JP2022518113A - ナノ結晶サイズのセリウム-ジルコニウム酸化物材料およびその製造方法 - Google Patents
ナノ結晶サイズのセリウム-ジルコニウム酸化物材料およびその製造方法 Download PDFInfo
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- JP2022518113A JP2022518113A JP2021533692A JP2021533692A JP2022518113A JP 2022518113 A JP2022518113 A JP 2022518113A JP 2021533692 A JP2021533692 A JP 2021533692A JP 2021533692 A JP2021533692 A JP 2021533692A JP 2022518113 A JP2022518113 A JP 2022518113A
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- mixed oxide
- zirconium
- oxide material
- cerium
- nanocrystal
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- 239000000463 material Substances 0.000 title claims abstract description 98
- 238000004519 manufacturing process Methods 0.000 title description 6
- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 title description 5
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 5
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 36
- 229910052726 zirconium Inorganic materials 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 31
- 230000032683 aging Effects 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- 239000010419 fine particle Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- -1 rare earth salt Chemical class 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 230000000536 complexating effect Effects 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 8
- 239000003929 acidic solution Substances 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- 239000013081 microcrystal Substances 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 150000000703 Cerium Chemical class 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 150000003890 succinate salts Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 abstract description 8
- 238000000227 grinding Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- XNHWVNMBVKUKMM-UHFFFAOYSA-N [Cs].[Zr] Chemical compound [Cs].[Zr] XNHWVNMBVKUKMM-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical class [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 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 description 2
- 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 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- 229910004625 Ce—Zr Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical class [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
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Abstract
Description
(a)重合したジルコニウムオリゴマーを含有する酸性溶液を調製する工程と、
(b)セリウム塩と希土類塩の酸性溶液をジルコニウム含有溶液と混合し、多価金属含有混合物を作る工程と、
(c)酸性の多価金属含有混合物を錯化試薬の溶液と混合する工程と、
(d)工程(c)で得られた混合物に、構成金属水酸化物を含有するジルコニウムベースの前駆体スラリーを生成させる工程と、
(e)ジルコニウム含有前駆体スラリーを塩基で中和し、構成金属水酸化物の共沈と、沈殿させる混合酸化物材料の生成とを達成する工程と、
(f)沈殿させた混合酸化物材料を水で洗浄し、未反応のカチオン性混和物およびアニオン性混和物を除去する工程と、
(g)沈殿させた混合酸化物材料を洗浄したものを回収する工程と、
(h)沈殿させた混合酸化物材料を洗浄したものを、周囲温度または高めの温度で所定の時間、時効する工程と、
(i)時効した混合酸化物材料を乾燥させる工程と、
(j)乾燥した時効済の混合酸化物材料を焼成し、セリウム-ジルコニウム混合酸化物材料を形成する工程と、
(k)焼成したセリウム-ジルコニウム混合酸化物材料を、d50粒度が1.5μm未満になるまで粉砕する工程と、を含む。
Claims (22)
- ナノ結晶サイズのセリウム-ジルコニウム混合酸化物材料であって、
少なくとも30質量%の酸化ジルコニウムと、
5~55質量%の酸化セリウムと、
合計25質量%以下の、ランタン、ネオジム、プラセオジムおよびイットリウムからなる群から選択される希土類金属の少なくとも1種の酸化物と、を含み、
前記ナノ結晶サイズのセリウム-ジルコニウム混合酸化物は、d50粒度が1.5μm未満の階層的秩序構造の強凝集体を呈し、
前記ナノ結晶サイズのセリウム-ジルコニウム混合酸化物が、1,000℃以上で少なくとも6時間の時効前後で、特徴的な比表面積(SSA)および細孔容積(PV)を示し、時効後のSSA及びPVが、時効前のSSAおよびPVの70%以上である、ナノ結晶サイズのセリウム-ジルコニウム混合酸化物材料。 - 前記酸化物材料は、酸化ジルコニウムを少なくとも40%含む、請求項1に記載の混合酸化物材料。
- 前記階層的秩序構造の強凝集体は、粒度が500nm未満である、請求項1または2に記載の混合酸化物材料。
- 階層的秩序構造の強凝集体は、大きさが5nm~20nmの範囲の酸化物微結晶からなる、請求項1~3のいずれか1項に記載の混合酸化物材料。
- 時効後の前記混合酸化物材料のSSAおよびPVは、時効前のSSAおよびPVの少なくとも75%である、請求項1~4のいずれか1項に記載の混合酸化物材料。
- 時効後の前記混合酸化物材料のSSAおよびPVは、時効前のSSAおよびPVの少なくとも85%である、請求項1~5のいずれか1項に記載の混合酸化物材料。
- 前記混合酸化物は、600℃~1,100℃の温度範囲で細孔径分布が変化しない、請求項1~6のいずれかに記載の混合酸化物材料。
- 前記混合酸化物は、酸素貯蔵場所が動きやすい、請求項1~7のいずれか1項に記載の混合酸化物材料。
- ナノ結晶サイズのセリウム-ジルコニウム混合酸化物材料を形成する方法であって、
(a)重合したジルコニウムオリゴマーを含有する酸性溶液を調製する工程と、
(b)セリウム塩と希土類塩の酸性溶液を、前記ジルコニウムオリゴマー含有溶液と混合し、多価金属含有混合物を作る工程と、
(c)前記酸性の多価金属含有混合物を錯化試薬の溶液と混合する工程と、
(d)工程(c)で得られた前記混合物に、構成金属水酸化物を含有するジルコニウムベースの前駆体スラリーを形成させる工程と、
(e)前記ジルコニウム含有前駆体スラリーを塩基で中和し、前記構成金属水酸化物の共沈と、沈殿した混合酸化物材料の形成とを達成する工程と、
(f)前記沈殿した混合酸化物材料を水で洗浄し、未反応のカチオン性混和物およびアニオン性混和物を除去する工程と、
(g)前記洗浄した、沈殿した混合酸化物材料を回収する工程と、
(h)前記洗浄した、沈殿した混合酸化物材料を、周囲温度または高めの温度で所定の時間、時効させる工程と、
(i)前記時効した混合酸化物材料を乾燥させる工程と、
(j)前記乾燥させた、時効した混合酸化物材料を焼成し、前記セリウム-ジルコニウム混合酸化物材料を形成する工程と、
(k)前記焼成したセリウム-ジルコニウム混合酸化物材料を、d50粒度が1.5μm未満になるまで粉砕する工程と、を含む、方法。 - 前記焼成したセリウム-ジルコニウム混合酸化物材料の粉砕により、d50粒度が500nm未満になる、請求項9に記載の方法。
- 重合したジルコニウムオリゴマーは、約30~100%の量のジルコニウムオクタマーを含む、請求項9または10に記載の方法。
- 前記重合したジルコニウムオリゴマーは、ジルコニアゾル粒子を含有しない、請求項9~11のいずれか1項に記載の方法。
- 前記錯化試薬は、ジルコニウムに親和性のあるアニオンを含み、前記錯化剤が、硫酸塩、シュウ酸塩、コハク酸塩、フマル酸塩およびそれらの組み合わせからなる群から選択される、請求項9~12のいずれか1項に記載の方法。
- 前記ジルコニウムベースの前駆体スラリーを生成する前記酸性の多価金属含有混合物中の錯化試薬の量およびジルコニウムの量は、ジルコニウムに対する錯化剤のモル比が約0.35~約1.05の範囲になるように存在する、請求項9~13のいずれか1項に記載の方法。
- 前記多価金属含有混合物が、水溶性の硝酸塩、塩化物、硫酸塩、酢酸塩またはそれらの組み合わせを含む、請求項9~14のいずれか1項に記載の方法。
- 前記塩基が、アルカリ金属水酸化物、アンモニア水および水酸化テトラアルキルアンモニウムからなる群から選択される、請求項9~15のいずれか1項に記載の方法。
- 請求項1~8のいずれか1項に記載の前記ナノ結晶サイズのセリウム-ジルコニウム混合酸化物材料を含む、微粒子フィルター。
- 請求項9~16のいずれか1項に記載の方法に従って形成された前記ナノ結晶サイズのセリウム-ジルコニウム混合酸化物材料を含む、微粒子フィルター。
- 1,000℃で5時間の時効後に、前記ナノ結晶サイズのセリウム-ジルコニウム混合酸化物材料のD50粒度が1.5μm未満、比表面積が少なくとも40m2/gである、請求項17または18に記載の微粒子フィルター。
- 前記ナノ結晶サイズのセリウム-ジルコニウム混合酸化物材料が、1,000℃で5時間の時効前後で、特徴的な比表面積(SSA)を示し、時効後のSSAが、時効前のSSAの85%超に維持される、請求項19に記載の微粒子フィルター。
- 前記微粒子フィルターを形成するために、前記ナノ結晶サイズのセリウム-ジルコニウム混合酸化物材料がウォッシュコートとして基材に塗布されている、請求項17または18に記載の微粒子フィルター。
- フロースルー型三元触媒コンバータ(TWC)への適用、ガソリン微粒子フィルター(GPF)への適用またはディーゼル微粒子フィルター(DPF)への適用における、請求項17~21のいずれか1項に記載の微粒子フィルターの使用。
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