JP2019518587A - Scr活性コーティングを有する触媒 - Google Patents
Scr活性コーティングを有する触媒 Download PDFInfo
- Publication number
- JP2019518587A JP2019518587A JP2018543128A JP2018543128A JP2019518587A JP 2019518587 A JP2019518587 A JP 2019518587A JP 2018543128 A JP2018543128 A JP 2018543128A JP 2018543128 A JP2018543128 A JP 2018543128A JP 2019518587 A JP2019518587 A JP 2019518587A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- zeolite
- length
- catalytically active
- zone
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000000576 coating method Methods 0.000 title description 11
- 239000011248 coating agent Substances 0.000 title description 10
- 239000000463 material Substances 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 63
- 239000010457 zeolite Substances 0.000 claims abstract description 55
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 45
- 239000011149 active material Substances 0.000 claims abstract description 45
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 33
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical group O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims abstract description 27
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 40
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000002245 particle Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 229910002089 NOx Inorganic materials 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 229910052676 chabazite Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052878 cordierite Inorganic materials 0.000 description 6
- 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 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- SHPBBNULESVQRH-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[Zr+4] Chemical compound [O-2].[O-2].[Ti+4].[Zr+4] SHPBBNULESVQRH-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 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
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
-
- 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
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0246—Coatings comprising a zeolite
-
- 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
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
- F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2067—Urea
-
- 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
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/903—Multi-zoned catalysts
- B01D2255/9032—Two zones
-
- 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
- B01D2255/9205—Porosity
-
- 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
-
- 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
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
- F01N2370/04—Zeolitic material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
- Processes For Solid Components From Exhaust (AREA)
Abstract
Description
SCR触媒活性材料Aは、イオン交換鉄及び/又は銅を含有する、レビナイト構造型のゼオライトを含み、SCR触媒活性材料Bは、イオン交換鉄及び/又は銅を含有する、チャバザイト構造型のゼオライトを含み、
(i)SCR触媒活性材料A及びBは、2つの材料ゾーンA及びBの形態で存在し、触媒基板の第1の端部から生じる材料ゾーンAは、少なくとも長さLの一部にわたって延在し、触媒基板の第2の端部から生じる材料ゾーンBは、少なくとも長さLの一部にわたって延在し、
又は
(ii)触媒基板は、SCR触媒活性材料A及びマトリックス成分から形成され、SCR触媒活性材料Bは、材料ゾーンBの形態で、少なくとも触媒基板の長さLの一部にわたって延在し、
又は
(iii)触媒基板は、SCR触媒活性材料B及びマトリックス成分から形成され、SCR触媒活性材料Aは、材料ゾーンAの形態で、少なくとも触媒基板の長さLの一部にわたって延在する。
SCR触媒活性材料Bは、鉄交換鉄及び/又は銅を含有する、チャバザイト構造型のゼオライトを含有し、
SCR触媒活性材料A及びBは、2つの材料ゾーンA及びBの形態で存在し、触媒基板の第1の端部から生じる材料ゾーンAは、少なくとも長さLの一部にわたって延在し、触媒基板の第2の端部から生じる材料ゾーンBは、少なくとも長さLの一部にわたって延在する。
a)一方の端部から生じる、コーディエライトからなる従来の壁流フィルタを、4.0重量%の銅と交換されたチャバザイト構造型のゼオライトを含有するウォッシュコートで、従来の浸漬方法によってその長さの50%にわたってコーティングした。ゼオライトのSAR値は、30であった。次いで、フィルタを120℃で乾燥させた。
実施例1を繰り返したが、コーディエライトからなる従来の壁流フィルタの代わりに、コーディエライトからなる従来のフロースルー基板を使用したことが異なる。4.0重量%の銅と交換されたチャバザイト構造型のゼオライト、並びに3.5重量%の銅と交換されたレビナイト構造型のゼオライトの両方を、200g/Lの量で基板に塗布した。実施例1とは対照的に、レビナイト構造型のゼオライトは、30のSAR値を有する。
実施例2を繰り返したが、工程a)において、250g/Lの、4.0重量%の銅と交換されたチャバザイト構造型のゼオライトを塗布したこと、及び工程a)において既に使用した4.0重量%の銅と交換されたチャバザイト構造型のゼオライトを、工程b)において、150g/Lの量で基板に塗布したことが異なる。
a)実施例2及び比較実施例1による触媒を、800℃で16時間水熱的にエージングした。
1.10分間にわたり600℃のN2中で前処理を行う
2.目標温度に対して試験サイクルを繰り返す
a.ガス混合物1の目標温度に近づける
b.NOx(ガス混合物2)を加える
c.NH3(ガス混合物3)を加え、NH3が20ppmを超えるまで、又は最長30分間、待機する
d.最高500℃で昇温脱離を行う(ガス混合物3)
Claims (15)
- 長さLの触媒基板、並びに互いに異なる2つのSCR触媒活性材料A及びBを備える触媒であって、
前記SCR触媒活性材料Aが、イオン交換鉄及び/又は銅を含有する、レビナイト構造型のゼオライトを含み、前記SCR触媒活性材料Bが、イオン交換鉄及び/又は銅を含有する、チャバザイト構造型のゼオライトを含み、
(i)前記SCR触媒活性材料A及びBが、2つの材料ゾーンA及びBの形態で存在し、前記触媒基板の第1の端部から生じる材料ゾーンAが、少なくとも前記長さLの一部にわたって延在し、前記触媒基板の第2の端部から生じる材料ゾーンBが、少なくとも前記長さLの一部にわたって延在し、
又は
(ii)前記触媒基板が、前記SCR触媒活性材料A及びマトリックス成分から形成され、前記SCR触媒活性材料Bが、材料ゾーンBの形態で、少なくとも前記触媒基板の前記長さLの一部にわたって延在し、
又は
(iii)前記触媒基板が、前記SCR触媒活性材料B及びマトリックス成分から形成され、前記SCR触媒活性材料Aが、材料ゾーンAの形態で、少なくとも前記触媒基板の前記長さLの一部にわたって延在する、触媒。 - 前記チャバザイト構造型の前記ゼオライトが、6〜40のSAR値を有することを特徴とする、請求項1に記載の触媒。
- 前記レビナイト構造型の前記ゼオライトが、15を超えるSAR値を有することを特徴とする、請求項1及び/又は2に記載の触媒。
- 前記チャバザイト構造型の前記ゼオライト及び前記レビナイト構造型の前記ゼオライトの両方が、イオン交換銅を含有することを特徴とする、請求項1〜3の1つ以上に記載の触媒。
- 前記チャバザイト構造型の前記ゼオライト中の、及び前記レビナイト構造型の前記ゼオライト中の前記銅が、CuOとして前記交換ゼオライトの総重量に関して算出したときに、各事例において0.2〜6重量%の量で独立して存在することを特徴とする、請求項4に記載の触媒。
- 前記チャバザイト構造型の前記ゼオライト中の、及び前記レビナイト構造型の前記ゼオライト中の銅とアルミニウムとの原子比率が、互いに独立して0.25〜0.6であることを特徴とする、請求項1〜5の1つ以上に記載の触媒。
- 20〜80重量%の前記触媒活性材料が、材料ゾーンB中にあることを特徴とする、請求項1〜6の1つ以上に記載の触媒。
- 材料ゾーンAが、前記触媒基板の前記長さLの全体にわたって延在し、前記触媒基板の前記第2の端部から生じる材料ゾーンBが、その長さLの10〜80%にわたって延在することを特徴とする、請求項1〜7の1つ以上に記載の触媒。
- 前記触媒基板の前記第1の端部から生じる材料ゾーンAが、その長さLの20〜90%にわたって延在し、前記触媒基板の前記第2の端部から生じる材料ゾーンBが、その長さLの10〜70%にわたって延在することを特徴とする、請求項1〜7の1つ以上に記載の触媒。
- 前記触媒基板の前記第1の端部から生じる材料ゾーンAが、その長さLの20〜100%にわたって延在し、材料ゾーンBが、前記触媒基板の長さの全体にわたって延在することを特徴とする、請求項1〜7の1つ以上に記載の触媒。
- 前記触媒基板が、壁流フィルタであり、前記壁流フィルタの第1の端部において開放され、第2の端部において閉鎖されたチャネルが、材料ゾーンAによってコーティングされ、前記壁流フィルタの前記第1の端部において閉鎖され、前記第2の端部において開放されたチャネルが、材料ゾーンBによってコーティングされることを特徴とする、請求項1〜10の1つ以上に記載の触媒。
- リーン運転の内燃エンジンからの排気ガスを浄化するための方法であって、前記排気ガスが、請求項1〜11の1つ以上に記載の触媒を通じて伝導され、材料ゾーンAが、材料ゾーンBの前で、浄化されるべき前記排気ガスと接触することを特徴とする、方法。
- リーン運転の内燃エンジンからの排気ガスを浄化するためのシステムであって、請求項1〜11の1つ以上に記載の触媒、並びに尿素水溶液用の注入器を備え、前記注入器が、前記触媒基板の前記第1の端部の前に位置付けられることを特徴とする、システム。
- 前記排気ガスの流れの方向において、酸化触媒、尿素水溶液用の注入器、及び請求項1〜10の1つ以上に記載の触媒を有し、前記注入器が、前記触媒基板の前記第1の端部の前に位置付けられることを特徴とする、請求項13に記載のシステム。
- 担体材料上の白金が、前記酸化触媒として使用されることを特徴とする、請求項14に記載のシステム。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2022005655A JP7322206B2 (ja) | 2016-04-13 | 2022-01-18 | Scr活性コーティングを有する触媒 |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16165078.3 | 2016-04-13 | ||
EP16165078 | 2016-04-13 | ||
PCT/EP2017/058900 WO2017178575A1 (de) | 2016-04-13 | 2017-04-13 | Katalysator mit scr-aktiver beschichtung |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2022005655A Division JP7322206B2 (ja) | 2016-04-13 | 2022-01-18 | Scr活性コーティングを有する触媒 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2019518587A true JP2019518587A (ja) | 2019-07-04 |
JP7013378B2 JP7013378B2 (ja) | 2022-02-15 |
Family
ID=55759483
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2018543128A Active JP7013378B2 (ja) | 2016-04-13 | 2017-04-13 | Scr活性コーティングを有する触媒 |
JP2022005655A Active JP7322206B2 (ja) | 2016-04-13 | 2022-01-18 | Scr活性コーティングを有する触媒 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2022005655A Active JP7322206B2 (ja) | 2016-04-13 | 2022-01-18 | Scr活性コーティングを有する触媒 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20190105650A1 (ja) |
EP (1) | EP3442686A1 (ja) |
JP (2) | JP7013378B2 (ja) |
KR (1) | KR20180127514A (ja) |
CN (2) | CN114160188A (ja) |
WO (1) | WO2017178575A1 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11691106B2 (en) * | 2018-10-30 | 2023-07-04 | Basf Corporation | Selective catalytic reduction catalyst on a filter substrate |
US20220154611A1 (en) * | 2019-04-15 | 2022-05-19 | Basf Corporation | A selective catalytic reduction catalyst on a filter |
EP3782726A1 (en) * | 2019-08-20 | 2021-02-24 | Umicore Ag & Co. Kg | Catalyst for the abatement of ammonia and nitrogen oxide emissions from the exhaust gases of combustion engines |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013507321A (ja) * | 2009-10-14 | 2013-03-04 | ビーエーエスエフ ソシエタス・ヨーロピア | NOxの選択的還元用の銅含有レビ沸石モレキュラーシーブ |
JP2013532049A (ja) * | 2010-05-05 | 2013-08-15 | ビー・エイ・エス・エフ、コーポレーション | 触媒化煤煙フィルターおよび排出処理システムおよび方法 |
JP2014528350A (ja) * | 2011-07-28 | 2014-10-27 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Publiclimited Company | 排ガスの処理のためのゾーン触媒フィルター |
JP2016518244A (ja) * | 2013-03-14 | 2016-06-23 | ビーエーエスエフ コーポレーション | 選択接触還元触媒系 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1291928A (en) * | 1970-01-30 | 1972-10-04 | British Petroleum Co | Improvements relating to the isomerisation of alkyl aromatics |
WO2011125049A1 (en) * | 2010-04-08 | 2011-10-13 | Basf Se | Cu-cha/fe-mfi mixed zeolite catalyst and process for treating nox in gas streams using the same |
MX2015004812A (es) * | 2012-10-19 | 2016-03-11 | Basf Corp | Composiciones de catalizador de tamiz molecular de poro pequeño de 8 anillos de metales mezclados, artículos catalíticos y métodos. |
KR101522857B1 (ko) * | 2013-05-02 | 2015-05-26 | 희성촉매 주식회사 | 복합형 선택적 환원 촉매 |
GB2520776A (en) * | 2013-12-02 | 2015-06-03 | Johnson Matthey Plc | Wall-flow filter comprising catalytic washcoat |
EP3077112B1 (en) * | 2013-12-06 | 2022-02-16 | Johnson Matthey Public Limited Company | Exhaust gas catalyst containing two different palladium-molecular sieve catalysts |
US20150231617A1 (en) * | 2014-02-19 | 2015-08-20 | Ford Global Technologies, Llc | Fe-SAPO-34 CATALYST FOR USE IN NOX REDUCTION AND METHOD OF MAKING |
US20150231620A1 (en) * | 2014-02-19 | 2015-08-20 | Ford Global Technologies, Llc | IRON-ZEOLITE CHABAZITE CATALYST FOR USE IN NOx REDUCTION AND METHOD OF MAKING |
US9561469B2 (en) * | 2014-03-24 | 2017-02-07 | Johnson Matthey Public Limited Company | Catalyst for treating exhaust gas |
US20150290632A1 (en) * | 2014-04-09 | 2015-10-15 | Ford Global Technologies, Llc | IRON AND COPPER-CONTAINING CHABAZITE ZEOLITE CATALYST FOR USE IN NOx REDUCTION |
GB2530129B (en) * | 2014-05-16 | 2016-10-26 | Johnson Matthey Plc | Catalytic article for treating exhaust gas |
WO2015193210A1 (en) * | 2014-06-16 | 2015-12-23 | Umicore Ag & Co. Kg | Exhaust gas treatment system |
EP2985068A1 (de) * | 2014-08-13 | 2016-02-17 | Umicore AG & Co. KG | Katalysator-System zur Reduktion von Stickoxiden |
GB2548261B (en) * | 2014-10-07 | 2020-07-15 | Johnson Matthey Plc | Molecular sieve catalyst for treating exhaust gas |
-
2017
- 2017-04-13 KR KR1020187032743A patent/KR20180127514A/ko not_active Application Discontinuation
- 2017-04-13 CN CN202111514436.9A patent/CN114160188A/zh active Pending
- 2017-04-13 WO PCT/EP2017/058900 patent/WO2017178575A1/de active Application Filing
- 2017-04-13 EP EP17716275.7A patent/EP3442686A1/de not_active Withdrawn
- 2017-04-13 CN CN201780010184.1A patent/CN108712927B/zh active Active
- 2017-04-13 JP JP2018543128A patent/JP7013378B2/ja active Active
- 2017-04-13 US US16/086,720 patent/US20190105650A1/en not_active Abandoned
-
2022
- 2022-01-18 JP JP2022005655A patent/JP7322206B2/ja active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013507321A (ja) * | 2009-10-14 | 2013-03-04 | ビーエーエスエフ ソシエタス・ヨーロピア | NOxの選択的還元用の銅含有レビ沸石モレキュラーシーブ |
JP2013532049A (ja) * | 2010-05-05 | 2013-08-15 | ビー・エイ・エス・エフ、コーポレーション | 触媒化煤煙フィルターおよび排出処理システムおよび方法 |
JP2014528350A (ja) * | 2011-07-28 | 2014-10-27 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Publiclimited Company | 排ガスの処理のためのゾーン触媒フィルター |
JP2016518244A (ja) * | 2013-03-14 | 2016-06-23 | ビーエーエスエフ コーポレーション | 選択接触還元触媒系 |
Also Published As
Publication number | Publication date |
---|---|
JP2022058647A (ja) | 2022-04-12 |
CN108712927A (zh) | 2018-10-26 |
JP7013378B2 (ja) | 2022-02-15 |
CN108712927B (zh) | 2022-01-04 |
CN114160188A (zh) | 2022-03-11 |
WO2017178575A1 (de) | 2017-10-19 |
US20190105650A1 (en) | 2019-04-11 |
EP3442686A1 (de) | 2019-02-20 |
KR20180127514A (ko) | 2018-11-28 |
JP7322206B2 (ja) | 2023-08-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6899834B2 (ja) | 活性コーティングを有する粒子フィルタ | |
JP6470734B2 (ja) | 選択的接触還元触媒システム | |
JP6437520B2 (ja) | 選択接触還元触媒系 | |
JP7322206B2 (ja) | Scr活性コーティングを有する触媒 | |
JP7008692B2 (ja) | Scr活性コーティングを有する粒子フィルタ | |
RU2770116C2 (ru) | Изделия и системы для селективного каталитического восстановления | |
KR20110127225A (ko) | 압축점화 엔진으로부터 배출된 배기가스로부터 미립자 물질을 여과하기 위한 필터 | |
KR101831933B1 (ko) | 촉매화 미립자 필터 및 미립자 필터의 코팅 방법 | |
JP2020508843A (ja) | ディーゼルエンジンの排気ガス浄化用触媒 | |
US11376550B2 (en) | Nitrogen oxide storage catalyst | |
JP2023542828A (ja) | ディーゼル酸化触媒を含有するビスマット | |
US20140170033A1 (en) | Method for coating a catalysed particulate filter and a particulate filter | |
CN112672811B (zh) | 低温氮氧化物吸附剂 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200403 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20210120 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210125 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210420 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210906 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20211125 |
|
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: 20211220 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220119 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7013378 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |