JP2016159222A - Method for producing polymer protection material-free supported catalyst - Google Patents
Method for producing polymer protection material-free supported catalyst Download PDFInfo
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- JP2016159222A JP2016159222A JP2015039661A JP2015039661A JP2016159222A JP 2016159222 A JP2016159222 A JP 2016159222A JP 2015039661 A JP2015039661 A JP 2015039661A JP 2015039661 A JP2015039661 A JP 2015039661A JP 2016159222 A JP2016159222 A JP 2016159222A
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- Prior art keywords
- supported catalyst
- protective material
- ether
- polymer protective
- nanoparticles
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229920000642 polymer Polymers 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims description 54
- 239000002245 particle Substances 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- 241000003832 Lantana Species 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 6
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 claims description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- SNAQINZKMQFYFV-UHFFFAOYSA-N 1-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOC SNAQINZKMQFYFV-UHFFFAOYSA-N 0.000 claims description 3
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- RERATEUBWLKDFE-UHFFFAOYSA-N 1-methoxy-2-[2-(2-methoxypropoxy)propoxy]propane Chemical compound COCC(C)OCC(C)OCC(C)OC RERATEUBWLKDFE-UHFFFAOYSA-N 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 3
- RJBIZCOYFBKBIM-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]propane Chemical compound COCCOCCOC(C)C RJBIZCOYFBKBIM-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 claims description 3
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 3
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 239000002116 nanohorn Substances 0.000 claims description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 3
- -1 perovskite Chemical compound 0.000 claims description 3
- 229960005323 phenoxyethanol Drugs 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 230000001603 reducing effect Effects 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- HYLLZXPMJRMUHH-UHFFFAOYSA-N 1-[2-(2-methoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOC HYLLZXPMJRMUHH-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims 1
- 229910052586 apatite Inorganic materials 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 3
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 9
- RTZYCRSRNSTRGC-LNTINUHCSA-K (z)-4-oxopent-2-en-2-olate;ruthenium(3+) Chemical compound [Ru+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O RTZYCRSRNSTRGC-LNTINUHCSA-K 0.000 description 8
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000006228 supernatant Substances 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
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
Description
本発明は、ナノ粒子が担持体に担持され、高分子保護材を含有しない高分子保護材フリー担持触媒の製造方法に関する。 The present invention relates to a method for producing a polymer protective material-free supported catalyst in which nanoparticles are supported on a carrier and does not contain a polymer protective material.
従来、化学反応触媒又は燃料電池などでは、カーボン系の担体にナノ粒子を担持した不均一系触媒が用いられている。また、ボイラー又は排ガスの浄化などでは、セラミックス系の担体にナノ粒子を担持した不均一系触媒が用いられている。不均一系触媒に用いるナノ粒子として（ｆｃｃ）Ｒｕナノ粒子が開示されている（例えば、特許文献１、又は非特許文献１を参照。）。非特許文献１では、（ｆｃｃ）Ｒｕナノ粒子を担体に担持して不均一系触媒として使用する場合、ポリビニルピロリドンなどの高分子保護材を用いてナノ粒子を合成・精製した後に、得られたナノ粒子を担体に担持している。 Conventionally, in a chemical reaction catalyst or a fuel cell, a heterogeneous catalyst in which nanoparticles are supported on a carbon-based carrier has been used. In addition, in the purification of boilers or exhaust gases, heterogeneous catalysts in which nanoparticles are supported on a ceramic carrier are used. (Fcc) Ru nanoparticles are disclosed as nanoparticles used for heterogeneous catalysts (see, for example, Patent Document 1 or Non-Patent Document 1). In Non-Patent Document 1, when (fcc) Ru nanoparticles were supported on a carrier and used as a heterogeneous catalyst, the nanoparticles were synthesized and purified using a polymer protective material such as polyvinylpyrrolidone. Nanoparticles are supported on a carrier.
しかし、ナノ粒子の合成時に用いた高分子保護材が触媒中に残っていると、触媒の効果が十分に発揮されない場合がある。高分子保護材の除去を目的としてナノ粒子の精製を繰り返すと、精製回数が増加するにつれて得られるナノ粒子の収量が少なくなるという問題である。 However, if the polymer protective material used in the synthesis of the nanoparticles remains in the catalyst, the effect of the catalyst may not be sufficiently exhibited. If the purification of the nanoparticles is repeated for the purpose of removing the polymer protective material, the yield of nanoparticles obtained decreases as the number of purification increases.
本発明の目的は、触媒の性能を低下させる高分子保護材を用いず、触媒の効果を十分に発揮できる高分子保護材フリー担持触媒を、従来の方法よりも効率的に得ることができる製造方法を提供することである。 An object of the present invention is to produce a polymer protective material-free supported catalyst capable of fully exhibiting the effect of the catalyst without using a polymer protective material that lowers the performance of the catalyst, more efficiently than conventional methods. Is to provide a method.
本発明に係る高分子保護材フリー担持触媒の製造方法は、ナノ粒子が担持体に担持され、高分子保護材を含有しない高分子保護材フリー担持触媒の製造方法であって、前記ナノ粒子の合成原料となる化合物と、前記担持体と、炭素数が２以上の還元性をもつ有機溶媒と、を含有し、かつ、前記高分子保護材を含有しない混合物を加熱して、前記ナノ粒子を合成するとともに、該ナノ粒子を前記担持体に担持させる工程１を有することを特徴とする。 The method for producing a polymer protective material-free supported catalyst according to the present invention is a method for producing a polymer protective material-free supported catalyst in which nanoparticles are supported on a carrier and does not contain a polymer protective material, Heating a mixture containing a compound as a synthetic raw material, the support, and an organic solvent having a reducing property having 2 or more carbon atoms and not containing the polymer protective material, In addition to the synthesis, the method has a step 1 of supporting the nanoparticles on the support.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記有機溶媒の沸点は１００℃以上であることが好ましい。取り扱い性に優れる。また、担持触媒をより安全に得ることができる。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, the boiling point of the organic solvent is preferably 100 ° C. or higher. Excellent handleability. In addition, the supported catalyst can be obtained more safely.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記有機溶媒は、多価アルコール、ブタノール、イソブタノール、エトキシエタノール、ジメチルホルムアミド、キシレン、Ｎ−メチルピロリジノン、ジクロロベンゼン、トルエン、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセテート、エチルラクテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールイソプロピルメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールブチルメチルエーテル、トリプロピレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、ジエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、リエチレングリコールモノメチルエーテル、ジエチレングリコールジブチルエーテル、トリエチレングリコールブチルメチルエーテル、ポリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル及びポリエチレングリコールモノメチルエーテルの中から選ばれる１種以上であることが好ましい。担持触媒をより安全、かつ、より効率的に得ることができる。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, the organic solvent is a polyhydric alcohol, butanol, isobutanol, ethoxyethanol, dimethylformamide, xylene, N-methylpyrrolidinone, dichlorobenzene, toluene, propylene glycol. Monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol Rubutyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, reethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and One or more selected from polyethylene glycol monomethyl ether is preferred. The supported catalyst can be obtained more safely and more efficiently.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記多価アルコールは、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール及びブチレングリコールの中から選ばれる１種以上であることが好ましい。担持触媒をより安全、かつ、より効率的に得ることができる。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, the polyhydric alcohol is preferably one or more selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and butylene glycol. The supported catalyst can be obtained more safely and more efficiently.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記担持体は、カーボン若しくはセラミックスのいずれか一方又は両方である形態を包含する。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, the carrier includes one or both of carbon and ceramics.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記担持体は、アルミナ、シリカ、シリカアルミナ、カルシア、マグネシア、チタニア、セリア、ジルコニア、セリアジルコニア、ランタナ、ランタナアルミナ、酸化スズ、酸化タングステン、アルミノシリケート、アルミノホスフェート、ボロシリケート、リンタングステン酸、ヒドロキシアパタイト、ハイドロタルサイト、ペロブスカイト、コージェライト、ムライト、シリコンカーバイド、活性炭、カーボンブラック、アセチレンブラック、カーボンナノチューブ及びカーボンナノホーンの中から選ばれる１種以上である形態を包含する。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, the support is alumina, silica, silica alumina, calcia, magnesia, titania, ceria, zirconia, ceria zirconia, lantana, lantana alumina, tin oxide, oxidation Tungsten, aluminosilicate, aluminophosphate, borosilicate, phosphotungstic acid, hydroxyapatite, hydrotalcite, perovskite, cordierite, mullite, silicon carbide, activated carbon, carbon black, acetylene black, carbon nanotube and carbon nanohorn The form which is 1 or more types is included.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記ナノ粒子がＲｕ粒子であり、該Ｒｕ粒子はｆｃｃ構造を有していることが好ましい。ｈｃｐ構造を有するＲｕ粒子を担持させた触媒と比較し、異なる触媒活性を得ることができる。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, the nanoparticles are preferably Ru particles, and the Ru particles preferably have an fcc structure. Compared with a catalyst supporting Ru particles having an hcp structure, a different catalytic activity can be obtained.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記ナノ粒子がＲｕ粒子であり、前記ナノ粒子の合成原料となる化合物はＲｕ有機化合物であることが好ましい。担持触媒をより効率的に得ることができる。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, the nanoparticles are preferably Ru particles, and the compound that is a raw material for synthesizing the nanoparticles is preferably a Ru organic compound. A supported catalyst can be obtained more efficiently.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記Ｒｕ有機化合物は、ジケトナート又はアセテートを含有する化合物であることが好ましい。担持触媒をより効率的に得ることができる。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, the Ru organic compound is preferably a compound containing diketonate or acetate. A supported catalyst can be obtained more efficiently.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記Ｒｕ有機化合物がＲｕ（ａｃａｃ）３又は酢酸Ｒｕであることが好ましい。担持触媒をより効率的に得ることができる。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, the Ru organic compound is preferably Ru (acac) 3 or Ru acetate. A supported catalyst can be obtained more efficiently.
本発明は、触媒の性能を低下させる高分子保護材を用いず、触媒の効果を十分に発揮できる高分子保護材フリー担持触媒を、従来の方法よりも効率的に得ることができる製造方法を提供することができる。 The present invention provides a production method capable of obtaining a polymer protective material-free supported catalyst capable of fully exhibiting the effect of the catalyst without using a polymer protective material that lowers the performance of the catalyst more efficiently than the conventional method. Can be provided.
次に本発明について実施形態を示して詳細に説明するが本発明はこれらの記載に限定して解釈されない。本発明の効果を奏する限り、実施形態は種々の変形をしてもよい。 Next, although an embodiment is shown and explained in detail about the present invention, the present invention is limited to these descriptions and is not interpreted. As long as the effect of the present invention is exhibited, the embodiment may be variously modified.
本実施形態に係る高分子保護材フリー担持触媒の製造方法は、ナノ粒子が担持体に担持され、高分子保護材を含有しない高分子保護材フリー担持触媒の製造方法であって、ナノ粒子の合成原料となる化合物と、担持体と、炭素数が２以上の還元性をもつ有機溶媒と、を含有し、かつ、高分子保護材を含有しない混合物を加熱して、ナノ粒子を合成するとともに、該ノ粒子を前記担持体に担持させる工程１を有する。 The method for producing a polymer protective material-free supported catalyst according to the present embodiment is a method for producing a polymer protective material-free supported catalyst in which nanoparticles are supported on a carrier and does not contain a polymer protective material. While synthesizing nanoparticles by heating a mixture containing a compound as a raw material for synthesis, a support, and an organic solvent having a reducing property having 2 or more carbon atoms and not containing a polymer protective material And step 1 of supporting the nanoparticles on the carrier.
本実施形態に係る担持触媒の製造方法は、高分子保護材を用いずにナノ粒子を合成する点、及びナノ粒子の合成とナノ粒子の担持体への担持とを同時に行う点が、例えば非特許文献１に記載されたような従来の製造方法と異なる点である。高分子保護材を用いないことで、触媒の作用を十分の発揮させることができる担持触媒を製造することができる。また、ナノ粒子の合成とナノ粒子の担持体への担持とを同時に行うことで、従来の製造方法と比較して製造工程を少なくすることができる。本明細書において、ナノ粒子とは、平均粒子径が１００ｎｍ以下の微細粒子をいう。ナノ粒子の平均粒子径は、透過型電子顕微鏡（ＴＥＭ）によって得られた粒子像から少なくとも１００個以上の粒子の粒子径を計測し、その平均を求めることによって算出した値である。ＴＥＭの観察倍率は、例えば、１２００００倍又は１５００００倍であることが好ましい。ナノ粒子は、例えば、Ｒｕ粒子、Ｐｄ粒子、Ｐｔ粒子、Ｉｒ粒子、Ａｕ粒子である。ナノ粒子の平均粒子径の下限は、特に限定されないが、１ｎｍ以上であることが好ましい。 The method for producing a supported catalyst according to the present embodiment is, for example, that nanoparticle synthesis is performed without using a polymer protective material, and that nanoparticle synthesis and nanoparticle support are performed simultaneously. This is a point different from the conventional manufacturing method described in Patent Document 1. By not using the polymer protective material, it is possible to produce a supported catalyst that can sufficiently exert the action of the catalyst. In addition, by simultaneously performing the synthesis of the nanoparticles and the loading of the nanoparticles on the carrier, the number of manufacturing steps can be reduced as compared with the conventional manufacturing method. In this specification, a nanoparticle means the fine particle whose average particle diameter is 100 nm or less. The average particle diameter of the nanoparticles is a value calculated by measuring the particle diameter of at least 100 particles from a particle image obtained by a transmission electron microscope (TEM) and obtaining the average. The observation magnification of TEM is preferably 120,000 times or 150,000 times, for example. The nanoparticles are, for example, Ru particles, Pd particles, Pt particles, Ir particles, and Au particles. Although the minimum of the average particle diameter of a nanoparticle is not specifically limited, It is preferable that it is 1 nm or more.
次に、工程１で用いる各物質について説明する。 Next, each substance used in step 1 will be described.
（ナノ粒子の合成原料となる化合物）
本実施形態に係る高分子保護材フリー担持触媒の製造方法では、ナノ粒子がＲｕ粒子であるとき、合成原料はＲｕ化合物である。Ｒｕ化合物はＲｕ有機化合物であることが好ましい。担持触媒をより効率的に得ることができる。Ｒｕ有機化合物は、ジケトナート又はアセテートを含有する化合物であることが好ましい。ジケトナートを含有するＲｕ有機化合物は、例えば、トリス（アセチルアセナト）ルテニウム（ＩＩＩ）（以降、Ｒｕ（ａｃａｃ）３という。）である。アセテートを含有するＲｕ有機化合物は、例えば、酢酸ルテニウム（以降、酢酸Ｒｕという。）である。
(Compound that is a raw material for the synthesis of nanoparticles)
In the method for producing a polymer protective material-free supported catalyst according to the present embodiment, when the nanoparticles are Ru particles, the synthetic raw material is a Ru compound. The Ru compound is preferably a Ru organic compound. A supported catalyst can be obtained more efficiently. The Ru organic compound is preferably a compound containing diketonate or acetate. An example of the Ru organic compound containing diketonate is tris (acetylacetonato) ruthenium (III) (hereinafter referred to as Ru (acac) 3 ). The Ru organic compound containing acetate is, for example, ruthenium acetate (hereinafter referred to as Ru acetate).
（担持体）
担持体は、カーボン若しくはセラミックスのいずれか一方又は両方である形態を包含する。セラミックスは、例えば、アルミナ、シリカ、シリカアルミナ、カルシア、マグネシア、チタニア、セリア、ジルコニア、セリアジルコニア、ランタナ、ランタナアルミナ、酸化スズ、酸化タングステン、アルミノシリケート、アルミノホスフェート、ボロシリケート、リンタングステン酸、ヒドロキシアパタイト、ハイドロタルサイト、ペロブスカイト、コージェライト、ムライト又はシリコンカーバイドである。カーボンは、例えば、活性炭、カーボンブラック、アセチレンブラック、カーボンナノチューブ又はカーボンナノホーンである。本実施形態では、これらの担持体の中から１種だけを使用するか、又は２種以上を併用してもよい。２種以上を併用する場合は、セラミックスから２種以上を組合せて用いるか、カーボンから２種以上を組合せて用いるか、又はセラミックスから１種以上及びカーボンから１種以上を組合せて用いてもよい。より好ましくは、アルミナ、シリカ、チタニア、セリア、ジルコニア、活性炭及びカーボンブラックの中から選ばれる１種以上を用いる。
(Carrier)
The support includes a form that is one or both of carbon and ceramics. Ceramics include, for example, alumina, silica, silica alumina, calcia, magnesia, titania, ceria, zirconia, ceria zirconia, lantana, lantana alumina, tin oxide, tungsten oxide, aluminosilicate, aluminophosphate, borosilicate, phosphotungstic acid, hydroxy Apatite, hydrotalcite, perovskite, cordierite, mullite or silicon carbide. The carbon is, for example, activated carbon, carbon black, acetylene black, carbon nanotube, or carbon nanohorn. In this embodiment, only 1 type may be used from these support bodies, or 2 or more types may be used together. When two or more types are used in combination, two or more types from ceramics may be used in combination, two or more types from carbon may be used in combination, or one or more types from ceramics and one or more types from carbon may be used in combination. . More preferably, at least one selected from alumina, silica, titania, ceria, zirconia, activated carbon and carbon black is used.
（有機溶媒）
有機溶媒は、炭素数が２以上であり、還元性をもつ。有機溶媒の炭素数は、４以上であることがより好ましい。有機溶媒の炭素数の上限は、特に限定されないが、常温において液体であることが望ましい。
(Organic solvent)
The organic solvent has 2 or more carbon atoms and has reducibility. More preferably, the organic solvent has 4 or more carbon atoms. The upper limit of the carbon number of the organic solvent is not particularly limited, but is preferably liquid at room temperature.
有機溶媒の沸点は１００℃以上であることが好ましい。取り扱い性に優れる。また、担持触媒をより安全に得ることができる。有機溶媒の沸点は、１６０℃以上であることがより好ましい。有機溶媒の沸点の上限は、特に限定されないが、担持触媒から溶媒をより容易に除去できる点で、３００℃以下であることが好ましく、２９０℃以下であることがより好ましい。 The boiling point of the organic solvent is preferably 100 ° C. or higher. Excellent handleability. In addition, the supported catalyst can be obtained more safely. The boiling point of the organic solvent is more preferably 160 ° C. or higher. Although the upper limit of the boiling point of the organic solvent is not particularly limited, it is preferably 300 ° C. or lower, more preferably 290 ° C. or lower, from the viewpoint that the solvent can be more easily removed from the supported catalyst.
有機溶媒は、多価アルコール、ブタノール、イソブタノール、エトキシエタノール、ジメチルホルムアミド、キシレン、Ｎ−メチルピロリジノン、ジクロロベンゼン、トルエン、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセテート、エチルラクテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールイソプロピルメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールブチルメチルエーテル、トリプロピレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、ジエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、リエチレングリコールモノメチルエーテル、ジエチレングリコールジブチルエーテル、トリエチレングリコールブチルメチルエーテル、ポリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル及びポリエチレングリコールモノメチルエーテルの中から選ばれる１種以上であることが好ましい。担持触媒をより安全、かつ、より効率的に得ることができる。このうち、多価アルコールがより好ましい。 Organic solvents are polyhydric alcohol, butanol, isobutanol, ethoxyethanol, dimethylformamide, xylene, N-methylpyrrolidinone, dichlorobenzene, toluene, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethyl lactate, Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl Ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, reethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and polyethylene glycol monomethyl ether It is preferable that it is 1 or more types. The supported catalyst can be obtained more safely and more efficiently. Of these, polyhydric alcohols are more preferred.
多価アルコールは、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール及びブチレングリコールの中から選ばれる１種以上であることが好ましい。このうち、トリエチレングリコールがより好ましい。担持触媒をより安全、かつ、より効率的に得ることができる。 The polyhydric alcohol is preferably at least one selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and butylene glycol. Of these, triethylene glycol is more preferable. The supported catalyst can be obtained more safely and more efficiently.
（高分子保護材）
本実施形態では、高分子保護材を用いない。高分子保護材は、例えば、ポリビニルピロリドン（ＰＶＰ）である。
(Polymer protective material)
In this embodiment, a polymer protective material is not used. The polymer protective material is, for example, polyvinyl pyrrolidone (PVP).
次に、工程１について、ナノ粒子がＲｕ粒子である形態を例にとって説明する。 Next, step 1 will be described taking an example in which the nanoparticles are Ru particles.
本実施形態に係る担持触媒の製造方法では、ナノ粒子がＲｕ粒子であり、工程１が、Ｒｕ化合物と、担持体と、有機溶媒と、を含有し、高分子保護材を含有しない混合物を作製した後に加熱する工程であることが好ましい。 In the method for producing a supported catalyst according to this embodiment, the nanoparticles are Ru particles, and Step 1 includes a Ru compound, a support, and an organic solvent, and a mixture that does not contain a polymer protective material is produced. It is preferable that it is the process of heating after performing.
工程１では、まず、Ｒｕ化合物と、担持体と、有機溶媒と、を含有する混合物を作製する。混合物中のＲｕ化合物の濃度は、１２５ｍＭ（ｍｍｏｌ／ｌ）以下であることが好ましく、１００ｍＭ（ｍｍｏｌ／ｌ）以下であることがより好ましい。また、Ｒｕ化合物と担持体との割合は、担持触媒中のＲｕ粒子の担持量が所定の範囲となるように調整する。担持触媒中のＲｕ粒子の担持量は、０．００１〜６０質量％であることが好ましい。ここで、担持量は、乾燥状態の担持触媒の質量に対するナノ粒子の質量の割合であり、例えば用高周波誘導結合プラズマ発光分光分析、原子吸光分光光度分析で測定することができる。 In step 1, first, a mixture containing a Ru compound, a support, and an organic solvent is prepared. The concentration of the Ru compound in the mixture is preferably 125 mM (mmol / l) or less, and more preferably 100 mM (mmol / l) or less. The ratio between the Ru compound and the support is adjusted so that the amount of Ru particles supported in the supported catalyst falls within a predetermined range. The supported amount of Ru particles in the supported catalyst is preferably 0.001 to 60% by mass. Here, the supported amount is the ratio of the mass of the nanoparticles to the mass of the supported catalyst in a dry state, and can be measured by, for example, high frequency inductively coupled plasma emission spectrometry or atomic absorption spectrophotometry.
混合物の作製にあたり、Ｒｕ化合物及び担持体を有機溶媒中に懸濁させた後、例えば超音波などの分散機を用いて分散させることが好ましい。本発明は、各物質の添加順は特に限定されない。 In preparing the mixture, it is preferable to suspend the Ru compound and the support in an organic solvent and then disperse the mixture using a disperser such as an ultrasonic wave. In the present invention, the order of addition of each substance is not particularly limited.
次いで、混合物を加熱する。加熱方法は、特に限定されず、例えば、オイルバス、マントルヒーター、ブロックヒーター若しくは熱媒循環式ジャケットなどの外部加熱方式、又はマイクロ波照射方式である。加熱温度は、１００〜３００℃であることが好ましく、１８０〜２３０℃であることがより好ましい。目的とする加熱温度に到達させるまでの昇温速度は、４℃／分以上であることが好ましく、６℃／分以上であることがより好ましい。昇温速度を所定の範囲とすることで、ｆｃｃ構造を有するＲｕ粒子を形成することができる。また、目的とする加熱温度で保持する時間は、使用する化合物の種類、混合物の液量又は加熱温度などに依存するが、例えば、１０〜３００分であることが好ましく、１２０〜２４０分であることがより好ましい。 The mixture is then heated. The heating method is not particularly limited, and is, for example, an external heating method such as an oil bath, a mantle heater, a block heater or a heat medium circulation jacket, or a microwave irradiation method. The heating temperature is preferably 100 to 300 ° C, and more preferably 180 to 230 ° C. The rate of temperature rise until reaching the target heating temperature is preferably 4 ° C./min or more, and more preferably 6 ° C./min or more. By setting the temperature rising rate within a predetermined range, Ru particles having an fcc structure can be formed. Moreover, although the time to hold | maintain at the target heating temperature is dependent on the kind of compound to be used, the liquid quantity of a mixture, or heating temperature, it is preferable that it is 10 to 300 minutes, for example, and is 120 to 240 minutes. It is more preferable.
工程１では、Ｒｕ化合物が有機溶媒によって還元され、担持体の表面でＲｕ粒子の核生成及び粒成長が起こる。そして、Ｒｕ粒子が担持体に担持された担持触媒が得られる。このＲｕ粒子はｆｃｃ構造を有している。Ｒｕ粒子がｆｃｃ構造を有することで、ｈｃｐ構造を有するＲｕ粒子を担持させた触媒と比較し、異なる触媒活性を得ることができる。Ｒｕ粒子の結晶構造は、例えば、Ｘ線回折パターン（ＸＲＤパターン）によって確認できる。Ｒｕ粒子の平均粒子径は、３０ｎｍ以下であることが好ましく、１０ｎｍ以下であることがより好ましい。Ｒｕ粒子の平均粒子径の下限は、特に限定されないが、１ｎｍ以上であることが好ましい。 In step 1, the Ru compound is reduced by an organic solvent, and Ru particle nucleation and grain growth occur on the surface of the support. A supported catalyst in which Ru particles are supported on a support is obtained. The Ru particles have an fcc structure. Since the Ru particles have an fcc structure, different catalytic activity can be obtained as compared with a catalyst supporting Ru particles having an hcp structure. The crystal structure of the Ru particles can be confirmed by, for example, an X-ray diffraction pattern (XRD pattern). The average particle size of the Ru particles is preferably 30 nm or less, and more preferably 10 nm or less. The lower limit of the average particle diameter of the Ru particles is not particularly limited, but is preferably 1 nm or more.
工程１の後、担持触媒を溶媒から分離精製することが好ましい。担持触媒を分離精製する方法は、特に限定されないが、例えば、温度が下がった混合物をろ過し、洗浄・乾燥する方法である。 After step 1, the supported catalyst is preferably separated and purified from the solvent. The method for separating and purifying the supported catalyst is not particularly limited. For example, the method is a method of filtering, washing and drying a mixture having a lowered temperature.
本実施形態に係る製造方法で得られた担持触媒は、担持触媒の外表面に高分子保護材が存在しない。また、ナノ粒子と担持体との間に高分子保護材が介在しないことが好ましい。担持触媒が高分子保護材を含有するか否かは、例えば、Ｘ線回折パターン（ＸＲＤパターン）によって確認できる。例えば高分子保護材がＰＶＰであるとき、室温でλ＝ＣｕＫαの測定条件で測定したＸＲＤパターンにおいて、１０°付近にＰＶＰ由来のパターンの有無によって確認することができる。 The supported catalyst obtained by the production method according to this embodiment does not have a polymer protective material on the outer surface of the supported catalyst. Moreover, it is preferable that a polymer protective material does not intervene between a nanoparticle and a support body. Whether or not the supported catalyst contains a polymer protective material can be confirmed by, for example, an X-ray diffraction pattern (XRD pattern). For example, when the polymer protective material is PVP, the XRD pattern measured at room temperature under the measurement condition of λ = CuKα can be confirmed by the presence or absence of a PVP-derived pattern around 10 °.
以降、実施例を示しながら本発明についてさらに詳細に説明するが、本発明は実施例に限定して解釈されない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not construed as being limited to the examples.
（実施例１Ａ）
フラスコにトリエチレングリコール（以下、ＴＥＧ）を１２５ｍＬ投入した。トリス（アセチルアセトナト）ルテニウム（ＩＩＩ）（以下、Ｒｕ（ａｃａｃ）３）を１．９９１８ｇ（５ｍｍｏｌ）と活性炭（ＦＡＭ−５０、日本エンバイロケミカルズ社製）を４．５０３１ｇとを秤とり前記ＴＥＧ中に添加し、超音波で３０ｍｉｎ分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を６℃／分の昇温速度で２００℃まで加熱し、２００℃で３ｈｒ加熱撹拌し、その後冷却した。冷却した混合液を減圧ろ過し、固体成分（濾物）をエタノールで十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
Example 1A
125 mL of triethylene glycol (hereinafter, TEG) was charged into the flask. In the TEG, 1.9918 g (5 mmol) of tris (acetylacetonato) ruthenium (III) (hereinafter Ru (acac) 3 ) and 4.5031 g of activated carbon (FAM-50, manufactured by Nippon Envirochemicals) were weighed. And mixed with an ultrasonic wave for 30 minutes to prepare a mixed solution. The polymer protective material was not added to the mixed solution. The mixture was heated to 200 ° C. at a rate of temperature increase of 6 ° C./min, heated and stirred at 200 ° C. for 3 hours, and then cooled. The cooled mixture was filtered under reduced pressure, and the solid component (filtered material) was thoroughly washed with ethanol and then dried under reduced pressure to obtain a supported catalyst.
（実施例２Ａ）
フラスコにＴＥＧを４０ｍＬ投入した。Ｒｕ（ａｃａｃ）３を１．９９２０ｇ（５ｍｍｏｌ）と活性炭（ＦＡＭ−５０）を４．５０２２ｇとを秤とり前記ＴＥＧ中に添加し、超音波で３０ｍｉｎ分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を６℃／分の昇温速度で２００℃まで加熱し、２００℃で３ｈｒ加熱撹拌し、その後冷却した。冷却した混合液を減圧ろ過し、固体成分（濾物）をエタノールで十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
(Example 2A)
40 mL of TEG was charged into the flask. 1.9920 g (5 mmol) of Ru (acac) 3 and 4.5022 g of activated carbon (FAM-50) were weighed and added to the TEG, and dispersed by ultrasonication for 30 min to prepare a mixed solution. The polymer protective material was not added to the mixed solution. The mixture was heated to 200 ° C. at a rate of temperature increase of 6 ° C./min, heated and stirred at 200 ° C. for 3 hours, and then cooled. The cooled mixture was filtered under reduced pressure, and the solid component (filtered material) was thoroughly washed with ethanol and then dried under reduced pressure to obtain a supported catalyst.
（実施例３Ａ）
フラスコにＴＥＧを１８５ｍＬ投入した。Ｒｕ（ａｃａｃ）３を５．９０５６ｇ（１４．８ｍｍｏｌ）とケッチェンブラック（ＥＣ３００Ｊ、ライオン社製）とを４．５０２２ｇ秤とり前記ＴＥＧ中に添加し、超音波で３０ｍｉｎの間分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を６℃／分の昇温速度で２００℃まで加熱し、２００℃で３ｈｒ加熱撹拌し、その後冷却した。冷却した混合液を減圧ろ過し、固体成分（濾物）をエタノールで十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
(Example 3A)
185 mL of TEG was charged into the flask. 5.9056 g (14.8 mmol) of Ru (acac) 3 and 4.5022 g of Ketjen Black (EC300J, manufactured by Lion Corporation) are weighed and added to the TEG, and dispersed by mixing with ultrasonic waves for 30 min. Was made. The polymer protective material was not added to the mixed solution. The mixture was heated to 200 ° C. at a rate of temperature increase of 6 ° C./min, heated and stirred at 200 ° C. for 3 hours, and then cooled. The cooled mixture was filtered under reduced pressure, and the solid component (filtered material) was thoroughly washed with ethanol and then dried under reduced pressure to obtain a supported catalyst.
（実施例４Ａ）
フラスコにＴＥＧを１２５ｍＬ投入した。Ｒｕ（ａｃａｃ）３を０．９８６９ｇ（２．５ｍｍｏｌ）と活性炭（ＦＡＭ−５０）を４．７４９６ｇとを秤とり前記ＴＥＧ中に添加し、超音波で３０ｍｉｎの間分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を６℃／分の昇温速度で２００℃まで加熱し、２００℃で３ｈｒ加熱撹拌し、その後冷却した。遠心分離を用いて冷却後の混合液から固体成分を沈降させ上澄みを除去し、固体成分をエタノールで十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
(Example 4A)
125 mL of TEG was charged into the flask. 0.9869 g (2.5 mmol) of Ru (acac) 3 and 4.796 g of activated carbon (FAM-50) were weighed and added to the TEG, and dispersed for 30 min with ultrasound to prepare a mixed solution. . The polymer protective material was not added to the mixed solution. The mixture was heated to 200 ° C. at a rate of temperature increase of 6 ° C./min, heated and stirred at 200 ° C. for 3 hours, and then cooled. The solid component was precipitated from the cooled mixed solution using centrifugal separation, the supernatant was removed, the solid component was sufficiently washed with ethanol, and then dried under reduced pressure to obtain a supported catalyst.
（Ｒｕ粒子の平均粒子径）
実施例１Ａ及び実施例２Ａの担持触媒をＴＥＭでそれぞれ倍率１５００００倍、２０００００倍で観察し、得られた粒子像から１００個の粒子の粒子径を計測し、その平均を求め、Ｒｕ粒子の平均粒子径とした。図１に実施例１ＡのＴＥＭ像を、図２に実施例２ＡのＴＥＭ像を示す。実施例１Ａの平均粒子径は３．３４ｎｍ、実施例２Ａの平均粒子径は３．１４ｎｍであった。また、図１及び図２から、凝集した粒子の存在は確認されなかった。
(Average particle diameter of Ru particles)
The supported catalysts of Example 1A and Example 2A were observed with a TEM at a magnification of 150,000 times and 200000 times, respectively, and the particle diameter of 100 particles was measured from the obtained particle images, the average was obtained, and the average of Ru particles The particle diameter was taken. FIG. 1 shows a TEM image of Example 1A, and FIG. 2 shows a TEM image of Example 2A. The average particle size of Example 1A was 3.34 nm, and the average particle size of Example 2A was 3.14 nm. Further, from FIG. 1 and FIG. 2, the presence of aggregated particles was not confirmed.
（結晶状態）
実施例１Ａ及び実施例２Ａの担持触媒について、ＸＲＤ測定を行った。ＸＲＤ測定条件は、室温でλ＝ＣｕＫαである。図３に実施例１ＡのＸＲＤパターンを、図４に実施例２ＡのＸＲＤパターンを示す。図３において、Ｒｕのパターンは（ｆｃｃ）Ｒｕのパターンを示しており、Ｒｕ粒子がｆｃｃ構造を有することが確認できた。図４において、Ｒｕのパターンは（ｆｃｃ）Ｒｕのパターン及び（ｈｃｐ）Ｒｕのパターンを含むことが示されていた。
(Crystal state)
XRD measurement was performed on the supported catalysts of Example 1A and Example 2A. The XRD measurement condition is λ = CuKα at room temperature. FIG. 3 shows the XRD pattern of Example 1A, and FIG. 4 shows the XRD pattern of Example 2A. In FIG. 3, the Ru pattern shows the (fcc) Ru pattern, and it was confirmed that the Ru particles have the fcc structure. In FIG. 4, it was shown that the pattern of Ru includes a pattern of (fcc) Ru and a pattern of (hcp) Ru.
Claims (10)
前記ナノ粒子の合成原料となる化合物と、前記担持体と、炭素数が２以上の還元性をもつ有機溶媒と、を含有し、かつ、前記高分子保護材を含有しない混合物を加熱して、前記ナノ粒子を合成するとともに、該ナノ粒子を前記担持体に担持させる工程１を有することを特徴とする高分子保護材フリー担持触媒の製造方法。 A method for producing a polymer protective material-free supported catalyst in which nanoparticles are supported on a carrier and does not contain a polymer protective material,
Heating a mixture containing the compound as a raw material for synthesizing the nanoparticles, the support, and a reducing organic solvent having 2 or more carbon atoms, and not containing the polymer protective material; A method for producing a polymer protective material-free supported catalyst, comprising the step of synthesizing the nanoparticles and supporting the nanoparticles on the support.
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| WO2013038674A1 (en) * | 2011-09-16 | 2013-03-21 | 独立行政法人科学技術振興機構 | Ruthenium microparticles having essentially face-centered cubic structure and method for producing same |
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| JP6369848B2 (en) * | 2013-11-07 | 2018-08-08 | 国立大学法人北陸先端科学技術大学院大学 | Metal nanoparticle-supporting carbon material and method for producing the same, and method for producing functionalized exfoliated carbon material |
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| JPH01307445A (en) * | 1988-06-02 | 1989-12-12 | Matsushita Electric Ind Co Ltd | Preparation of catalyst |
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| WO2013038674A1 (en) * | 2011-09-16 | 2013-03-21 | 独立行政法人科学技術振興機構 | Ruthenium microparticles having essentially face-centered cubic structure and method for producing same |
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