WO2020026597A1 - 水蒸気改質触媒 - Google Patents
水蒸気改質触媒 Download PDFInfo
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- WO2020026597A1 WO2020026597A1 PCT/JP2019/023054 JP2019023054W WO2020026597A1 WO 2020026597 A1 WO2020026597 A1 WO 2020026597A1 JP 2019023054 W JP2019023054 W JP 2019023054W WO 2020026597 A1 WO2020026597 A1 WO 2020026597A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 151
- 238000000629 steam reforming Methods 0.000 title claims abstract description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 243
- 239000011572 manganese Substances 0.000 claims abstract description 120
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 118
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 118
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 113
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 82
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 82
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003426 co-catalyst Substances 0.000 abstract description 15
- 230000008021 deposition Effects 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 7
- 238000011156 evaluation Methods 0.000 description 129
- 238000006243 chemical reaction Methods 0.000 description 113
- 238000004939 coking Methods 0.000 description 56
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 44
- 229910052707 ruthenium Inorganic materials 0.000 description 44
- 238000001179 sorption measurement Methods 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 38
- 239000007789 gas Substances 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 13
- 229910052721 tungsten Inorganic materials 0.000 description 13
- 239000010937 tungsten Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 230000007423 decrease Effects 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 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 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture 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
- 239000000377 silicon dioxide Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- -1 naphtha Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002453 autothermal reforming Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 150000002604 lanthanum compounds Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 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 2
- 238000013507 mapping Methods 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241000275031 Nica Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 150000004729 acetoacetic acid derivatives Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Classifications
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Definitions
- the present invention relates to a steam reforming catalyst used in a steam reforming system for producing hydrogen by reforming a hydrocarbon raw material gas and steam into carbon monoxide and hydrogen.
- hydrocarbon-based raw materials such as natural gas and coal-based hydrocarbons can be used.
- Hydrocarbons are suitably available.
- these hydrocarbon-based raw materials produce a synthesis gas of carbon monoxide and hydrogen by a reforming reaction with steam, and convert or select carbon monoxide in the synthesis gas.
- Hydrogen is produced by being removed by oxidation treatment or the like.
- Ni nickel
- Ru ruthenium
- Ni catalysts are generally widely used as industrial steam reforming catalysts or partial oxidation / autothermal reforming catalysts.
- the reforming reaction can be carried out regardless of the supported catalyst, impregnated catalyst, or kneading catalyst.
- the conditions especially, natural gas containing naphtha, LP gas and heavy hydrocarbons
- carbon deposition is remarkable and cannot withstand actual use. Therefore, potassium (K) or magnesium (Mg), which has carbon deposition suppressing effect, is used as a co-catalyst. It is added, put into practical use, and widely used worldwide (see Patent Document 3 and the like).
- Ru catalysts also have better sintering resistance than Ni catalysts. Therefore, if a high-performance desulfurization technology is adopted and sulfur poisoning is completely prevented, a compact reactor and a long service life can be achieved at the same time, so a fuel cell reformer expected to have a catalyst replacement cycle of 5 years or more is expected. Adoption to is progressing.
- Ru has a particularly low yield among platinum group metals, and is one order of magnitude less than platinum (Pt) and palladium (Pd), but has high performance as a reforming catalyst for hydrogen production because of its excellent properties.
- the required use as a fuel cell reforming catalyst is rapidly increasing, and it is expected that it will be used in large quantities in the future.
- the annual production amount (20 t) of Ru is consumed only by the reforming catalyst for 4 million kW of the domestic fuel cell.
- the replacement of the Ru catalyst is an option. This makes it possible to provide a high-performance steam reforming catalyst stably without being affected by the resource constraints of Ru.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a Ni-based steam reforming catalyst having excellent carbon deposition resistance and sintering resistance.
- the steam reforming catalyst according to the present invention comprises nickel as a catalytically active metal, lanthanum as a first promoter component, manganese as a second promoter component, and a carrier containing ⁇ -alumina as a main component, It is characterized by including.
- the steam reforming catalyst having the above-mentioned characteristics is characterized in that the catalytically active metal, the first co-catalyst component, the second co-catalyst component, and the total weight of the carrier are:
- the content of the catalytically active metal is 11 wt% or more and 18 wt% or less;
- the content of the first promoter component is 8% by weight or more and 12% by weight or less; It is preferable that the content of the second promoter component is 0.05% by weight or more and 3% by weight or less.
- the steam reforming catalyst having the above characteristics, the first co-catalyst component and the first co-catalyst component, the second co-catalyst component, and the carrier based on the total weight of the first co-catalyst component, the second co-catalyst component, and the carrier. It is preferable that the total content of the second promoter component is not less than 10.05% by weight and not more than 15% by weight.
- the steam reforming catalyst having the above-mentioned characteristics is characterized in that the catalytically active metal, the second promoter and the second promoter are added to the total weight of the catalytically active metal, the first promoter component, the second promoter component and the carrier. It is more preferable that the total content of the catalyst components is not less than 11.05% by weight and not more than 21% by weight.
- the weight ratio of the first promoter component to the catalytically active metal is preferably 50% or more and 120% or less.
- the weight ratio of the second promoter component to the catalytically active metal is preferably 0.33% or more and 20% or less.
- nickel as a catalytically active metal and lanthanum and manganese as co-catalysts are present as aggregates on a carrier containing ⁇ -alumina as a main component.
- This suppresses a decrease in the catalytic activity of nickel can achieve a high hydrocarbon conversion rate comparable to that of the Ru catalyst, and causes a decrease in the catalytic activity as compared with a case where another metal is used as a promoter.
- Carbon deposition and sintering (aggregation) of catalytically active metals are suppressed, and a high-performance Ni-based steam reforming catalyst can be provided.
- the steam reforming catalyst according to the present embodiment promotes a steam reforming reaction in which steam is brought into contact with hydrocarbons to generate a synthesis gas containing carbon monoxide and hydrogen. It is a catalyst.
- the steam reforming reaction includes an autothermal reforming reaction accompanied by a partial oxidation reaction with an oxygen-containing gas when reacting with steam.
- the hydrocarbon for example, a hydrocarbon gas having 1 to 4 carbon atoms such as methane, ethane, propane, and butane, and an alcohol such as methanol, ethanol, and propanol are used.
- the raw material gas of the steam reforming reaction using the present catalyst is not limited to one example of the hydrocarbon.
- the catalyst includes nickel as a catalytically active metal, lanthanum as a first promoter component, manganese as a second promoter component, and a carrier containing ⁇ -alumina as a main component.
- Nickel, lanthanum, and manganese are dispersed and supported on the same granular carrier, for example, and exist as an aggregate.
- lanthanum and manganese are present on the same support as nickel, which is a catalytically active metal, the function as a co-catalyst that suppresses carbon deposition and sintering of the catalytically active metal, which causes a decrease in catalytic activity, It has been found by the inventor of the present invention that lanthanum is more improved than when used alone as the cocatalyst.
- the present catalyst is based on the research results of the present inventors.
- the carrier of the present catalyst contains ⁇ -alumina as a main component (for example, 80% by weight or more and 100% by weight or less).
- ⁇ -alumina a small amount of inorganic oxides ( ⁇ -alumina, silica (silicon oxide), zirconia (Zirconium oxide), titania (titanium oxide), lanthanum oxide, calcium oxide, or the like, or a trace amount of an impurity element (sulfur, potassium, iron, or the like).
- the total content of inorganic oxides other than ⁇ -alumina is preferably about 0 to 10% by weight, and the total content of impurity elements is preferably 1% by weight or less based on the total weight of the carrier.
- the BET specific surface area of the carrier is not particularly limited, but the BET specific surface area is preferably about 90 to 300 m 2 / g so that the three components of nickel, lanthanum and manganese can be sufficiently dispersed.
- the ⁇ -alumina of the carrier is in the form of a powder, but a needle-like or fibrous form may be used as a lump, or a powdery, needle-like or fibrous form may be used. May be mixed.
- the nickel content is preferably about 11 to 18% by weight, more preferably about 13 to 17% by weight, based on the total weight of the three components of nickel, lanthanum and manganese and the carrier (hereinafter referred to as "total weight of the catalyst"). More preferred. When the content of nickel exceeds 18% by weight based on the total weight of the catalyst, the dispersibility is impaired, and the proportion of active metal exposed on the surface due to agglomeration is reduced, leading to a reduction in catalytic activity. On the other hand, when the nickel content is lower than 11% by weight based on the total weight of the catalyst, a reduction in the amount of nickel carried causes a reduction in catalytic activity.
- the lanthanum content is preferably about 8 to 12% by weight, more preferably about 10 to 12% by weight, based on the total weight of the catalyst.
- the manganese content is preferably about 0.05 to 3% by weight, more preferably about 0.5 to 2.5% by weight, and further preferably about 1 to 1.5% by weight, based on the total weight of the catalyst. preferable.
- the lanthanum content exceeds 12% by weight with respect to the total weight of the catalyst, the dispersibility is impaired, and the proportion of the cocatalyst component exposed on the surface due to agglomeration is reduced, resulting in a decrease in the function of the cocatalyst.
- the content of lanthanum is lower than 8% by weight based on the total weight of the catalyst, the function as a cocatalyst is lowered due to a reduction in the amount of lanthanum carried.
- the total content of the two components of nickel and manganese is preferably about 11.05 to 21% by weight, more preferably about 11.05 to 18% by weight, and more preferably 13 to 17% by weight based on the total weight of the catalyst. More preferred.
- the total content of the two components of lanthanum and manganese is preferably about 8.05 to 15% by weight, more preferably about 10.05 to 15% by weight, and more preferably about 10.5 to 14. 5% by weight is more preferred.
- the weight ratio of lanthanum to nickel is preferably about 50 to 120%, more preferably about 75 to 100%.
- the weight ratio of manganese to nickel (Mn / Ni) is preferably about 0.33 to 20%, more preferably about 3.33 to 20%, and more preferably about 6.66 to 15%.
- the method for preparing the present catalyst will be described with reference to a known impregnation method (same as the evaporation to dryness method).
- the method for preparing the present catalyst is not limited to the impregnation method, and a neutralization method or the like may be used.
- a mixed solution is prepared by dissolving a nickel compound, a lanthanum compound, and a manganese compound in a solvent such as water, ethanol, and acetone.
- a solvent such as water, ethanol, and acetone.
- the compounds of nickel, lanthanum and manganese nitrates, acetates, sulfates, acetoacetates, hydroxides, chlorides, and the like are used.
- nitrates and acetates can be suitably used.
- a powdery carrier or the like is added to the above mixed solution, and the mixture is stirred using an evaporator to evaporate the solvent. Subsequently, the mixture is dried at a predetermined temperature (for example, 80 ° C. to 120 ° C.), and evaporated to dryness. After solidification, finally, the catalyst is prepared through a calcination treatment at a predetermined temperature (for example, 400 ° C. to 700 ° C.). The drying atmosphere and the firing atmosphere are preferably in the air. It is preferable that the powdery carrier is sieved in advance to adjust the particle size within a predetermined range (for example, about 200 ⁇ m or less).
- the content of each of the three components nickel, lanthanum, and manganese is such that the content of the oxide (nickel oxide, lanthanum oxide, manganese oxide) after the calcination treatment is the content (wt%).
- the content of each of the three components is the content of each oxide of the three components (value in terms of oxide), and the weight of the three components constituting the total weight of the catalyst is also the weight of each of the three components.
- the weight of the oxide is set.
- nickel, lanthanum, and manganese supported on the carrier are present as oxides (nickel oxide, lanthanum oxide, and manganese oxide). Therefore, it is preferable to perform a reduction treatment in a hydrogen atmosphere or a hydrogen-containing atmosphere before using the present catalyst.
- nickel nitrate, lanthanum nitrate, and manganese nitrate are used as the nickel compound, the lanthanum compound, and the manganese compound
- the content of each of nickel, lanthanum, and manganese is 13.5% by weight, 10% by weight, and 1.5% by weight.
- 8.50 g of the carrier was mixed with 50 ml of a 500 mM aqueous nickel nitrate solution, 13.35 ml of a 500 mM aqueous lanthanum nitrate solution, 5.94 ml of a 500 mM aqueous manganese nitrate solution, and 69 ml of pure water.
- the amounts of the aqueous solutions may be appropriately adjusted.
- concentration of each aqueous solution and the amount of pure water can be changed as appropriate.
- the evaluation of the catalyst performance is carried out by examining the preferred range of the content of nickel and lanthanum with respect to the total weight of the catalyst, examining the preferred range of the content of manganese with respect to the total weight of the catalyst, and The study was carried out in the examination of the optimal use of manganese as a catalyst, the study of the carrier components, and the study of long-term stability. Therefore, in each examination section, the description of the overlapping evaluation methods is omitted.
- the conversion rate of C 3 H 8 was determined using a catalyst activity evaluation device manufactured by Henmi Keizoku Co., Ltd., and a TCD (thermal conduction type detector) Model-802 manufactured by Okura Giken (currently Hemi Kazoku Co., Ltd.) as a gas chromatograph.
- a reaction tube is charged in advance with 0.5 g of a catalyst, subjected to a reduction treatment with hydrogen gas at 600 ° C. for 1 hour, and mixed gas of N 2 , C 3 H 8 , H 2 , H 2 O (steam) (supply gas).
- the sample was burned in a high-temperature furnace using a carbon / sulfur analyzer CS744 manufactured by LECO Japan GK, and the concentration of carbon contained in the sample was measured.
- the carbon concentration (% by weight) is calculated from the ratio of the weight of carbon in the medium, and is defined as the coking amount (%).
- a total of 16 types of samples C1 to C4 were prepared. Further, as comparative samples for the samples C1 to C4, a commercially available ruthenium catalyst X1 (ruthenium loading: 2% by weight, carrier: ⁇ -alumina) and a commercial nickel catalyst X2 (NiCa catalyst, nickel loading) : 17 to 18% by weight, carrier: ⁇ -alumina).
- ruthenium catalyst X1 ruthenium loading: 2% by weight, carrier: ⁇ -alumina
- nickel catalyst X2 NiCa catalyst, nickel loading
- Samples A1 to A6, B0 to B5, and C1 to C4 each used those prepared by the above-described catalyst preparation method (impregnation method).
- the mixed solution a solution obtained by mixing a predetermined amount of an aqueous solution of nickel nitrate and an aqueous solution of lanthanum nitrate so that the content of nickel and lanthanum is a predetermined value is used.
- the carrier the content of ⁇ -alumina is used.
- a ⁇ -alumina support having a silica content of about 3% by weight or more and a BET specific surface area of about 180 to 200 m 2 / g is dried at 80 ° C. for 16 hours in advance, and then has a particle size of 96% by weight or more.
- a mixture sieved to have a thickness of about 200 ⁇ m or less an amount of the carrier in which the content of nickel and lanthanum became a predetermined value was added to the mixed solution.
- the nickel content increases, the H 2 unit adsorption amount and the C 3 H 8 conversion in the initial evaluation also increase, but the coking amount after the initial evaluation shows that the nickel content is 10% by weight. It can be seen that when the ratio exceeds%, the value rapidly increases. From the results, it is preferable to set the nickel content to 10% by weight or more from the viewpoint of the adsorption amount of H 2 units and the conversion of C 3 H 8. However, in order to increase the nickel content to more than 10% by weight. Considering the effect of suppressing the coking of lanthanum shown in FIG. 2 described below, it can be seen that the lanthanum content of 5% by weight is too small. That is, it is understood that the lower limit of the preferable range of the weight ratio of lanthanum to nickel is 50% or more.
- FIG. 2 shows the conversion of C 3 H 8 (initial evaluation at a reaction temperature of 400 ° C., 500 ° C., and 600 ° C.) and the H 2 unit adsorption before the initial evaluation, along with the nickel and lanthanum contents of Samples B0 to B5.
- the results of the evaluation of the amount and the amount of coking after the initial evaluation are shown in a table.
- the lanthanum contents of the samples B0 to B5 were 0% by weight, 5% by weight, 8% by weight, 10% by weight, 12% by weight and 20% by weight, respectively, and the nickel content was 10% by weight, respectively. It is constant.
- FIG. 3 shows the conversion rates of C 3 H 8 of the samples C1 to C4 and the comparative samples X1 and X2 (reaction temperatures of 400 ° C., 500 ° C., and 600 ° C.) along with the respective contents of nickel and lanthanum of the samples C1 to C4.
- initial evaluation shows an initial evaluation before H 2 adsorption (H 2 units adsorption amount, metal dispersion degree, average particle diameter), and, a summary of the evaluation results of the coking amount after initial evaluation tabulated.
- the ruthenium catalyst X1 was CO adsorption evaluation instead of H 2 adsorption evaluation.
- the nickel contents of samples C1 to C4 are 10% by weight, 12% by weight, 15% by weight, and 20% by weight, respectively, and the lanthanum content is constant at 10% by weight, respectively.
- the C 3 H 8 conversion increases as the nickel content increases from 10% by weight to 15% by weight, but when the nickel content increases to 20% by weight, the C 3 H 8 conversion increases. On the contrary, it is falling. Therefore, considering the C 3 H 8 conversion at a reaction temperature of 400 ° C., the upper limit of the preferable range of the nickel content is in the middle between 15% by weight and 20% by weight (for example, about 17.5% by weight). And the lower limit is presumed to be between 10% and 12% by weight. Therefore, the preferred range of the nickel content is estimated to be 11% to 18% by weight, more preferably 13% to 17% by weight, and the optimal value of the nickel content is estimated to be about 15% by weight. You.
- the coking amount after the initial evaluation naturally increases as the nickel content increases, but when the nickel content is 12% by weight or more, the coking amount of the ruthenium catalyst X1 is larger than that of the sample C2 (nickel content). : About 1.8 times for sample C3 (nickel content: 15% by weight) and about 2.7 times for sample C3 (nickel content: 20% by weight). is there. However, as compared with the samples A1 to A6 having a lanthanum content of 5% by weight, the samples C1 to C4 having a lanthanum content of 10% by weight have a reduced coking amount even if the nickel content exceeds 10% by weight. The rapid increase is sufficiently suppressed.
- the preferable range of the lanthanum content is 8% by weight to 12% by weight, more preferably 10% by weight. It is estimated to be between 12% and 12% by weight. Further, judging comprehensively from the evaluation results shown in FIGS. 1 to 3, the suitable range of the weight ratio of lanthanum to nickel is estimated to be 50% to 120%, more preferably 75% to 100%.
- the coking amount was about twice that of the ruthenium catalyst X1 even if the nickel content and the lanthanum content were respectively within the preferred ranges. Therefore, in order to suppress the coking amount to the same extent as that of the ruthenium catalyst X1, it is necessary to add manganese as the second promoter component as described later.
- FIG. 4 shows the results of evaluating the C 3 H 8 conversion at a reaction temperature of 450 ° C. for 96 hours continuously (eight times every 12 hours) together with the samples X1 and X2.
- the vertical axis of the graph in FIG. 4 is the C 3 H 8 conversion (%), and the horizontal axis is the elapsed time.
- Evaluation conditions of C 3 H 8 conversion, except the reaction temperature is the same as the evaluation condition of C 3 H 8 conversion of the initial evaluation of the samples C1 ⁇ C4 shown in FIG.
- the C 3 H 8 conversion up to 96 hours at the reaction temperature of 450 ° C. was higher than the C 3 H 8 conversion of the ruthenium catalyst X1 not only for the sample C3 but also for the sample C1, and the C 3 H 8 conversion was up to 96 hours. Also in the evaluation, the sample C3 has the highest evaluation.
- the C 3 H 8 conversion of the added sample C5 is significantly lower than that of the ruthenium catalyst X1 because the nickel content is as low as 8% by weight.
- Samples D1 to D7 and E1 to E6 used were each prepared by the above-described catalyst preparation method (impregnation method).
- As the mixed solution nickel, lanthanum, and a mixture of a predetermined amount of an aqueous solution of nickel nitrate, an aqueous solution of lanthanum nitrate, and an aqueous solution of manganese nitrate are used such that the content of manganese becomes a predetermined value.
- a ⁇ -alumina carrier having a ⁇ -alumina content of 96% by weight or more, a silica content of about 3% by weight, and a BET specific surface area of about 180 to 200 m 2 / g was previously placed at 80 ° C. for 16 hours. After drying, the carrier was sieved to a particle size of about 200 ⁇ m or less, and the carrier was added to the mixed solution in an amount such that the content of nickel, lanthanum, and manganese became a predetermined value.
- the manganese content of Samples D1 to D7 was, in order, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.5% by weight, 1.0% by weight, 1.5% by weight, 2.0% by weight.
- the nickel content and the lanthanum content of the samples D0 to D7 are constant at 15% by weight and 10% by weight, respectively.
- the effect of the addition is apparent.
- the coking amount of sample D5 (the manganese content was 1% by weight) was the smallest, and decreased to the same value as the coking amount (0.14%) of comparative sample (ruthenium catalyst) X1.
- the coking amount tends to slightly increase.
- the coking amount is 1.0 to 1.71 times the coking amount (0.14%) of the comparative sample (ruthenium catalyst) X1. It has become.
- FIG. 6 shows the conversion rates of C 3 H 8 of the samples E1 to E6 and the comparative sample (ruthenium catalyst) X1 (reaction temperature of 400 ° C., 500 ° C.) along with the respective contents of nickel, lanthanum, and manganese of the samples E1 to E6.
- the results of the evaluation of the initial evaluation at 600 ° C. and 600 ° C.), the adsorption amount of H 2 units (before the initial evaluation), and the coking amount after the initial evaluation are shown in a table.
- the evaluation result of the ruthenium catalyst X1 is the same as the content shown in FIG.
- the manganese contents of samples E1 to E3 were 0.75% by weight, 1.5% by weight, and 3.0% by weight, respectively.
- the total content of nickel and manganese and the content of lanthanum were all , 15% by weight and 10% by weight.
- the manganese contents of samples E4 to E6 were 0.5% by weight, 1.0% by weight, and 2.0% by weight, respectively.
- the total content of nickel and manganese and the content of lanthanum were all Is constant at 10% by weight and 10% by weight.
- C 3 H 8 conversion initial evaluation results shown in Figure 6 the reaction temperature is 400 ° C., 500 ° C., in either 600 °C, C 3 H 8 conversion of the sample E1 ⁇ E6 is the comparative sample X1 It is larger than the C 3 H 8 conversion and both catalyst activities are high. In the reaction temperature is 400 ° C., between the sample E1 ⁇ E6, difference occurs in the C 3 H 8 conversion. From the results of the initial evaluation of the C 3 H 8 conversion of the samples C1 to C4 to which manganese was not added as shown in FIG. 3, when the lanthanum content was constant at 10% by weight, the nickel content was 15% by weight. %, The conversion rate of C 3 H 8 increases with the increase.
- the upper limit of the preferred range is considered to be 2.5 to 3.0% by weight, and more preferably 2.0 to 2.5% by weight.
- the lower limit of the preferred range is considered to be 0.05% by weight, more preferably 0.5% by weight.
- the coking amounts of the samples E1 to E3 were smaller than those of the samples E4 to E6 despite the higher nickel content, and the coking amounts of the samples E1 to E3 were:
- the coking amount (0.14%) of the comparative sample (ruthenium catalyst) X1 is not more than the above.
- C 3 H 8 conversion (initial evaluation) and coking of evaluation results at the 400 ° C., in a sample D0 ⁇ D7 shown in FIG. 5, in the samples D5 (content of 1% by weight of manganese), C 3 H 8 conversion is highest, coking amount smallest, in the sample E1 ⁇ E3 shown in FIG. 6, in the sample E2 (1.5% by weight manganese content), C 3 H 8 conversion is most
- the optimum value of the manganese content is 1.0 to 1.5% by weight (based on the amount of nickel supported, 6.66 to (Corresponding to 10% by weight).
- the nickel content was reduced from 15% by weight to 0.75 to 3% by weight. It can be understood that, by setting the content of 0.75 to 3% by weight, the coking amount can be suppressed to be equal to or less than that of the comparative sample X1 while maintaining the catalytic activity higher than that of the comparative sample (ruthenium catalyst) X1. Thus, by replacing a portion of nickel having a content within the preferred range with manganese having a content within the preferred range, coking while maintaining a higher catalytic activity than the comparative sample (ruthenium catalyst) X1 was performed. It is considered that the amount can be suppressed to be equal to or less than that of the comparative sample X1.
- Nickel 11 to 18% by weight, more preferably 13 to 17% by weight.
- Lanthanum 8 to 12% by weight, more preferably 10 to 12% by weight.
- Manganese 0.05 to 3% by weight, more preferably 0.5 to 2.5% by weight, still more preferably 1 to 1.5% by weight.
- a preferable range of the total content of nickel and manganese is assumed to be 11.05 to 21% by weight, more preferably 11.05 to 18% by weight, and still more preferably 13 to 17% by weight.
- a preferable range of the total content of lanthanum and manganese is 8.05 to 15% by weight, more preferably 10.05 to 15% by weight, and further preferably 10.5 to 14.5% by weight. You.
- a preferable range of the weight ratio of lanthanum to nickel (La / Ni) is assumed to be 50 to 120%, more preferably 75 to 100%.
- a preferable range of the weight ratio of manganese to nickel is 0.33 to 20%, more preferably 3.33 to 20%, and further preferably 6.66 to 15%. .
- FIG. 7 shows samples F1 to F9, sample E2, and a comparison sample (ruthenium catalyst) together with the metals used as the second promoter components of samples F1 to F9, nickel, lanthanum, and the respective contents of the metals.
- C 3 H 8 conversion of X1 reaction temperature 400 ° C., 500 ° C., the initial evaluation at 600 ° C.
- H 2 unit adsorption amount initial evaluation before
- the evaluation result of the sample E2 is the same as the content shown in FIG. 6, and the evaluation result of the ruthenium catalyst X1 is the same as the content shown in FIG.
- Sample F4 (iron), which has the second lowest coking amount, has a low C 3 H 8 conversion.
- Sample F3 (chromium), sample F1 (calcium), sample F7 (zinc), and sample F2 (vanadium) having relatively good C 3 H 8 conversion have a higher coking amount than the comparative sample (ruthenium catalyst) X1.
- H 2 unit amount of adsorbed sample E2 (manganese) higher sample F1 (calcium), the sample F6 (cobalt), sample F8 (molybdenum) is either C 3 H 8 conversion is lower than comparative sample (ruthenium catalyst) X1
- the coking amount is from the comparative sample (ruthenium catalyst) X1 or both.
- Sample F9 (tungsten) has a lower H 2 unit adsorption amount and C 3 H 8 conversion at 400 ° C. than sample E2 (manganese), but has the lowest coking amount, and has a lower coking amount than sample E2 (manganese). Since the sample (ruthenium catalyst) is lower than the sample X1, it is determined that the sample F1 to F9 is more suitable as the second promoter component than manganese.
- the contents of nickel, lanthanum, and the second promoter component are the same as those of the samples E1 and E2, and the second promoter component is tungsten samples F10 and F11 (using the same preparation method as the sample F9).
- the prepared sample was additionally prepared, and C 3 H 8 at a reaction temperature of 450 ° C. was added to the samples E1 to E3, the samples F9 to F11, and the comparative sample (ruthenium catalyst) X1 together with the comparative sample X1. Conversion was evaluated for 96 consecutive hours (8 times every 12 hours).
- sample F10 The content of nickel, lanthanum, and tungsten in sample F10 was 14.25% by weight, 10% by weight, and 0.75% by weight, and the content of nickel, lanthanum, and tungsten in sample F11 was 12% by weight. %, 10% by weight, and 3% by weight.
- Samples E1 to E3 were prepared separately from the sample used in the evaluation shown in FIG. 6, sample F9 was prepared separately from the sample used in the evaluation shown in FIG. 7, and sample X1 for comparison was prepared in FIG. Were prepared separately from the samples used in the evaluation shown in FIG.
- FIG. 8 shows the evaluation results of the C 3 H 8 conversion up to 96 hours. From the results shown in FIG. 8, C 3 H 8 conversion of up to 96 hours at the reaction temperature 450 ° C., the Sample E1 ⁇ E3 (manganese), in all combinations of three different content of three components, C 3 H 8 conversion was 100%, whereas in Samples F9 to F11 (tungsten), the C 3 H 8 conversion did not reach 100%, and the tungsten content was 0.75% by weight. In the samples F10 and F9 of 1.5% by weight, the C 3 H 8 conversion of the comparative sample (ruthenium catalyst) X1 was higher than that of the sample F11. In the sample F11 of 3% by weight of tungsten, the comparative sample (ruthenium catalyst) was used. ) X1 is significantly lower than the C 3 H 8 conversion.
- Sample F9 in which the second co-catalyst component was tungsten, had a good result with a slightly lower coking amount than Sample E2 (manganese), but from the viewpoint of the C 3 H 8 conversion, the samples E1 to E3 ( Manganese) clearly outperforms Samples F9-F11 (tungsten).
- the carrier of the present catalyst is configured to contain ⁇ -alumina as a main component.
- the catalytic performance of the present catalyst was evaluated by comparing the main component of the carrier with a comparative example in which ⁇ -alumina was changed to ⁇ -alumina, and the evaluation results will be described.
- Samples G1 and G2 are comparative samples in which nickel, lanthanum, and manganese are supported on a carrier A containing ⁇ -alumina as a main component.
- Samples G3 and G4 are comparative samples in which nickel, lanthanum, and manganese are supported on a carrier B containing ⁇ -alumina as a main component.
- the contents of nickel, lanthanum, and manganese in Samples G1 and G3 are the same as in Sample D2, and are 15% by weight, 10% by weight, and 0.1% by weight, respectively, in that order.
- the contents of nickel, lanthanum, and manganese in Samples G2 and G4 are the same as in Sample E2, and are 13.5% by weight, 10% by weight, and 1.5% by weight, respectively.
- the support A is an ⁇ -alumina support having an ⁇ -alumina content of about 99.5% by weight, a silica content of about 0.5% by weight, and a BET specific surface area of about 6.1 m 2 / g.
- the support B is an ⁇ -alumina support having a content of ⁇ -alumina of about 99.4% by weight, a silica content of about 0.6% by weight, and a BET specific surface area of about 1.8 m 2 / g.
- Samples G1 to G4 were prepared by exactly the same preparation method as samples D2 and E2, except that the carriers were different from samples D2 and E2. Note that the carriers A and B used were dried at 80 ° C. for 16 hours in advance before preparing the samples G1 to G4, and then sieved so as to have a particle size of about 200 ⁇ m or less.
- FIG. 9 shows the C 3 H 8 conversion of the samples D2, E2, G1 to G4 (the reaction temperature was 400 ° C., and the support of the samples D2, E2, G1 to G4, and the respective contents of nickel, lanthanum, and manganese).
- the evaluation results of the initial evaluation at 500 ° C. and 600 ° C.), the adsorption amount of H 2 unit (before the initial evaluation and after the initial evaluation), and the coking amount (before the initial evaluation and after the initial evaluation) are summarized in a list. Show. Note that the evaluation results of the samples D2 and E2 have slight errors with respect to the evaluation results shown in FIGS. 5 and 6, respectively.
- the samples G1 to G4 in which the main component of the carrier is ⁇ -alumina have a higher catalyst composition (in comparison with the samples D2 and E2 in which the main component of the carrier is ⁇ -alumina). Irrespective of the content of the three components), the initial catalytic activity is very low, about 10 to 60% of the samples D2 and E2.
- FIG. 10 shows the results of the C 3 H 8 conversion of the samples E2, C3, and X1 continuously evaluated for 1008 hours.
- the vertical axis in FIG. 10 is the C 3 H 8 conversion (%), and the horizontal axis is the duration (hour) of the steam reforming reaction.
- the sample E2 of the present catalyst maintained a higher C 3 H 8 conversion than the ruthenium catalyst X1, and at 1000 hours, a higher C 3 H 8 conversion of about 1.9 times that of the ruthenium catalyst X1 and 95.9%. Is shown.
- the comparative sample C3 to which manganese was not added maintained a higher C 3 H 8 conversion than the ruthenium catalyst X1 until 500 hours had elapsed, but gradually C 3 H 8 from the start of the evaluation. The conversion decreases, and after 504 hours, the C 3 H 8 conversion is lower than that of the ruthenium catalyst X1. From the above results, it can be seen that by adding manganese as the second cocatalyst, the sample E2 of the present catalyst can stably maintain a high catalytic activity for a long period of time.
- the present invention is useful as a nickel-based steam reforming catalyst, and is suitably used for a steam reforming system.
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Abstract
Description
前記触媒活性金属の含有率が、11重量%以上18重量%以下であり、
前記第1助触媒成分の含有率が、8重量%以上12重量%以下であり、
前記第2の助触媒成分の含有率が、0.05重量%以上3重量%以下であることが好ましい。
次に、本触媒の触媒性能を評価した結果について説明する。尚、触媒性能の評価は、水蒸気改質反応の原料ガスがプロパンである場合のC3H8転化率、H2吸着、及び、コーキング量(析出炭素量)の3項目で行った。
C3H8転化率(%)=(供給ガス中のC3H8濃度(%)-生成ガス中のC3H8濃度(%))/(供給ガス中のC3H8濃度(%))×100
以下の説明では、説明の便宜上、ニッケルとランタンとマンガンの各成分または2以上の成分の触媒総重量に対する含有率を、単に「含有率」または「合計含有率」と称す。
次に、マンガンの含有率の好適範囲の検討を、ニッケルとランタンの含有率の最適な組み合わせと考えられる15重量%と10重量%の組み合わせに対して、マンガンの含有率を0.05重量%~2重量%の間で変化させたサンプルD1~D7と、ニッケルとランタンの含有率の15重量%と10重量%の組み合わせに対して、ニッケルの含有率の一部(0.75重量%~3重量%の間で変化)をマンガンで置換したサンプルE1~E3と、ニッケルとランタンの含有率の10重量%と10重量%の組み合わせに対して、ニッケルの含有率の一部(0.5重量%~2重量%の間で変化)をマンガンで置換したサンプルE4~E6を用いて行った。尚、本検討では、C3H8転化率、H2吸着評価(H2単位吸着量)、及び、コーキング量評価の3種類の評価を行った。
ニッケル:11~18重量%、更に好ましくは、13~17重量%。
ランタン:8~12重量%、更に好ましくは、10~12重量%。
マンガン:0.05~3重量%、より好ましくは、0.5~2.5重量%、更に好ましくは、1~1.5重量%。
本触媒の第2の助触媒成分としてマンガンを選択するに際して、第2の助触媒成分として、マンガン以外に、カルシウム(Ca)、バナジウム(V)、クロム(Cr)、鉄(Fe)、コバルト(Co)、銅(Cu)、亜鉛(Zn)、モリブデン(Mo)、タングステン(W)を使用したサンプルF1~F9を準備して、C3H8転化率(反応温度が400℃、500℃、600℃での初期評価)、H2単位吸着量、及び、初期評価後のコーキング量の評価を行った。尚、サンプルF1~F9は、ニッケル、ランタン、及び、第2の助触媒成分の各含有率が、13.5重量%、10重量%、1.5重量%であり、サンプルE2と同じ調製方法により、サンプルE2の硝酸マンガンに代えて第2の助触媒成分の各金属の硝酸塩を用いて調製した。
本触媒の担体は、γ-アルミナを主成分として含んで構成されている。当該担体の主成分を、γ-アルミナをα‐アルミナに変更した比較例と対比して、本触媒の触媒性能を評価したので、評価結果を説明する。
次に、本触媒の長期安定性を、反応温度が450℃におけるC3H8転化率を1008時間に亘り連続して(12時間毎に84回)評価した結果を説明する。本触媒として、ニッケル、ランタン、マンガンの各含有率が13.5重量%、10重量%、1.5重量%のサンプルE2を、図6に示す評価で使用したサンプルとは別に準備し、比較用のサンプルとして、本触媒に対してマンガンを添加していない比較用のサンプルC3(Ni-La触媒)を、図3に示す評価で使用したサンプルとは別に準備し、比較用サンプルX1(ルテニウム触媒:ルテニウム担持量:2重量%、担体:γ-アルミナ)を、図3に示す評価で使用したサンプルとは別に準備した。
Claims (6)
- 触媒活性金属としてのニッケルと、第1の助触媒成分としてのランタンと、第2の助触媒成分としてマンガンと、γ-アルミナを主成分として含む担体と、を含むことを特徴とする水蒸気改質触媒。
- 前記触媒活性金属と前記第1の助触媒成分と前記第2の助触媒成分と前記担体の合計重量に対して、
前記触媒活性金属の含有率が、11重量%以上18重量%以下であり、
前記第1助触媒成分の含有率が、8重量%以上12重量%以下であり、
前記第2の助触媒成分の含有率が、0.05重量%以上3重量%以下であることを特徴とする請求項1に記載の水蒸気改質触媒。 - 前記触媒活性金属と前記第1の助触媒成分と前記第2の助触媒成分と前記担体の合計重量に対して、
前記第1の助触媒成分と前記第2助触媒成分の合計含有率が、10.05重量%以上15重量%以下であることを特徴とする請求項1または2に記載の水蒸気改質触媒。 - 前記触媒活性金属と前記第1の助触媒成分と前記第2の助触媒成分と前記担体の合計重量に対して、
前記触媒活性金属と前記第2助触媒成分の合計含有率が、11.05重量%以上21重量%以下であることを特徴とする請求項1~3の何れか1項に記載の水蒸気改質触媒。 - 前記触媒活性金属に対する前記第1の助触媒成分の重量比が、50%以上120%以下であることを特徴とする請求項1~4の何れか1項に記載の水蒸気改質触媒。
- 前記触媒活性金属に対する前記第2の助触媒成分の重量比が、0.33%以上20%以下であることを特徴とする請求項1~5の何れか1項に記載の水蒸気改質触媒。
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