JP2023039982A - 窒素酸化物吸蔵材及び排ガス浄化用触媒 - Google Patents
窒素酸化物吸蔵材及び排ガス浄化用触媒 Download PDFInfo
- Publication number
- JP2023039982A JP2023039982A JP2022197477A JP2022197477A JP2023039982A JP 2023039982 A JP2023039982 A JP 2023039982A JP 2022197477 A JP2022197477 A JP 2022197477A JP 2022197477 A JP2022197477 A JP 2022197477A JP 2023039982 A JP2023039982 A JP 2023039982A
- Authority
- JP
- Japan
- Prior art keywords
- storage material
- oxide
- storage
- mao
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011232 storage material Substances 0.000 title claims abstract description 96
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims description 40
- 239000007789 gas Substances 0.000 title claims description 27
- 238000004140 cleaning Methods 0.000 title 1
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 55
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 48
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 48
- 150000001553 barium compounds Chemical class 0.000 claims abstract description 39
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 12
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 8
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 8
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 31
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 7
- 229910020068 MgAl Inorganic materials 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 102000010909 Monoamine Oxidase Human genes 0.000 description 58
- 108010062431 Monoamine oxidase Proteins 0.000 description 58
- 239000000843 powder Substances 0.000 description 44
- 239000002245 particle Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 6
- 229910008337 ZrO(NO3)2.2H2O Inorganic materials 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000009566 Mao-to Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 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 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 1
- 229910020203 CeO Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- -1 ZrO2 Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 1
- QKYBEKAEVQPNIN-UHFFFAOYSA-N barium(2+);oxido(oxo)alumane Chemical compound [Ba+2].[O-][Al]=O.[O-][Al]=O QKYBEKAEVQPNIN-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 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
- 229910001873 dinitrogen Inorganic materials 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
- 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 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
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- 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
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3289—Coatings involving more than one layer of same or different nature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/005—Spinels
-
- 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
-
- 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
- B01J23/42—Platinum
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B01J35/613—
-
- 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
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
-
- 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
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
- F01N3/0842—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2042—Barium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2066—Praseodymium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20715—Zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
- B01D2255/405—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/91—NOx-storage component incorporated in the catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
- B01D2255/9207—Specific surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
-
- 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
- F01N2250/00—Combinations of different methods of purification
- F01N2250/12—Combinations of different methods of purification absorption or adsorption, and catalytic conversion
-
- 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
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
- F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
-
- 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
- F01N2570/14—Nitrogen oxides
Abstract
Description
例えば、特許文献1には、MgAl2O4スピネル粉末にジルコニアゾルを添加し、更にPtとカリウムを配合してなる浄化性触媒が記載されている。
また特許文献2にも、MgAl2O4粉末にアルカリ金属及びPtを担持させたNOx吸蔵材が記載されている。特許文献2には、「NOx吸蔵材としてアルカリ土類金属を担持したNOx吸蔵還元型触媒では、高温におけるNOx吸蔵量が低いという不具合がある。そこで塩基性担体にアルカリ金属と貴金属を担持したNOx吸蔵還元型触媒とすれば、高温までNOxを多量に吸蔵することができることがわかっている。」として、アルカリ土類金属がアルカリ金属に比べて、高温におけるNOx吸蔵量を向上させるのに不利であることが記載されている。
また、NOx吸蔵還元型触媒は、上述したようにディーゼルエンジンとリーンバーンガソリンエンジンの両方で使用される排ガス後処理技術であるが、ディーゼルエンジンとリーンバーンガソリンエンジンでは排ガスの温度にそれぞれ特徴があり、ディーゼルエンジンは排ガス温度が比較的低い(例えば450℃以下)が、リーンバーンガソリンエンジンにおいてはディーゼルエンジンより排ガスが平均的に高温(例えば450℃以上)となっている。したがって、ディーゼルエンジンだけでなく、リーンバーンガソリンエンジンとしても好適に利用できる、高温でのNOx吸蔵量が高いNOx吸蔵還元型触媒が求められている。
特許文献3は、上述した通り、塩基性担体以外の多孔質担体で貴金属を担持して貴金属の活性低下を回避しようとするものであるが、塩基性担体以外の多孔質担体のNOx吸蔵性能は、一般に塩基性担体よりも低い。このため、特許文献3のように塩基性担体以外の担体に貴金属を担持することには、低温でのNOx吸蔵性能や高温でのNOx吸蔵量の点で改善の余地がある。
前記金属酸化物として、酸化ジルコニウム、酸化プラセオジム、酸化ニオブ及び酸化鉄から選ばれる少なくとも一種の金属酸化物を含む、窒素酸化物吸蔵材を提供するものである。
本発明のNOx吸蔵材は、Mg1-yAl2O4-y(式中、yは0≦y≦0.2の数を示す)と、該Mg1-yAl2O4-yに担持されている貴金属、貴金属以外の金属酸化物及びバリウム化合物と、を有する窒素酸化物吸蔵材であって、
前記金属酸化物として、酸化ジルコニウム、酸化プラセオジム、酸化ニオブ及び酸化鉄の少なくとも一種の酸化物(以下、「特定の金属酸化物」又は単に「金属酸化物」ということもある)を含む。
また、一の粒子に対し大幅に小さい粒径の他の粒子が、SEMで観察するには小さすぎ、SEMではその粒径が確認できない場合には、以下(1)及び(2)が確認できることにより、一の粒子に対し他の粒子が担持されていることを確認できる。(1)SEMに備わっているエネルギー分散型X線分析装置や、波長分散型X線分析装置を用いて、粒径の大きな一の粒子が観察される範囲に、他の粒子を構成する元素が分布していることが確認できること。(2)一の粒子を構成する元素と、他の粒子を構成する元素からなる複合化合物が粉末X線回折法で観測されないことが確認できること。
また一の粒子に対し大幅に小さい粒径の他の粒子が、SEMで観察するには小さすぎ、SEMではその粒径が確認できない場合であって、他の粒子が貴金属からなる粒子の場合、選択的に貴金属粒子のみにCOなどの吸着ガスを吸着させ、担持されている貴金属量の内、どの程度の割合が貴金属粒子の表面に出ているかを分析することによって貴金属粒子の平均的な粒径を求める方法もある。この方法はパルスインジェクション化学吸着量測定法、又は、いわゆる金属分散度測定法ともいわれる。
バリウム化合物の担持量は、NOx吸蔵材全量中、5質量%以上であることが、NOx吸蔵材全体のNOx吸蔵量を高いものとする点で好ましく、NOx吸蔵材全量中、30質量%以下とすることが、高温でのNOx吸蔵性能の点で好ましい。これらの観点から、バリウム化合物の担持量としては、NOx吸蔵材全量中、6質量%以上25質量%以下であることがより好ましく、8質量%以上20質量%以下であることが特に好ましい。バリウム化合物の担持量は、NOx吸蔵材中のバリウム化合物の含有量として求めることができ、例えば、NOx吸蔵材をアルカリ溶融等で溶解して得られる溶液中のBaの量をICP-AESで測定することにより求めることができる。
バリウム化合物担持工程:前記 M1/MAOを、バリウム水溶性塩を含有する水溶液と混合し得られた混合物をエバポレーターで蒸発乾固した後に焼成して、MAOに特定の金属酸化物及びバリウム化合物が担持された粉末(M1/Ba/MAO)を得る。
貴金属担持工程:前記M1/Ba/MAOを、貴金属M2の水溶性塩を含有する水溶液と混合し、得られた混合物をエバポレーターで蒸発乾固した後に焼成して、MAOに特定の金属酸化物、バリウム化合物及び貴金属M2が担持された粉末M2/M1/Ba/MAO)を得る。
(1)Zr濃度を0.2mol/Lとするオキシ硝酸ジルコニウム(ZrO(NO3)2・2H2O)水溶液を調製した。この水溶液に、MgAl2O4粉末を分散させ、得られた分散液をロータリーエバポレーターで蒸発乾固した。乾燥物を大気中で600℃で5時間焼成して、MAO粉末に対して酸化ジルコニウム(ZrO2)が担持された粉末(以下「Zr/MAO粉末」ともいう)を得た。
(2)Ba濃度を0.2mol/Lとする酢酸バリウム(Ba(CH3COO)2)水溶液に、前記のZr/MAO粉末を分散させた。得られた分散液をロータリーエバポレーターで蒸発乾固した。乾燥物を大気中、600℃で5時間焼成し、MAO粉末に対してZrO2及び炭酸バリウム(BaCO3)を担持させた粉末(以下「Ba/Zr/MAO粉末」ともいう)を得た。
(3)蒸留水に対して、Ba/Zr/MAO粉末を分散させ、次いでPt(NO2)2(NH3)2水溶液を分散液中のPt濃度が0.01mol/Lとなるように添加した。得られた分散液をロータリーエバポレーターで蒸発乾固した。乾燥物を大気中、600℃で5時間焼成し、MAO粉末に対してZrO2、BaCO3及びPtを担持させたNOx吸蔵材粉末(以下「Pt/Ba/Zr/MAO粉末」ともいう)を得た。
なおNOx吸蔵材粉末において、ZrO2の担持量はNOx吸蔵材粉末全量中、10質量%であり、炭酸バリウムの担持量はNOx吸蔵材粉末全量中、10質量%であり、白金の担持量はNOx吸蔵材粉末全量中、1質量%であった。
オキシ硝酸ジルコニウム(ZrO(NO3)2・2H2O)の代わりに、硝酸プラセオジム(Pr(NO3)3・6H2O)を用いた。その点以外は実施例1と同様にして、MAO粉末に対してPr6O11及びBaCO3に加えて更にPtを担持させたNOx吸蔵材粉末(以下「Pt/Ba/Pr/MAO」ともいう)を得た。
オキシ硝酸ジルコニウム(ZrO(NO3)2・2H2O)の代わりに、硝酸鉄(Fe(NO3)3・9H2O)を用いた。その点以外は実施例1と同様にして、MAO粉末に対してFe2O3及びBaCO3に加えて更にPtを担持させたNOx吸蔵材粉末(以下「Pt/Ba/Fe/MAO」ともいう)を得た。
オキシ硝酸ジルコニウム(ZrO(NO3)2・2H2O)の代わりに、ニオブ酸及び0.01mol/L シュウ酸水溶液を用いた。その点以外は実施例1と同様にして、MAO粉末に対してNb2O5及びBaCO3に加えて更にPtを担持させたNOx吸蔵材粉末(以下「Pt/Ba/Nb/MAO」ともいう)を得た。
オキシ硝酸ジルコニウム(ZrO(NO3)2・2H2O)水溶液とMAOとの混合比率を、Pt/Ba/Zr/MAOにおけるZrO2の量がNOx吸蔵材全量中、表1に記載の量となるように調整した。その点以外は実施例1と同様にしてMAO粉末に対してZrO2、BaCO3及びPtを担持させた実施例5~8のNOx吸蔵材粉末を得た(以下それぞれ「Pt/Ba/5Zr/MAO」「Pt/Ba/15Zr/MAO」「Pt/Ba/20Zr/MAO」「Pt/Ba/30Zr/MAO」ともいう)。
実施例1においてバリウム化合物を担持させず、前記の(3)で蒸留水に、Zr/MAO粉末をそのまま分散させて、Pt(NO2)2(NH3)2水溶液を添加した。その点以外は、実施例1と同様にして、MAO粉末に対してZrO2及びPtを担持させた比較例1のNOx吸蔵材粉末(以下「Pt/Zr/MAO」ともいう)を得た。
実施例1においてZrO2を担持させず、(2)で酢酸バリウム(Ba(CH3COO)2)水溶液にMAO粉末をそのまま分散させた。その点以外は、実施例1と同様にして、MAO粉末に対してBaCO3及びPtを担持させた比較例2のNOx吸蔵材粉末(以下「Pt/Ba/MAO」ともいう)を得た。
オキシ硝酸ジルコニウム(ZrO(NO3)2・2H2O)の代わりに、硝酸セリウム(Ce(NO3)3・6H2O)を用いた。その点以外は、実施例1と同様にして、MAO粉末に対してCeO2、BaCO3及びPtを担持させた比較例3のNOx吸蔵材粉末(以下「Pt/Ba/Ce/MAO」ともいう)を得た。
実施例1及び2、比較例2及び3で調製したNOx吸蔵材粉末について、以下の方法にて、BET比表面積を測定したところ、実施例1で調製したNOx吸蔵材粉末のBET比表面積は75.6m2/g、実施例2で調製したNOx吸蔵材粉末のBET比表面積は49m2/g、比較例2で調製したNOx吸蔵材粉末のBET比表面積は81.9m2/g、比較例3で調製したNOx吸蔵材粉末のBET比表面積は68.2m2/gであった。
(BET比表面積の測定方法)
比表面積計QUADRASORB SI(Quantachrome社製)を用いてBET3点法にて測定した。測定の際に使用するガスは、窒素ガスとした。
(NOx吸蔵速度及び吸蔵量評価方法)
固定床流通式反応装置を用いて下記の評価を行った。NOx吸蔵材粉末100mgを、He流通下700℃に昇温して30分間、当該温度を保持する前処理をした。その後、200℃まで降温させた。前処理後の200℃の状態で、100ml/minの流量のNOxガス(組成:0.1体積%NO、10体積%O2、残分He)に30分間接触させた。この時の流通ガス中のNOx濃度から、200℃における、NOxガスとの接触開始から200秒間におけるNOx吸蔵量(mol/g)をNOx吸蔵速度として求めた。なお秒あたりのNOx吸蔵速度(mol/(g・sec))は、ここでいうNOx吸蔵量をNOxガスとの接触時間である200秒で割ることにより求まる。
次いで(He100体積%)を流通させながら、NOx吸蔵材粉末を更に40分間200℃で保持した後に、700℃まで昇温10℃/分で昇温させ、この時の流通ガス中のNOx濃度から、450℃から700℃に昇温した際に脱離したNOx量を求めた。NOx吸蔵材は、ヘリウム雰囲気中において温度上昇に伴い、吸蔵していたNOxを放出する。特定温度範囲における脱離NOx量は、同温度範囲におけるNOxの吸蔵量を意味する。
なお、これらのNOx濃度の測定には、化学発光式NOx測定器NOA-7000((株)島津製作所製)を用いた。
一方、バリウム化合物を担持していない比較例1のNOx吸蔵材では、低温でのNOx吸蔵速度は実施例と同等であるものの、各実施例に比べて高温でのNOx吸蔵量に大幅に劣ることが判る。また特定の金属酸化物を担持していない比較例2のNOx吸蔵材や特定の金属酸化物の代わりにセリアを担持した比較例3のNOx吸蔵材では、高温でのNOx吸蔵量は、実施例と同等であるものの、各実施例に比べて低温でのNOx吸蔵速度に劣ることが判る。
Claims (10)
- Mg1-yAl2O4-y(式中、yは0≦y≦0.2の数を示す)を含有し、
更に該Mg1-yAl2O4-yに担持されている成分として、
貴金属と、
酸化ジルコニウム、酸化プラセオジム、酸化ニオブ及び酸化鉄から選ばれる少なくとも一種の金属酸化物と、
バリウム化合物と、を含有する窒素酸化物吸蔵材。 - 前記金属酸化物の含有割合が、窒素酸化物吸蔵材中、1質量%以上50質量%以下である、請求項1に記載の窒素酸化物吸蔵材。
- 前記金属酸化物の含有割合が、窒素酸化物吸蔵材中、5質量%以上20質量%以下である、請求項2に記載の窒素酸化物吸蔵材。
- 前記金属酸化物が、酸化ジルコニウム、酸化プラセオジム及び酸化ニオブから選ばれる少なくとも一種である、請求項1~3の何れか1項に記載の窒素酸化物吸蔵材。
- 前記金属酸化物が酸化ジルコニウムである、請求項4に記載の窒素酸化物吸蔵材。
- バリウム化合物が炭酸バリウムである、請求項1~5の何れかに記載の窒素酸化物吸蔵材。
- 貴金属がPtである、請求項1~6の何れかの窒素酸化物吸蔵材。
- Mg1-yAl2O4-yがMgAl2O4である、請求項1~7の何れか1項に記載の窒素酸化物吸蔵材。
- 粉末状であると共に、BET比表面積が10m2/g以上200m2/g以下である請求項1~8の何れか1項に記載の窒素酸化物吸蔵材。
- 請求項1~9の何れか1項記載の窒素酸化物吸蔵材を含む排ガス浄化用触媒。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017217974 | 2017-11-13 | ||
JP2017217974 | 2017-11-13 | ||
PCT/JP2018/041396 WO2019093391A1 (ja) | 2017-11-13 | 2018-11-07 | 窒素酸化物吸蔵材及び排ガス浄化用触媒 |
JP2019552357A JP7213821B2 (ja) | 2017-11-13 | 2018-11-07 | 窒素酸化物吸蔵材及び排ガス浄化用触媒 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2019552357A Division JP7213821B2 (ja) | 2017-11-13 | 2018-11-07 | 窒素酸化物吸蔵材及び排ガス浄化用触媒 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2023039982A true JP2023039982A (ja) | 2023-03-22 |
JP7448620B2 JP7448620B2 (ja) | 2024-03-12 |
Family
ID=66438430
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2019552357A Active JP7213821B2 (ja) | 2017-11-13 | 2018-11-07 | 窒素酸化物吸蔵材及び排ガス浄化用触媒 |
JP2022197477A Active JP7448620B2 (ja) | 2017-11-13 | 2022-12-09 | 窒素酸化物吸蔵材及び排ガス浄化用触媒 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2019552357A Active JP7213821B2 (ja) | 2017-11-13 | 2018-11-07 | 窒素酸化物吸蔵材及び排ガス浄化用触媒 |
Country Status (5)
Country | Link |
---|---|
US (1) | US11465120B2 (ja) |
EP (1) | EP3711853A4 (ja) |
JP (2) | JP7213821B2 (ja) |
CN (1) | CN111315476A (ja) |
WO (1) | WO2019093391A1 (ja) |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19813655C2 (de) * | 1998-03-27 | 2000-04-27 | Degussa | Speichermaterial für Schwefeloxide, Verfahren zu dessen Herstellung und Verwendung |
US6350421B1 (en) * | 1998-08-24 | 2002-02-26 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Nitrogen oxide storage material and nitrogen oxide storing catalyst prepared therefrom |
US6306360B1 (en) | 1998-09-30 | 2001-10-23 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Spinel powder and spinel slurry |
JP2001252563A (ja) | 2000-03-10 | 2001-09-18 | Toyota Motor Corp | 排ガス浄化用触媒及び排ガス浄化装置 |
JP2001259422A (ja) | 2000-03-17 | 2001-09-25 | Toyota Motor Corp | 排ガス浄化用触媒 |
JP2001259416A (ja) | 2000-03-23 | 2001-09-25 | Toyota Motor Corp | 窒素酸化物吸着材及び排ガス浄化方法 |
JP3551364B2 (ja) | 2000-04-26 | 2004-08-04 | トヨタ自動車株式会社 | 窒素酸化物吸着材 |
CN1091396C (zh) * | 2000-06-21 | 2002-09-25 | 中国科学院兰州化学物理研究所 | 用于净化废气的催化剂 |
EP1316354A1 (de) | 2001-11-30 | 2003-06-04 | OMG AG & Co. KG | Katalysator zur Verminderung der Stickoxide im Abgas von Magermotoren |
JP5216189B2 (ja) | 2005-12-22 | 2013-06-19 | 株式会社キャタラー | 排ガス浄化用触媒 |
JP5459927B2 (ja) | 2006-07-07 | 2014-04-02 | 株式会社キャタラー | 排ガス浄化用触媒 |
DE102009010711A1 (de) * | 2009-02-27 | 2010-09-30 | Umicore Ag & Co. Kg | Stickoxid-Speicherkatalysator zum Einsatz im Kraftfahrzeug in motornaher Position |
GB0922195D0 (en) * | 2009-12-21 | 2010-02-03 | Johnson Matthey Plc | Improvements in NOx traps |
GB201021649D0 (en) * | 2010-12-21 | 2011-02-02 | Johnson Matthey Plc | NOx Absorber catalyst |
WO2013111457A1 (ja) * | 2012-01-23 | 2013-08-01 | エヌ・イーケムキャット株式会社 | 硫酸バリウムを含むアルミナ材料、それを用いた排気ガス浄化用触媒 |
KR101438953B1 (ko) * | 2012-12-18 | 2014-09-11 | 현대자동차주식회사 | 저온에서의 NOx 흡장성능이 개선된 LNT촉매 |
KR101575327B1 (ko) * | 2014-04-24 | 2015-12-21 | 현대자동차 주식회사 | 질소산화물 저감 촉매, 이의 제조 방법, 및 질소산화물 저감 촉매 시스템 |
JP2015231598A (ja) | 2014-06-10 | 2015-12-24 | 株式会社豊田中央研究所 | 排ガス浄化用触媒 |
EP3067319A1 (en) * | 2015-03-09 | 2016-09-14 | SASOL Germany GmbH | Nox trap catalyst support material with improved stability against baal2o4 formation |
GB2540350A (en) * | 2015-07-09 | 2017-01-18 | Johnson Matthey Plc | Nitrogen oxides (NOx) storage catalyst |
EP3448549A1 (en) | 2016-04-29 | 2019-03-06 | Johnson Matthey Public Limited Company | Exhaust system |
GB2553339A (en) * | 2016-09-02 | 2018-03-07 | Johnson Matthey Plc | Improved NOx trap |
JP6408062B1 (ja) * | 2017-04-28 | 2018-10-17 | 株式会社キャタラー | 排ガス浄化用触媒 |
-
2018
- 2018-11-07 EP EP18876879.0A patent/EP3711853A4/en active Pending
- 2018-11-07 US US16/760,533 patent/US11465120B2/en active Active
- 2018-11-07 CN CN201880071093.3A patent/CN111315476A/zh active Pending
- 2018-11-07 JP JP2019552357A patent/JP7213821B2/ja active Active
- 2018-11-07 WO PCT/JP2018/041396 patent/WO2019093391A1/ja unknown
-
2022
- 2022-12-09 JP JP2022197477A patent/JP7448620B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
US11465120B2 (en) | 2022-10-11 |
US20210197171A1 (en) | 2021-07-01 |
JP7448620B2 (ja) | 2024-03-12 |
CN111315476A (zh) | 2020-06-19 |
JPWO2019093391A1 (ja) | 2020-11-26 |
EP3711853A1 (en) | 2020-09-23 |
JP7213821B2 (ja) | 2023-01-27 |
WO2019093391A1 (ja) | 2019-05-16 |
EP3711853A4 (en) | 2020-12-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2104567B2 (en) | Method of making a NOx storage material | |
JP5567923B2 (ja) | 排ガス浄化用触媒 | |
US20190126248A1 (en) | Exhaust gas purifying catalyst | |
WO2013136821A1 (ja) | 排気ガス浄化用触媒組成物および自動車用排気ガス浄化用触媒 | |
JP5674092B2 (ja) | 排気ガス浄化用触媒及びその製造方法 | |
US10704441B2 (en) | Exhaust gas-purifying catalyst | |
JP6499683B2 (ja) | コアシェル型酸化物材料、その製造方法、それを用いた排ガス浄化用触媒、及び排ガス浄化方法 | |
JP6906624B2 (ja) | 酸素吸放出材料、触媒、排ガス浄化システム、および排ガス処理方法 | |
WO2010010714A1 (ja) | 酸素貯蔵材料、排ガス浄化用触媒、及び排ガス浄化用ハニカム触媒構造体 | |
JP2014122149A (ja) | 複合酸化物粒子及びこれを用いた排ガス浄化用触媒 | |
JPWO2017203863A1 (ja) | ガソリンエンジン排気ガスの浄化用三元触媒 | |
JPH10286462A (ja) | 排気ガス浄化用触媒 | |
JP2012055842A (ja) | 排ガス浄化用触媒 | |
JP2007307485A (ja) | NOx吸蔵還元型触媒 | |
JP6256769B2 (ja) | 排気ガス浄化用触媒 | |
JP6339013B2 (ja) | 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 | |
US10449522B2 (en) | Process for manufacture of NOx storage materials | |
JP5794908B2 (ja) | 排気ガス浄化用触媒及び排気ガス浄化用触媒構成体 | |
JP6401740B2 (ja) | 排ガス浄化触媒及びその製造方法 | |
JP5120360B2 (ja) | 酸素吸放出材及びそれを設けた排ガス浄化用触媒 | |
JP7213821B2 (ja) | 窒素酸化物吸蔵材及び排ガス浄化用触媒 | |
JP2018038999A (ja) | 排ガス浄化用触媒 | |
JP2001232199A (ja) | 排ガス浄化用触媒 | |
JP6096818B2 (ja) | 排ガス浄化触媒、その製造方法、及び、それを用いた排ガス浄化方法 | |
JP2010227804A (ja) | 排ガス浄化触媒 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20221223 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20221223 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20240130 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240229 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7448620 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |