流通方式のいずれも採用できるが、好ましくは流通方式で実施される。流通方式で行う場合には、固定床方式、移動床方式、循環流動層方式等を適宜採用できる。本発明の方法を固定床方式で実施する場合には、触媒を管状反応器に充填して触媒充填層を設けることが好ましい。その際、触媒充填層の上下端部には炭素質物質の粒径より小さな細孔を有するフィルター層を積層して触媒層を固定することが望ましい。 The thermal decomposition method of the present invention can employ either a batch method or a distribution method, but is preferably carried out by a distribution method. In the case of performing the distribution method, a fixed bed method, a moving bed method, a circulating fluidized bed method, or the like can be appropriately employed. When the method of the present invention is carried out in a fixed bed system, it is preferable to provide a catalyst packed bed by packing a catalyst in a tubular reactor. At that time, it is desirable to fix the catalyst layer by laminating filter layers having pores smaller than the particle size of the carbonaceous material on the upper and lower ends of the catalyst packed layer.
本発明の新規なニッケル系触媒は、従来公知のニッケル系触媒とは異なり、(ii)の周期律表第6B族、7B族、第8族又はランタノイド族金属から選ばれた少なくとも一種の金属を含む物質(添加物(I))と、ニッケル及びジルコニアまたはアルミナ担体との相乗効果により、(i)ニッケル触媒上に堆積されている炭素がより効率的に水や酸素と反応して水素へと変換され、その水素生成速度、水素生成活性に優れることから、原料炭化水素として水素/炭素比の低い炭化水素や炭化水素油たとえばガソリンや灯油などの炭化水素混合油を用いたとしても、高選択率、高収率で水素を製造することができる。また前記添加物(I)の存在によりニッケル触媒の耐硫黄性も改善される。さらにアルカリ又はアルカリ土類金属(添加物(II))を含有させた触媒では水素生成活性がより一層高められる。 The novel nickel-based catalyst of the present invention differs from conventionally known nickel-based catalysts in that it comprises at least one metal selected from Group 6B, Group 7B, Group 8 or lanthanoid group metal of (ii) in the periodic table. Due to the synergistic effect of the contained material (additive (I)) and nickel and zirconia or alumina support, (i) the carbon deposited on the nickel catalyst reacts more efficiently with water and oxygen to hydrogen. Because it is converted, and its hydrogen production rate and hydrogen production activity are excellent, even if hydrocarbons with a low hydrogen / carbon ratio or hydrocarbon oils such as gasoline and kerosene are used as raw material hydrocarbons, they are highly selected. Hydrogen can be produced at a high yield. Further, the presence of the additive (I) improves the sulfur resistance of the nickel catalyst. Further, the catalyst containing an alkali or alkaline earth metal (additive (II)) further enhances the hydrogen generation activity.
次に、本発明を実施例によって更に詳細に説明する。
実施例1
硝酸ニッケル0.619g(ニッケルの担持率5wt%)と硝酸コバルト0.247gを(同2wt%)を蒸留水40gに溶かし、その後溶液に市販の活性アルミナ2.5gを懸濁させ、金属分をアルミナに担持する。蒸留水を蒸発乾固し、100℃で一晩放置後,500℃で6時間焼成し,2.81gのNi/Co/Al2O3触媒を得た。
こうして得た触媒1gをペレット化し、適度に分割した後、これを内径12mmの石英製反応管の中央に充填して触媒層を形成した。この場合、触媒層両端に石英ウールを充填して反応中に触媒が移動しないようにした。この反応管を電気炉内に装填し、空気600℃で30分、さらに水素400℃で2時間還元した。その後、メチルシクロヘキサン(MCH)/スチーム/窒素が1/7/2.2(モル比)の混合ガスを130cm3/minの速度で通しながら、反応管の内温を5℃/minの速度で580℃まで昇温させて反応を開始した。この時MCHは液体ポンプにて注入した。2時間後のガス組成をガスクロマトグラフにて分析したところ、MCH転化率、水素生成速度及び水素組成は表2のようになり、MCH転化率40.6%、水素生成速度78.3μmol/s/g、組成70.3%が得られた。副生物はメタン、CO、CO2であった。なお、MCH転化率(CHC%)、水素速度(F)、水素組成(Comp)は下式にて計算される。
Next, the present invention will be described in further detail with reference to examples.
Example 1
0.619g of nickel nitrate (5wt% of nickel support) and 0.247g of cobalt nitrate (2wt% of the same) are dissolved in 40g of distilled water, then 2.5g of commercially available activated alumina is suspended in the solution, and the metal content is supported on alumina. To do. Distilled water was evaporated to dryness, allowed to stand at 100 ° C. overnight and then calcined at 500 ° C. for 6 hours to obtain 2.81 g of Ni / Co / Al 2 O 3 catalyst.
1 g of the catalyst thus obtained was pelletized and appropriately divided, and then filled in the center of a quartz reaction tube having an inner diameter of 12 mm to form a catalyst layer. In this case, both ends of the catalyst layer were filled with quartz wool so that the catalyst did not move during the reaction. This reaction tube was loaded in an electric furnace and reduced at 600 ° C. for 30 minutes and further at 400 ° C. for 2 hours. Then, while passing a mixed gas of methylcyclohexane (MCH) / steam / nitrogen 1/7 / 2.2 (molar ratio) at a rate of 130 cm3 / min, the internal temperature of the reaction tube was increased to 580 ° C at a rate of 5 ° C / min. The reaction was started by raising the temperature. At this time, MCH was injected with a liquid pump. When the gas composition after 2 hours was analyzed by gas chromatography, the MCH conversion rate, hydrogen production rate and hydrogen composition were as shown in Table 2. MCH conversion rate 40.6%, hydrogen production rate 78.3μmol / s / g, composition 70.3% was obtained. By-products were methane, CO, and CO2. The MCH conversion rate (C HC %), hydrogen velocity (F), and hydrogen composition (Comp) are calculated by the following equations.
比較例1
硝酸ニッケルを用いない以外は実施例1と同様にして調製した触媒(Co/Al2O3)を用いて同様に反応させたところ、表2の比較例1のようになり、ほとんど活性は認められなかった。
Comparative Example 1
When the same reaction was carried out using a catalyst (Co / Al2O3) prepared in the same manner as in Example 1 except that nickel nitrate was not used, it was as shown in Comparative Example 1 in Table 2 and almost no activity was observed. .
比較例2
硝酸コバルトを用いない以外は実施例1と同様にして調製した触媒(Ni/Al2O3)を用いて同様に反応させたところ、表2の比較例2のようになり、MCH転化率は5.5%、水素生成速度16.6μmol/s/gと、転化率は実施例1の約1/7、水素生成速度は約1/5と少なかった。
Comparative Example 2
When the same reaction was carried out using a catalyst (Ni / Al2O3) prepared in the same manner as in Example 1 except that cobalt nitrate was not used, it was as shown in Comparative Example 2 in Table 2, with an MCH conversion of 5.5%, The hydrogen production rate was 16.6 μmol / s / g, the conversion rate was about 1/7 that of Example 1, and the hydrogen production rate was about 1/5.
実施例2、3
硝酸コバルトの代わりに、モリブデン酸アンモニウム、過レニウム酸アンモニウムを用いて、5wt%Ni/2wt%Mo(またはRe)/Al2O3触媒を調製し、実施例1と同様にして反応させたところ、表2のような結果となり、コバルトの場合より転化率、水素生成速度共に高められた結果となった。
Examples 2 and 3
A 5 wt% Ni / 2 wt% Mo (or Re) / Al 2 O 3 catalyst was prepared using ammonium molybdate and perrhenic acid ammonium instead of cobalt nitrate and reacted in the same manner as in Example 1. Table 2 As a result, both the conversion rate and the hydrogen production rate were increased as compared with the case of cobalt.
比較例3,4
硝酸ニッケルを用いないで、モリブデンまたはレニウムのみをアルミナに担持して調製した触媒を用いた以外は実施例2,3と同様にして反応させたところ、表2の比較例3及び4のようになり、Moではほとんど活性は認められず、レニウムでは、MCH転化率は14.3%、水素生成速度34.2μmol/s/gと、転化率は実施例3の約1/4以下、水素生成速度は約1/3と少なかった。
実施例4〜6
Ni/Al2O3と、Co/Al2O3、Mo/Al2O3、Re/Al2O3をそれぞれ物理混合した触媒を用いた以外は実施例1と同様に反応させたところ、表2の結果となり、Niとその他の活性成分の同時含浸で調製した触媒と同程度の性能が得られた。
Comparative Examples 3 and 4
The reaction was carried out in the same manner as in Examples 2 and 3 except that a catalyst prepared by supporting only molybdenum or rhenium on alumina without using nickel nitrate was used. As shown in Comparative Examples 3 and 4 in Table 2, In the case of rhenium, the MCH conversion rate is 14.3%, the hydrogen production rate is 34.2 μmol / s / g, the conversion rate is about 1/4 or less of Example 3, and the hydrogen production rate is about It was less than 1/3.
Examples 4-6
The reaction in the same manner as in Example 1 except that a catalyst in which Ni / Al2O3, Co / Al2O3, Mo / Al2O3, and Re / Al2O3 were each physically mixed was used. The results shown in Table 2 were obtained. Ni and other active ingredients The same performance as that of the catalyst prepared by simultaneous impregnation was obtained.
実施例7
硫黄20ppmを含むメチルシクロヘキサンを用いた以外は実施例3と同様にして反応させたところ、表2のような結果となり、硫黄なしの場合(実施例3)と比べて転化率や水素生成速度に悪影響は認められなかった。
Example 7
When the reaction was carried out in the same manner as in Example 3 except that methylcyclohexane containing 20 ppm of sulfur was used, the results shown in Table 2 were obtained, and the conversion rate and hydrogen production rate were improved compared to the case without sulfur (Example 3). No adverse effect was observed.
比較例5,6
Ni/Al2O3及びRe/Al2O3触媒を用いた以外は実施例7と同様にして反応させたところ、Ni/Al2O3では完全に失活し、またRe/Al2O3では、転化率22.1%、水素生成速度58.0μmol/s/gと、実施例7より1/3〜1/4となった。
Comparative Examples 5 and 6
The reaction was carried out in the same manner as in Example 7 except that Ni / Al2O3 and Re / Al2O3 catalysts were used. Ni / Al2O3 was completely deactivated, and Re / Al2O3 had a conversion rate of 22.1% and a hydrogen production rate of 58.0. μmol / s / g, which was 1/3 to 1/4 from Example 7.
実施例8
メチルシクロヘキサン(MCH)の代わりに、MCH75%/トルエン25%の混合物を用いた以外は実施例3と同様にして反応させたところ、表2のような結果となり、MCH単独の場合と同程度の性能が得られ、芳香族の影響は認められなかった。
Example 8
When the reaction was carried out in the same manner as in Example 3 except that a mixture of MCH75% / toluene 25% was used instead of methylcyclohexane (MCH), the results shown in Table 2 were obtained, which was similar to that of MCH alone. Performance was obtained and no aromatic effects were observed.
実施例9
硝酸ジルコニル21gを蒸留水100gに溶かし、水で希釈したアンモニア水100ml(アンモニア水25ml/水75ml)を滴下して水酸化ジルコニウムの沈殿を得る。100℃で一晩乾燥後、ここで、300℃で3時間焼成してアモルファスジルコニア(AZ)を得た。次に硝酸ニッケル2.48g(AZに対するニッケルの担持率10wt%)と硝酸ストロンチウム0.604gを(同5wt%),硝酸ランタン0.39g(同5wt%)を蒸留水40gに溶かし、その後溶液にAZ 2.5gを懸濁させ、金属分をジルコニアに担持する。蒸留水を蒸発乾固し、100℃で一晩放置後,700℃で3時間焼成し,2.85gのNi/Sr/La/ZrO2触媒を得た。
こうして得た触媒1gをペレット化し、適度に分割した後、粒径100〜1000μmの石英砂5gを良く混合し、これを内径12mmの石英製反応管の中央に充填して触媒層を形成した。この場合、触媒層両端に石英ウールを充填して反応中に触媒が移動しないようにした。この反応管を電気炉内に装填し、水素で600℃、2時間還元した。その後、10ppmの硫黄を含むメチルシクロヘキサン(MCH)を用い、MCH/H2O/O2/N2=5.18/59.16/28.53/7.13(スチーム/炭素比=1.63(モル比)、酸素/炭素比=0.44(モル比))の混合ガスを流しながら、反応管の内温を5℃/minの速度で800℃まで昇温させて反応を開始した。この時MCHは液体ポンプにて注入した。5時間後のガス組成をガスクロマトグラフにて分析したところ、MCH転化率100%、水素生成速度44.9μmol/s/gとなった。副生物はメタン、CO、CO2であり、エタン、エチレン、ベンゼン等の有機生成物は全く認められなかった。
Example 9
Zirconyl nitrate (21 g) is dissolved in distilled water (100 g), and 100 ml of ammonia water diluted with water (ammonia water 25 ml / water 75 ml) is added dropwise to obtain zirconium hydroxide precipitate. After drying at 100 ° C. overnight, it was calcined at 300 ° C. for 3 hours to obtain amorphous zirconia (AZ). Next, 2.48 g of nickel nitrate (10 wt% of nickel supported on AZ), 0.604 g of strontium nitrate (5 wt%) and 0.39 g of lanthanum nitrate (5 wt%) were dissolved in 40 g of distilled water, and then 2.5 g of AZ was added to the solution. Is suspended and the metal content is supported on zirconia. Distilled water was evaporated to dryness, allowed to stand at 100 ° C overnight, then calcined at 700 ° C for 3 hours to obtain 2.85 g of Ni / Sr / La / ZrO2 catalyst.
After pelletizing 1 g of the catalyst thus obtained and dividing it appropriately, 5 g of quartz sand having a particle diameter of 100 to 1000 μm was mixed well and filled in the center of a quartz reaction tube having an inner diameter of 12 mm to form a catalyst layer. In this case, both ends of the catalyst layer were filled with quartz wool so that the catalyst did not move during the reaction. The reaction tube was loaded into an electric furnace and reduced with hydrogen at 600 ° C. for 2 hours. Then, using methylcyclohexane (MCH) containing 10 ppm sulfur, MCH / H2O / O2 / N2 = 5.18 / 59.16 / 28.53 / 7.13 (steam / carbon ratio = 1.63 (molar ratio), oxygen / carbon ratio = 0.44 (molar) The reaction was started by increasing the internal temperature of the reaction tube to 800 ° C. at a rate of 5 ° C./min. At this time, MCH was injected with a liquid pump. When the gas composition after 5 hours was analyzed by gas chromatography, the MCH conversion rate was 100% and the hydrogen production rate was 44.9 μmol / s / g. By-products were methane, CO, and CO2, and organic products such as ethane, ethylene, and benzene were not observed at all.
実施例10
硝酸ランタンの代わりに過レニウム酸アンモンを用いて調製した触媒を用いた以外実施例9と同様にして反応させたところ、転化率99.9%、水素生成速度36.91μmol/s/gが得られた。
Example 10
The reaction was conducted in the same manner as in Example 9 except that a catalyst prepared using ammonium perrhenate instead of lanthanum nitrate was used. As a result, a conversion rate of 99.9% and a hydrogen production rate of 36.91 μmol / s / g were obtained.
比較例734
硝酸ストロンチウムも硝酸ランタンも共に用いない以外は実施例9と同様にして調製した触媒(Ni/ZrO2)を用いて同様に反応させたところ、表2の比較例7のようになり、MCH転化率は99.9%であったが、水素生成速度10.48μmol/s/gと1/4以下、水素組成26.6%と1/2以下であった。
Comparative Example 734
The reaction was carried out in the same manner using a catalyst (Ni / ZrO2) prepared in the same manner as in Example 9 except that neither strontium nitrate nor lanthanum nitrate was used. The hydrogen production rate was 10.48 μmol / s / g, 1/4 or less, and the hydrogen composition was 26.6%, 1/2 or less.
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JP2007054721A (en) * | 2005-08-24 | 2007-03-08 | National Institute Of Advanced Industrial & Technology | Reforming catalyst for hydrogen production, and method of producing hydrogen using the same |
JP2010155234A (en) * | 2008-12-30 | 2010-07-15 | Samsung Electronics Co Ltd | Hydrocarbon reforming catalyst, manufacturing method thereof and fuel cell containing this catalyst |
JP2019034259A (en) * | 2017-08-10 | 2019-03-07 | 国立研究開発法人物質・材料研究機構 | Catalyst for hydrogen production and method for producing the same, and hydrogen production device |
WO2020023452A1 (en) * | 2018-07-23 | 2020-01-30 | The Trustees Of Columbia University In The City Of New York | Methods and systems for the generation of high purity hydrogen with co2 capture from biomass and biogenic wastes |
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JP2007054721A (en) * | 2005-08-24 | 2007-03-08 | National Institute Of Advanced Industrial & Technology | Reforming catalyst for hydrogen production, and method of producing hydrogen using the same |
JP4500943B2 (en) * | 2005-08-24 | 2010-07-14 | 独立行政法人産業技術総合研究所 | Reforming catalyst for hydrogen production and method for producing hydrogen using the same |
JP2010155234A (en) * | 2008-12-30 | 2010-07-15 | Samsung Electronics Co Ltd | Hydrocarbon reforming catalyst, manufacturing method thereof and fuel cell containing this catalyst |
JP2019034259A (en) * | 2017-08-10 | 2019-03-07 | 国立研究開発法人物質・材料研究機構 | Catalyst for hydrogen production and method for producing the same, and hydrogen production device |
WO2020023452A1 (en) * | 2018-07-23 | 2020-01-30 | The Trustees Of Columbia University In The City Of New York | Methods and systems for the generation of high purity hydrogen with co2 capture from biomass and biogenic wastes |
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