WO2014175349A1 - 排気ガス浄化触媒用担体、排気ガス浄化用触媒及び排気ガス浄化用触媒構成体 - Google Patents
排気ガス浄化触媒用担体、排気ガス浄化用触媒及び排気ガス浄化用触媒構成体 Download PDFInfo
- Publication number
- WO2014175349A1 WO2014175349A1 PCT/JP2014/061470 JP2014061470W WO2014175349A1 WO 2014175349 A1 WO2014175349 A1 WO 2014175349A1 JP 2014061470 W JP2014061470 W JP 2014061470W WO 2014175349 A1 WO2014175349 A1 WO 2014175349A1
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- WIPO (PCT)
- Prior art keywords
- exhaust gas
- aluminum borate
- catalyst
- mass
- gas purification
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 74
- 238000000746 purification Methods 0.000 title claims description 31
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000007769 metal material Substances 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 50
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 31
- 239000000243 solution Substances 0.000 description 30
- 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 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 description 13
- 239000004327 boric acid Substances 0.000 description 12
- 229910002651 NO3 Inorganic materials 0.000 description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- -1 aluminum boric acid Chemical compound 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 125000005619 boric acid group Chemical group 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 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 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MVKZBFOMDQFANY-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Ca+2].[N+](=O)([O-])[O-].[Ca+2] Chemical compound [N+](=O)([O-])[O-].[Ca+2].[N+](=O)([O-])[O-].[Ca+2] MVKZBFOMDQFANY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- AKMADBIBLGBZQJ-UHFFFAOYSA-N neodymium;nitric acid Chemical compound [Nd].O[N+]([O-])=O AKMADBIBLGBZQJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JSLPYMQWMAAGGH-UHFFFAOYSA-N nitric acid;praseodymium Chemical compound [Pr].O[N+]([O-])=O JSLPYMQWMAAGGH-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
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- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/70—Non-metallic catalysts, additives or dopants
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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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- 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
- F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
- F01N2570/10—Carbon or carbon oxides
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to an exhaust gas purifying catalyst carrier, an exhaust gas purifying catalyst, and an exhaust gas purifying catalyst structure, and more particularly, exhaust gas purifying performance after high-temperature durability in a rich region, in particular, exhaust gas excellent in CO purifying performance.
- the present invention relates to a gas purification catalyst carrier, an exhaust gas purification catalyst, and an exhaust gas purification catalyst structure.
- Exhaust gas discharged from an internal combustion engine such as an automobile contains harmful components such as hydrocarbon (HC), carbon monoxide (CO), and nitrogen oxide (NO x ). Therefore, conventionally, a three-way catalyst has been used to purify and detoxify these harmful components.
- HC hydrocarbon
- CO carbon monoxide
- NO x nitrogen oxide
- noble metals such as Pt, Pd, and Rh are used as a catalytic active component, and alumina, ceria, zirconia, a ceria-zirconia composite oxide having oxygen storage ability, and the like are used as a carrier.
- a catalyst support having a shape such as a honeycomb, a plate, or a pellet made of a ceramic or metal material is used.
- Patent Documents 1, 2, and 3 There is also an example in which aluminum borate is used as a carrier, and the catalyst component is supported on a green compact including a powdery body that is covered with an aluminum borate whisker and has a hollow portion formed therein. The diffusibility is improved (see Patent Document 4).
- the exhaust gas purification catalyst using the substituted aluminum borate of Patent Document 5 is excellent in purification performance after endurance in the lean or stoichiometric region, but the purification performance after endurance in the rich region is inferior to that. It was.
- an exhaust gas purification catalyst is mounted on the car according to the design.
- an exhaust gas purification catalyst that has durability in the lean region is mounted on a vehicle that mainly burns in a lean region where the air-fuel ratio is high, and a vehicle that mainly burns in a rich region where the air-fuel ratio is low is rich. It is equipped with an exhaust gas purification catalyst that is durable in the region.
- An object of the present invention is to provide an exhaust gas purification catalyst carrier, an exhaust gas purification catalyst, and an exhaust gas purification catalyst structure excellent in exhaust gas purification performance after high-temperature durability in a rich region, particularly CO purification performance. It is in.
- the present inventors have reduced the electronegativity of the support by adding an alkaline earth or rare earth element to aluminum borate, so that the noble metal is converted to the support.
- the present inventors have found that the electrons are supplied and the noble metal is immobilized on the support even in the rich region, so that the Pd dispersion and the catalytic activity after rich endurance are excellent, and the present invention has been completed.
- aluminum boric acid had been displayed by the formula 9Al 2 O 3 ⁇ 2B 2 O 3 by a chemical analysis (Al 18 B 4 O 33) , Martin , etc., "Crystal-chemistry of mullite- type aluminoborates Al 18 B 4 O 33 and Al 5 BO 9 : A stoichiometry puzzle ”, Journal of Solid State Chemistry 184 (2011) 70-80, according to crystal structure analysis, aluminum borate is Al 5 BO 9 (5Al 2 O 3 : B 2 O 3, Al 20 B 4 O 36), i.e., that represented by formula 10Al 2 O 3 ⁇ 2B 2 O 3, relative to the aluminum borate formula 9Al 2 O 3 ⁇ 2B 2 O 3 (Al 18 It is described that both B 4 O 33 ) and Al 5 BO 9 (5Al 2 O 3 : B 2 O 3 , Al 20 B 4 O 36 ) are allowed (ie, they are the same substance).
- aluminum borate used in the present invention have the formula 10Al 2 O 3 ⁇ 2B 2 O 3 (5Al 2 O 3: B 2 O 3, Al 20 B 4 O 36) intended to be displayed in, or formula 9Al 2 O it is intended to include those represented by 3 ⁇ 2B 2 O 3 (Al 18 B 4 O 33).
- the exhaust gas purifying catalyst carrier of the present invention is obtained by adding at least one element selected from the group consisting of rare earth elements and alkaline earth metals to aluminum borate, particularly aluminum borate having a cage structure, Aluminum borate having a negative degree of 2.732 or less is contained, or at least one element selected from the group consisting of rare earth elements and alkaline earth metals in aluminum borate as an oxide, 6% by mass It contains aluminum borate added as described above.
- the aluminum borate in the present invention is an aluminum borate in which the ratio of aluminum oxide to boron oxide is 10: 2 to 9: 2, and the formula 10Al 2 O 3 ⁇ 2B 2 O 3 (5Al 2 O 3 : B 2 O 3 , Al 20 B 4 O 36 ), or those represented by the formula 9Al 2 O 3 ⁇ 2B 2 O 3 (Al 18 B 4 O 33 ).
- Such aluminum borate is by X-ray diffraction can be identified as the aluminum borate of the formula 10Al 2 O 3 ⁇ 2B 2 O 3, wherein 9Al 2 O 3 ⁇ 2B 2 O 3 as a standard X-ray diffraction chart (Al 18 B 4 O 33 ) is also present and can be identified as the formula 9Al 2 O 3 .2B 2 O 3 (Al 18 B 4 O 33 ).
- the additive element is preferably selected from the group consisting of Ca, Sr, Ba, La, Pr, Nd, and Ce.
- the exhaust gas purifying catalyst of the present invention includes the above exhaust gas purifying catalyst carrier and Pd supported on the carrier. Further, the exhaust gas purifying catalyst component of the present invention comprises a catalyst support made of ceramics or a metal material, and the exhaust gas purifying catalyst layer supported on the catalyst support. To do.
- the exhaust gas purifying catalyst carrier, the exhaust gas purifying catalyst, and the exhaust gas purifying catalyst structure of the present invention are excellent in exhaust gas purifying performance after high temperature durability in a rich region, particularly CO purifying performance.
- the carrier used for the exhaust gas purifying catalyst of the present invention has at least one element selected from the group consisting of rare earth elements and alkaline earth metals added to aluminum borate and has an electronegativity of 2.732 or less.
- the additive element contained in the aluminum borate used in the present invention does not exist by replacing boron or a part of aluminum in aluminum borate, but present in a form supported or modified on aluminum borate. In this case, for example, it exists as an oxide such as a crystal grain boundary.
- the peak shift of aluminum borate is not substantially observed, and the peak of the additive element is observed as a peak of an oxide or the like.
- such aluminum borate is also referred to as modified aluminum borate.
- the aluminum borate can be manufactured, for example, by the following method.
- ⁇ Solid phase method Boric acid weighed so as to have a predetermined ratio of the target compound aluminum borate (general formula Al 20 B 4 O 36 ) is dissolved in ion-exchanged water. Thereafter, the boehmite sol weighed to have a predetermined ratio is mixed and heated and stirred. The obtained gel product is dried at about 120 ° C. for 12 hours or more. After drying, it is fired at about 300 ° C. for about 1 hour in air, and further fired at about 1000 ° C. for about 5 hours to obtain aluminum borate.
- the target compound aluminum borate generally formula Al 20 B 4 O 36
- boric acid weighed so as to have a predetermined ratio of the target compound aluminum borate (Al 20 B 4 O 36 ) is dissolved in ion-exchanged water. Thereafter, the boehmite sol weighed to have a predetermined ratio is mixed and heated and stirred. The obtained gel product is dried at 120 ° C. for 12 hours or more. After drying, it is fired in air at 300 ° C. for 1 hour, and further fired at 1000 ° C. for 5 hours to obtain aluminum borate.
- ⁇ Reverse coprecipitation method Boric acid weighed to a predetermined ratio of the target compound aluminum borate (general formula Al 20 B 4 O 36 ) is dissolved in pure warm water, and aluminum nitrate weighed to a predetermined ratio is mixed with the solution. To dissolve. The solution is then added dropwise to the aqueous ammonium carbonate solution. The obtained precipitate is filtered and washed with pure water, filtered, dried at about 120 ° C. overnight, baked at about 300 ° C. in air for about 1 hour, and further baked at about 1000 ° C. in air for about 5 hours. Thus, aluminum borate can be obtained.
- aluminum borate can be obtained.
- boric acid weighed so as to have a predetermined ratio of the target compound aluminum borate (Al 20 B 4 O 36 ) is dissolved in ion-exchanged water.
- Aluminum nitrate nonahydrate weighed to a predetermined ratio is mixed and dissolved in the solution.
- the solution was then added dropwise to an aqueous ammonium carbonate solution.
- the obtained precipitate is filtered and washed with pure water and dried at 120 ° C. for 12 hours or more. Subsequently, after baking at 300 degreeC in the air for 1 hour, it further baked at 1000 degreeC in the air for 5 hours, and obtains aluminum borate.
- the carrier used in the exhaust gas purifying catalyst of the present invention is modified by modifying (or supporting) at least one element selected from the group consisting of rare earth elements and alkaline earth metals on the aluminum borate produced as described above. It contains aluminum borate.
- a method for producing such modified aluminum borate is obtained by immersing aluminum borate in a solution of a compound containing an additive element, specifically, an aqueous solution containing a predetermined amount of a compound such as nitrate, sulfate, or acetate of the additive element. It is manufactured by evaporating to dryness and baking at a predetermined temperature, for example, 400 to 1000 ° C.
- the content of the additive element is 0.1 to 20% by mass, preferably 3 to 15% by mass, as an oxide, that is, a value determined by additive element oxide / (aluminum borate + additive element oxide). More preferably, it is selected from the range of 6 to 13% by mass, and even more preferably from 7 to 13% by mass.
- Such modified aluminum borate has an electronegativity of 2.732 or less, or at least one element selected from the group consisting of rare earth elements and alkaline earth metals as oxides, and is preferably 6% by mass or more, preferably 7 Those added by mass% or more.
- the electronegativity is higher than the above value, the supported Pd component tends to be stabilized as PdO, and tends to be inactive to a reduction reaction such as NOx, which is not preferable.
- the lower limit of the electronegativity is not limited, it is considered to be about 2.700 in practice.
- the exhaust gas purifying catalyst of the present invention is one in which Pd is supported on a carrier containing the above modified aluminum borate. By supporting Pd on the modified aluminum borate, it becomes an exhaust gas purification catalyst having excellent exhaust gas purification performance after high-temperature durability in a rich region, particularly CO purification performance.
- the amount is preferably 0.05 to 5% by mass, more preferably 0.4 to 3% by mass based on the mass. If the amount of Pd supported is 0.05% by mass or more based on the mass of the carrier, the durability is improved, and if it is 5% by mass or less, highly dispersed support can be more stably performed.
- the supported amount of Pd is less than 0.05% by mass based on the mass of the support, the absolute amount of the noble metal is small, so that the durability is deteriorated. There are cases where the amount is too high to be supported with high dispersion.
- the amount of Pd supported is a value converted to the mass of Pd metal.
- the exhaust gas purifying catalyst of the present invention comprises, for example, a modified aluminum borate and a solution of a Pd compound (soluble Pd compound, for example, Pd nitrate, Pd chloride, and Pd sulfate). It can be produced by mixing in an amount ratio of 0.2 to 3% by mass on the basis, then evaporating to dryness and baking at 450 to 650 ° C.
- a Pd compound soluble Pd compound, for example, Pd nitrate, Pd chloride, and Pd sulfate
- the solvent constituting the “solution” is not particularly limited as long as it can form a solution, but water is generally used.
- a porous body of a compound selected from the group consisting of other carriers for example, silica, ceria, ceria zirconia, alumina, or titania, within a range not impairing the effects of the present invention. Also good.
- the exhaust gas purifying catalyst structure of the present invention is formed by forming and supporting a layer made of the above-described exhaust gas purifying catalyst of the present invention on a catalyst support made of ceramics or a metal material.
- the shape of the catalyst support made of a ceramic or metal material is not particularly limited, but is generally a shape of a honeycomb, a plate, a pellet or the like.
- the supported amount of the exhaust gas purifying catalyst supported on the catalyst support is preferably 70 to 300 g / L, more preferably 100 to 200 g / L. When this carrying amount is less than 70 g / L, the durability tends to deteriorate due to insufficient carrying amount.
- Examples of the material for such a catalyst support include ceramics such as alumina (Al 2 O 3 ), mullite (3Al 2 O 3 -2SiO 2 ), cordierite (2MgO-2Al 2 O 3 -5SiO 2 ), and the like. And metal materials such as stainless steel.
- the exhaust gas purifying catalyst component of the present invention can be manufactured, for example, by the following method. Modified aluminum borate 50-70 parts by mass, preferably 50-60 parts by mass, La stabilized alumina 20-40 parts by mass, preferably 20-30 parts by mass, barium hydroxide 0-3 parts by mass, preferably 1-3 Part by mass and 5 to 10 parts by mass of an alumina binder are mixed with a solution of the Pd compound and wet pulverized to prepare a slurry.
- the obtained slurry is applied to a catalyst support made of a ceramic or metal material, preferably a honeycomb-shaped catalyst support according to a well-known method, dried, fired at 450 to 650 ° C., and a catalyst support;
- An exhaust gas purifying catalyst structure including the exhaust gas purifying catalyst layer supported on the catalyst support is obtained.
- the present invention will be specifically described below based on reference examples, examples and comparative examples.
- the content of the additive element is a value obtained by adding element oxide / (aluminum borate + additive element oxide).
- 10A2B of Tables 1 to 3 is substantially the 10Al 2 O 3 ⁇ 2B 2 O 3.
- Aluminum borate (Al 20 B 4 O 36 ) was prepared by the solid phase method shown below. Boric acid weighed so as to have a predetermined ratio of the target compound was dissolved in ion-exchanged water. Then, the acetic acid boehmite sol weighed so that it might become a predetermined ratio was mixed, and it heat-stirred. The obtained gel product was dried at 120 ° C. for 12 hours or more. After drying, it was fired at 300 ° C. in air for 1 hour, and further fired at 1000 ° C. for 5 hours to obtain aluminum borate. The XRD pattern of this aluminum borate was as shown in FIG. The aluminum borate can be identified as the aluminum borate of the formula 10Al 2 O 3 ⁇ 2B 2 O 3 by X-ray diffraction.
- Aluminum borate (Al 20 B 4 O 36 ) was prepared by the reverse coprecipitation method shown below. Boric acid weighed so as to have a predetermined ratio of the target compound was dissolved in ion-exchanged water. Aluminum nitrate nonahydrate weighed to a predetermined ratio was mixed and dissolved in the solution. The solution was then added dropwise to an aqueous ammonium carbonate solution. The obtained precipitate was filtered and washed with pure water and dried at 120 ° C. for 12 hours or more. Subsequently, after baking at 300 degreeC in the air for 1 hour, it further baked at 1000 degreeC in the air for 5 hours, and obtained the aluminum borate. There was no difference between the aluminum borate prepared by the reverse coprecipitation method and the aluminum borate prepared by the solid phase method of Reference Example 1.
- the aluminum borate were identified as aluminum borate of the formula 10Al 2 O 3 ⁇ 2B 2 O 3 by X-ray diffraction.
- Example 1 The aluminum borate produced in Production Example 1 was immersed in a lanthanum nitrate aqueous solution and a strontium nitrate aqueous solution.
- the lanthanum nitrate solution and lanthanum nitrate and strontium nitrate in strontium nitrate aqueous solution amount is boric acid in the aluminum of formula 10Al 2 O 3 ⁇ 2B 2 O 3 modified with La 2 O 3 and SrO of interest The amount was such that La 2 O 3 was 5% by mass and SrO was 5% by mass. Thereafter, it is evaporated to dryness at 120 ° C. overnight (about 15 hours), calcined in air at 600 ° C. for 3 hours, and modified with 5% by mass of La 2 O 3 and 5% by mass of SrO, formula 10Al 2 O 3 It was obtained aluminum borate represented by ⁇ 2B 2 O 3.
- Example 2 Aluminum borate was immersed in an aqueous lanthanum nitrate solution and an aqueous praseodymium nitrate solution.
- the amount of La 2 O 3 in aluminum was 5% by mass, and Pr 6 O 11 was 5% by mass. Thereafter, it is evaporated to dryness at 120 ° C. overnight (about 15 hours), calcined in air at 600 ° C. for 3 hours and modified with 5% by mass of La 2 O 3 and 5% by mass of Pr 6 O 11
- An aluminum borate represented by 2 O 3 ⁇ 2B 2 O 3 was obtained.
- Example 3 Aluminum borate was immersed in an aqueous lanthanum nitrate solution and an aqueous calcium nitrate solution.
- the lanthanum nitrate solution and lanthanum nitrate and calcium nitrate calcium nitrate aqueous solution amount is boric acid in the aluminum of formula 10Al 2 O 3 ⁇ 2B 2 O 3 modified with La 2 O 3 and CaO of interest The amount was such that La 2 O 3 was 5% by mass and CaO was 5% by mass. Thereafter, it is evaporated to dryness at 120 ° C. overnight (about 15 hours), calcined in air at 600 ° C.
- Example 4 Aluminum borate was immersed in an aqueous lanthanum nitrate solution and an aqueous barium nitrate solution.
- the amount was such that La 2 O 3 was 5% by mass and BaO was 5% by mass. Thereafter, it is evaporated to dryness at 120 ° C. overnight (about 15 hours), calcined in air at 600 ° C. for 3 hours and modified with 5% by mass of La 2 O 3 and 5% by mass of BaO, formula 10Al 2 O 3 It was obtained aluminum borate represented by ⁇ 2B 2 O 3.
- Example 5 Aluminum borate was immersed in an aqueous lanthanum nitrate solution and an aqueous neodymium nitrate solution.
- the amount of La 2 O 3 in aluminum was 5% by mass and Nd 2 O 3 was 5% by mass. Thereafter, it is evaporated to dryness at 120 ° C. overnight (about 15 hours), calcined in air at 600 ° C. for 3 hours and modified with 5% by mass of La 2 O 3 and 5% by mass of Nd 2 O 3
- An aluminum borate represented by 2 O 3 ⁇ 2B 2 O 3 was obtained.
- Example 6 Aluminum borate was immersed in an aqueous lanthanum nitrate solution and an aqueous cerium nitrate solution.
- the amount of the aqueous solution of lanthanum nitrate and lanthanum nitrate and cerium nitrate in an aqueous solution of cerium nitrate is aluminum borate in the formula 10Al 2 O 3 ⁇ 2B 2 O 3 modified with La 2 O 3 and CeO 2 for the purpose
- the amount of La 2 O 3 was 5% by mass and CeO 2 was 5% by mass.
- the product was calcined for 3 hours at 600 ° C. in air modified with 5 wt% of La 2 O 3 and 5 wt% of CeO 2 Formula 10Al 2 O
- An aluminum borate represented by 3.2B 2 O 3 was obtained.
- Comparative Example 1 The slurry in which 99 parts by mass of ⁇ -Al 2 O 3 and 1 part by mass of Pd corresponding to 1 part by mass of Pd nitrate and an appropriate amount of ion-exchanged water were stirred, then dried, and calcined at 500 ° C. for 1 hour. .
- the outlet gas component was measured using a CO / NO analyzer ("PG240" manufactured by Horiba Ltd.) and an HC analyzer ("VMF-1000F” manufactured by Shimadzu Corporation).
- Table 1 shows the temperature (T50) when 50% NO and HC of each catalyst after purification are purged and the temperature (T70) when 70% of CO is purified. From this result, it can be seen that each example is superior in low temperature activity to the comparative example. Among the three components, it can be seen that the CO purification performance is particularly excellent.
- Table 2 shows the evaluation results of the Pd dispersion degree after aging of each catalyst. From this, it can be seen that each example has a higher degree of Pd dispersion than the comparative example.
- Table 3 shows the electronegativity of each carrier. This electronegativity is a weighted average of the electronegativity (Pauling electronegativity) of metal elements and oxygen constituting the metal oxide according to the ratio of these elements contained in the metal oxide. Calculated. From this, it can be understood that aluminum borate is an acidic carrier having a higher electronegativity compared to Al 2 O 3 . On the other hand, when alkaline earth or rare earth elements, which are electron-accepting elements, are modified with respect to aluminum borate, electrons are supplied from the noble metal to the carrier, and the noble metal is expected to be immobilized on the carrier even in the rich region.
- the electronegativity of the carrier is lowered, and it has a neutral electronegativity close to that of Al 2 O 3 , so that it is expected that the reaction surface is excellent in suppressing adsorption of exhaust gas components.
- this effect seems to have improved the Pd dispersion and the low temperature activity of each reaction (especially CO).
- the electronegativity of the carrier is preferably 2.732 or less.
- the purification performance and the Pd dispersibility are improved by setting the oxide to be modified to 7% by mass or more.
- Example 6 when Comparative Example 2 and Example 6 are compared, although the electronegativity of the carrier is not greatly changed, the catalytic activity is significantly better in Example 6, and there are two kinds of modifying elements for aluminum borate. It turns out that it is preferable to include above.
- the electronegativity can be obtained by calculating as follows.
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Abstract
Description
さらに、本発明の排気ガス浄化用触媒構成体はセラミックス又は金属材料からなる触媒支持体と、該触媒支持体上に担持されている上記の排気ガス浄化用触媒の層とを含むことを特徴とする。
このようなホウ酸アルミニウムを以下、修飾ホウ酸アルミニウムとも称する。
目的化合物のホウ酸アルミニウム(一般式Al20B4O36)の所定比となるように秤量したホウ酸をイオン交換水に溶解する。その後、所定比となるように秤量した酢酸ベーマイトゾルを混合し、加熱撹拌する。得られたゲル状生成物を120℃程度で12時間以上乾燥する。乾燥後、空気中300℃程度で1時間程度焼成し、更に1000℃程度で5時間程度焼成してホウ酸アルミニウムを得ることができる。
目的化合物のホウ酸アルミニウム(一般式Al20B4O36)の所定比となるように秤量したホウ酸を純温水に溶解させ、その溶液に所定比となるように秤量した硝酸アルミニウムを混合して溶解させる。次いで、その溶液を炭酸アンモニウム水溶液に滴下する。得られた沈殿物を純水でろ過洗浄し、ろ過し、120℃程度で一晩乾燥し、空気中300℃程度で1時間程度焼成した後、更に空気中1000℃程度で5時間程度焼成してホウ酸アルミニウムを得ることができる。
ホウ酸アルミニウム(Al20B4O36)を以下に示す固相法で調製した。目的化合物の所定比となるように秤量したホウ酸をイオン交換水に溶解した。その後、所定比となるように秤量した酢酸ベーマイトゾルを混合し、加熱撹拌した。得られたゲル状生成物を120℃で12時間以上乾燥した。乾燥後、空気中300℃で1時間焼成し、更に1000℃で5時間焼成してホウ酸アルミニウムを得た。このホウ酸アルミニウムのXRDパターンは図1に示す通りであった。このホウ酸アルミニウムはX線回折によって式10Al2O3・2B2O3で表わされるホウ酸アルミニウムであると同定できる。
ホウ酸アルミニウム(Al20B4O36)を以下に示す逆共沈法で調製した。目的化合物の所定比となるように秤量したホウ酸をイオン交換水に溶解した。その溶液に所定比となるように秤量した硝酸アルミニウム九水和物を混合して溶解させた。次いで、その溶液を炭酸アンモニウム水溶液に滴下した。得られた沈殿物を純水でろ過洗浄し、120℃で12時間以上乾燥した。次いで、空気中300℃で1時間焼成した後、更に空気中1000℃で5時間焼成してホウ酸アルミニウムを得た。この逆共沈法で調製したホウ酸アルミニウムと参考例1の固相法で調製したホウ酸アルミニウムとの間には差異は認められなかった。
50℃の湯浴に浸した三口フラスコ中に2-プロパノール1.5L、瑪瑙乳鉢にて粉砕したアルミニウムイソプロポキシド200g及びボロンn-プロポキシド40.9gを入れ、N2ガスにて置換しながら攪拌した。アルミニウムイソプロポキシドが完全に溶解した(溶液が透明になった)後、2-プロパノール:水=1:1の混合溶液24.6gをゆっくり滴下して徐々に加水分解させると白いゲル状物質が生成した。得られた沈殿物をエタノールで洗浄し、次いで純水で洗浄し、ろ過した。その後、120℃で一晩(約15時間)乾燥し、空気中300℃で3時間焼成し、更に空気中1,000℃で5時間焼成して白色生成物であるホウ酸アルミニウムを得た。このホウ酸アルミニウムはX線回折によって式10Al2O3・2B2O3で表わされるホウ酸アルミニウムであると同定できた。
製造例1で製造したホウ酸アルミニウムを硝酸ランタン水溶液及び硝酸ストロンチウム水溶液中に浸漬させた。この硝酸ランタン水溶液及び硝酸ストロンチウム水溶液中の硝酸ランタン及び硝酸ストロンチウムの量は、目的とするLa2O3及びSrOで修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウム中のLa2O3が5質量%、SrOが5質量%となる量であった。その後、120℃で一晩(約15時間)蒸発乾固させ、空気中600℃で3時間焼成して5質量%のLa2O3及び5質量%のSrOで修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウムを得た。
ホウ酸アルミニウムを硝酸ランタン水溶液及び硝酸プラセオジム水溶液中に浸漬させた。この硝酸ランタン水溶液及び硝酸プラセオジム水溶液中の硝酸ランタン及び硝酸プラセオジムの量は、目的とするLa2O3及びPr6O11で修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウム中のLa2O3が5質量%、Pr6O11が5質量%となる量であった。その後、120℃で一晩(約15時間)蒸発乾固させ、空気中600℃で3時間焼成して5質量%のLa2O3及び5質量%のPr6O11で修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウムを得た。
ホウ酸アルミニウムを硝酸ランタン水溶液及び硝酸カルシウム水溶液中に浸漬させた。この硝酸ランタン水溶液及び硝酸カルシウム水溶液中の硝酸ランタン及び硝酸カルシウムの量は、目的とするLa2O3及びCaOで修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウム中のLa2O3が5質量%、CaOが5質量%となる量であった。その後、120℃で一晩(約15時間)蒸発乾固させ、空気中600℃で3時間焼成して5質量%のLa2O3及び5質量%のCaOで修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウムを得た。5質量%のLa2O3及び5質量%のCaOで修飾された式10Al2O3・2B2O3で表されるホウ酸アルミニウムを99質量部とPdをメタル換算で1質量部に相当する硝酸Pdと適量のイオン交換水を添加したスラリーを撹拌し、その後、乾燥させ、500℃、1時間焼成した。
ホウ酸アルミニウムを硝酸ランタン水溶液及び硝酸バリウム水溶液中に浸漬させた。この硝酸ランタン水溶液及び硝酸バリウム水溶液中の硝酸ランタン及び硝酸バリウムの量は、目的とするLa2O3及びBaOで修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウム中のLa2O3が5質量%、BaOが5質量%となる量であった。その後、120℃で一晩(約15時間)蒸発乾固させ、空気中600℃で3時間焼成して5質量%のLa2O3及び5質量%のBaOで修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウムを得た。
ホウ酸アルミニウムを硝酸ランタン水溶液及び硝酸ネオジム水溶液中に浸漬させた。この硝酸ランタン水溶液及び硝酸ネオジム水溶液中の硝酸ランタン及び硝酸ネオジムの量は、目的とするLa2O3及びNd2O3で修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウム中のLa2O3が5質量%、Nd2O3が5質量%となる量であった。その後、120℃で一晩(約15時間)蒸発乾固させ、空気中600℃で3時間焼成して5質量%のLa2O3及び5質量%のNd2O3で修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウムを得た。
ホウ酸アルミニウムを硝酸ランタン水溶液及び硝酸セリウム水溶液中に浸漬させた。この硝酸ランタン水溶液及び硝酸セリウム水溶液中の硝酸ランタン及び硝酸セリウムの量は、目的とするLa2O3及びCeO2で修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウム中のLa2O3が5質量%、CeO2が5質量%となる量であった。その後、120℃で一晩(約15時間)蒸発乾固させ、空気中600℃で3時間焼成して5質量%のLa2O3及び5質量%のCeO2で修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウムを得た。
γ-Al2O3を99質量部とPdをメタル換算で1質量部に相当する硝酸Pdと適量のイオン交換水を添加したスラリーを撹拌し、その後、乾燥させ、500℃、1時間焼成した。
ホウ酸アルミニウムを硝酸ランタン水溶液中に浸漬させた。この硝酸ランタン水溶液中の硝酸ランタンの量は、目的とするLa2O3で修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウム中のLa2O3の量が5質量%となる量であった。その後、120℃で一晩(約15時間)蒸発乾固させ、空気中600℃で3時間焼成して5質量%のLa2O3で修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウムを得た。
ホウ酸アルミニウムを硝酸ランタン水溶液及び硝酸バリウム水溶液中に浸漬させた。この硝酸ランタン水溶液及び硝酸バリウム水溶液中の硝酸ランタン及び硝酸バリウムの量は、目的とするLa2O3及びBaOで修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウム中のLa2O3が1質量%、BaOが2質量%となる量であった。その後、120℃で一晩(約15時間)蒸発乾固させ、空気中600℃で3時間焼成して1質量%のLa2O3及び2質量%のBaOで修飾された式10Al2O3・2B2O3で表わされるホウ酸アルミニウムを得た。
各実施例及び比較例のサンプルについて、固定床流通型反応装置を用いて模擬排ガスの浄化性能を測定した。反応管に触媒粉を50mgセットし、0.05%NO、0.39%CO、1200ppmCのC3H6、0.4%O2、0.1%H2、10%H2O、残りがN2の完全燃焼を想定した模擬排ガスを、総流量1000cc/minで触媒粉に導入した。10℃/minで500℃まで昇温後10分間保持し、前処理を行った。その後、一旦冷却後、100℃~500℃まで10℃/minで昇温し測定を行った。
Pd分散度を公知手段であるCOパルス吸着法(T. Takeguchi、S. Manabe、R. Kikuchi、K. Eguchi、T. kanazawa、S. Matsumoto、Applied Catalysis A:293(2005)91.)に基づいて測定した。このPd分散度は式Pd分散度=CO吸着量に相当するPd量(モル)/含まれているPdの総量により計算された。
表1はAging後の各触媒のNO、HCの50%浄化したときの温度(T50)とCOの70%浄化したときの温度(T70)である。この結果から、各実施例は比較例に対して、低温活性が優れることがわかる。3成分の中でも、特にCOの浄化性能が優れていることがわかる。
Claims (6)
- ホウ酸アルミニウムに希土類元素及びアルカリ土類金属からなる群から選択される少なくとも一種の元素を添加し、電気陰性度が2.732以下であるホウ酸アルミニウムを含むことを特徴とする排気ガス浄化触媒用担体。
- ホウ酸アルミニウムに希土類元素及びアルカリ土類金属からなる群から選択される少なくとも一種の元素を酸化物として6質量%以上添加されたホウ酸アルミニウムを含むことを特徴とする排気ガス浄化触媒用担体。
- 前記添加元素として、2種以上の元素を含むことを特徴とする請求項1又は2記載の排気ガス浄化触媒用担体。
- 前記添加元素が、Ca、Sr、Ba、La、Pr、Nd、Ceからなる群から選択されたものであることを特徴とする請求項1~3の何れか1項記載の排気ガス浄化触媒用担体。
- 請求項1~4の何れか1項記載の排気ガス浄化触媒用担体と、該担体に担持されたPdとを含むことを特徴とする排気ガス浄化用触媒。
- セラミックス又は金属材料からなる触媒支持体と、該触媒支持体上に担持されている請求項5に記載の排気ガス浄化用触媒の層とを含むことを特徴とする排気ガス浄化用触媒構成体。
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US14/785,417 US20160082419A1 (en) | 2013-04-26 | 2014-04-23 | Carrier for exhaust gas purification catalyst, catalyst for exhaust gas purification, and catalyst structure for exhaust gas purification |
CN201480023693.4A CN105121007B (zh) | 2013-04-26 | 2014-04-23 | 排气净化催化剂用载体、排气净化用催化剂及排气净化用催化剂结构体 |
JP2014523527A JP6339013B2 (ja) | 2013-04-26 | 2014-04-23 | 排気ガス浄化触媒用担体、排気ガス浄化用触媒及び排気ガス浄化用触媒構成体 |
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WO2017022828A1 (ja) * | 2015-08-06 | 2017-02-09 | 国立大学法人熊本大学 | アンモニア燃焼触媒の製造方法、及びアンモニア触媒燃焼によって生成する熱の利用方法 |
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CN105121007B (zh) | 2018-06-26 |
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US20160082419A1 (en) | 2016-03-24 |
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US20170120221A1 (en) | 2017-05-04 |
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