WO2013000683A1 - Device for the purification of exhaust gases from a heat engine, comprising a ceramic carrier and an active phase mechanically anchored in the carrier - Google Patents
Device for the purification of exhaust gases from a heat engine, comprising a ceramic carrier and an active phase mechanically anchored in the carrier Download PDFInfo
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- WO2013000683A1 WO2013000683A1 PCT/EP2012/060904 EP2012060904W WO2013000683A1 WO 2013000683 A1 WO2013000683 A1 WO 2013000683A1 EP 2012060904 W EP2012060904 W EP 2012060904W WO 2013000683 A1 WO2013000683 A1 WO 2013000683A1
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- Prior art keywords
- crystallites
- same
- engine
- support
- catalytic
- Prior art date
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- 239000000919 ceramic Substances 0.000 title claims abstract description 37
- 238000000746 purification Methods 0.000 title claims abstract description 8
- 239000007789 gas Substances 0.000 title abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000002923 metal particle Substances 0.000 claims abstract description 16
- 238000004581 coalescence Methods 0.000 claims abstract description 10
- 230000006378 damage Effects 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 20
- 239000010948 rhodium Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052596 spinel Inorganic materials 0.000 claims description 12
- 239000011029 spinel Substances 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 2
- 229940075613 gadolinium oxide Drugs 0.000 claims description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 44
- 239000012072 active phase Substances 0.000 abstract description 12
- 239000000969 carrier Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 23
- 239000000758 substrate Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000009792 diffusion process Methods 0.000 description 10
- 150000002823 nitrates Chemical class 0.000 description 8
- 239000002689 soil Substances 0.000 description 8
- 241000264877 Hippospongia communis Species 0.000 description 7
- 230000032683 aging Effects 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 238000001991 steam methane reforming Methods 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002089 NOx Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 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 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 239000002082 metal nanoparticle Substances 0.000 description 2
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- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
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- 238000000629 steam reforming Methods 0.000 description 2
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- 239000002341 toxic gas Substances 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
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- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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- 230000007928 solubilization Effects 0.000 description 1
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- 150000003871 sulfonates Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
-
- B01J35/51—
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/38—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
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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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/393—
-
- B01J35/60—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- B01J37/0215—Coating
-
- 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
- B01J37/0242—Coating followed by impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
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- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F01N3/2832—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support granular, e.g. pellets
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
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- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
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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
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- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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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
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- Y02T10/12—Improving ICE efficiencies
Definitions
- the invention relates to a device for cleaning the exhaust gases of a heat engine, commonly called “ catalytic converter ", in particular for a motor vehicle, a device comprising a support on which at least one catalyst is deposited for the chemical destruction of impurities in the exhaust gases.
- the function of such a device is to eliminate, at least in part, the gases pollutants contained in the exhaust gases, in particular carbon monoxide, hydrocarbons and nitrogen oxides, by transforming them by reduction or oxidation reactions.
- the invention proposes exhaust gas purification devices comprising oxide ceramic supports and active metal particles whose structural characteristics and the anchoring of the particles in the support give superior performances to those of the catalyst oxide supports. conventional.
- a heterogeneous gas-solid catalyst is generally an inorganic material consisting of at least one oxide or non-oxide ceramic support on which is dispersed one or more active phases which convert reagents into products through repeated and uninterrupted cycles of elementary phases (adsorption, dissociation, diffusion, reaction-recombination, diffusion, desorption).
- the support can in some cases intervene no only from a physical point of view (high pore volume and high BET surface to improve the dispersion of the active phases) but also chemical (accelerate for example the adsorption, dissociation, diffusion and desorption of such and such molecules).
- the catalyst participates in the conversion by returning to its original state at the end of each cycle throughout its lifetime.
- a catalyst modifies / accelerates the reaction mechanism (s) and the kinetics of the associated reaction (s) without changing the thermodynamics thereof.
- the set of elementary steps are:
- a catalytic converter consists of a stainless conversion chamber in which the exhaust gas is introduced. These gases pass through a ceramic structure generally consisting of a ceramic honeycomb substrate of oxide nature (cordierite, mullite, ). On the walls of the ceramic substrate (honeycomb) is deposited a so-called three-way catalyst (TWC: Three Ways Catalysts). The catalyst accelerates the conversion kinetics of the reagents into products.
- the objective is to limit the release of toxic gases (CO, NOx and unburned hydrocarbons) by transforming them mainly into water, C0 2 and nitrogen.
- a 3-way catalyst is able to provide 3 types of reactions simultaneously:
- Oxidation reactions (requiring a high partial pressure of oxygen) and reduction (low partial pressure of oxygen) add stresses. They require a very precise amount of air to add to the fuel.
- a lambda probe placed on the exhaust measures the amount of oxygen output.
- a servo loop makes it possible to control the air / fuel ratio very precisely by keeping it at an ideal value.
- the catalytic converter is effective only from 250-300 ° C. That's why small trips are problematic.
- the ceramic architectures of catalytic converters for automotive pollution control are generally substrates in honeycombs and are for the most part made of cordierite (2 MgO-2 Al 2 O 3 -5 SiO 2 ) or mullite. These architectures develop a low surface area (a few m 2 / g) with a volume porosity of 20% to 40%.
- the supports of the classical active phases are oxides: alumina for its low temperature thermo-chemical stability ( ⁇ 800 ° C), ceria for its oxygen redox properties and zirconia for its chemical affinity with rhodium.
- alumina for its low temperature thermo-chemical stability ( ⁇ 800 ° C)
- ceria for its oxygen redox properties
- zirconia for its chemical affinity with rhodium.
- the specific surface development has been sought from alumina in its forms ⁇ , ⁇ and ⁇ (from 50 to 250 m 2 / g). Since then, supports ceria and zirconia developing from 20 to 100 m 2 / g have been made.
- the support collapses thermally after a few cycles inducing a drop in the specific surface, a drop in the pore volume and an acceleration of migration / diffusion / coalescence phenomena of the metal nanoparticles.
- the oxide supports In order to minimize these phenomena of thermal collapse under operating conditions of the oxide supports, the latter have been stabilized by additions of elements such as yttrium, gadolinium, lanthanum, etc. La-Al 2 0 3 is thus used . CeGdO, ZrYO, CeZrYO, ... This limits their thermal collapses but does not minimize the phenomena of migration / sintering of the metal particles.
- the noble metals and the support oxide of the active phases (for example the migration of the Rh 3+ ion in a structure ⁇ A1 2 0 3 ).
- a problem that arises is to provide a device for cleaning the exhaust gas of a heat engine comprising an improved catalyst capable of to stabilize, under conditions similar to those encountered during methane steam reforming, nanoparticles of active phases, so as to improve its performance.
- a solution of the invention is a device for cleaning the exhaust gases of a heat engine comprising:
- a catalytic ceramic support comprising an arrangement of crystallites of the same size, same isodiametric morphology and same chemical composition or substantially of the same size, same isodiametric morphology and same chemical composition in which each crystallite is in point contact or almost punctual with the crystallites which the surround, and
- an active phase for the chemical destruction of impurities in the exhaust gas comprising metal particles mechanically anchored in said catalytic support in such a way that the coalescence and mobility of each particle are limited to a maximum volume corresponding to that of a crystallite said catalytic ceramic support.
- the first advantage of the proposed solution relates to the ultra-divided mesoporous catalytic ceramic support of active phase (s). Indeed, it develops a large available surface area greater than or equal to 20 m 2 / g, due to the size of its nanoscale particles which constitutes it and their respective arrangement. Furthermore, the support is stable under the operating conditions of the catalytic converters; that is, the support is stable at temperatures between 600 ° C and 1000 ° C in an atmosphere containing an exhaust gas mixture (CO, H 2 O, NO, N 2 , C x H y , O 2 , N 2 0 ).
- an exhaust gas mixture CO, H 2 O, NO, N 2 , C x H y , O 2 , N 2 0 .
- This thermal stability is directly related to the microstructure of the synthesized material (arrangement of crystallites of the same size, same isodiametric morphology and same chemical composition or substantially of the same size, same isodiametric morphology and same chemical composition in which each crystallite is in point contact or almost punctual with surrounding crystallites) and associated synthesis method (s).
- the particular architecture of the catalytic support has a direct influence on the stability of the metal nanoparticles.
- the arrangement of the crystallites and the porosity makes it possible to develop a mechanical anchoring of said metallic nanoparticles on the surface of the support.
- the excellent dispersion of the active phases thus obtained makes it possible to envisage a significant reduction in the amount of noble metals employed without loss of catalytic performance.
- FIG. 2 illustrates the mechanical blocking of the metal particles by the catalytic ceramic support. Firstly, it is clear that the elementary active particles will be at most the size of a support crystallite. Second, their movement under the combined effect of a high temperature and an atmosphere rich in water vapor is still limited to potential wells that represents the space between two crystallites. The arrows represent the only possible movement of the metal particles.
- the device according to the invention may have one or more of the following characteristics:
- said arrangement is alumina (Al 2 O 3 ) stabilized or not with lanthanum, cerium or zirconium, or cerine (CeO 2 ) stabilized or not stabilized with gadolinium oxide, or zirconia (ZrO 2 ) stabilized or otherwise with yttrium oxide or spinel phase or lanthanum oxide (La 3 O 3 ) or a mixture of one or more of these compounds,
- the metal particles are chosen:
- noble metals selected from Ruthenium, Rhodium, Palladium, Silver, Osmium, Iridium, Platinum or an alloy between one, two or three of these noble metals, or
- transition metals selected from nickel, silver, gold, cobalt, and copper or an alloy between one, two or three of these transition metals, or
- the crystallites have a mean equivalent diameter of between 2 and 20 nm, preferably between 5 and 15 nm, and the metal particles have a mean equivalent diameter of between 2 and 20 nm, preferably less than 10 nm.
- the active phase support crystallite arrangement (s) is at best a hexagonal compact or cubic face-centered stack in which each crystallite is in punctual or near-point contact with at most 12 other crystallites in a 3-dimensional space.
- the catalytic assembly (substrate + catalyst) used in the purification device according to the invention may comprise a substrate of various architectures such as honeycomb structures, barrels, monoliths, honeycomb structures. bees, spheres, multi-scale structured reactors-reactors (reactors), ... of a ceramic or metallic or metallic nature coated with ceramics, and on which the active phase support (s) can be deposited (washcoat) .
- the present invention also relates to a method of cleaning the exhaust gas of a heat engine in which said exhaust gas is circulated through a device according to the invention.
- the heat engine is preferably a motor vehicle engine, in particular a diesel engine or a gasoline engine.
- a method for preparing a support assembly (s) ceramic (s) - phase (s) active (s) may include the following steps:
- a catalytic ceramic support comprising an arrangement of crystallites of the same size, same morphology and same chemical composition or substantially the same size, same morphology and same chemical composition in which each crystallite is in point contact or almost punctual with the crystallites who surround him,
- calcination in air of the impregnated catalyst at a temperature of between 350 ° C. and 1000 ° C., preferably at a temperature of between 450 ° C. and 700 ° C., still more preferably at a temperature of 500 ° C., so as to obtain an active phase (s) oxidized (s) deposited on the surface (s) support (s) ceramic (s) catalytic (s); and d) optionally reducing the oxidized active phase (s) between 300 ° C and 1000 ° C, preferably at a temperature between 300 ° C and 600 ° C, even more preferably at a temperature of 300 ° C.
- this method may include one or more of the following features:
- step b) of impregnation is carried out under vacuum for a period of between 5 and 60 minutes;
- the active phase solution (s) is a solution of rhodium nitrate (Rh (NO 3 ) 3 , 2H 2 O) or a solution of nickel nitrate (Ni (NO 3 ) 2 , 6H 2 O) or palladium ((Pd (NO 3 ) 3 , 2H 2 O) or platinum ((Pt (NO 3 ) x ), yH 2 O) or a mixture thereof.
- said method comprises, after step d) optionally a step e) of aging under operating conditions or close to the operating conditions of the catalyst.
- the first operating cycle stop / start
- the catalytic ceramic support described in step a) of the process for preparing the ceramic support-active phase (s) assembly (s) implemented in the purification device according to the invention can be prepared by two methods.
- a first method will result in a catalytic ceramic support comprising a substrate and a film on the surface of said substrate comprising an arrangement of crystallites of the same size, same isodiametric morphology and same or substantially the same chemical composition, same isodiametric morphology and same chemical composition in which each crystallite is in point or almost punctual contact with the crystallites which surround it.
- a second process will lead to a catalytic ceramic support comprising granules comprising an arrangement of crystallites of the same size, same isodiametric morphology and same chemical composition or substantially of the same size, same isodiametric morphology and same chemical composition in which each crystallite is in point contact or almost punctual with the crystallites that surround it.
- the granules are substantially spherical.
- the first method of preparing the catalytic ceramic support comprises the following steps:
- a sol comprising salts of nitrates and / or carbonates of aluminum and / or magnesium and / or cerium and / or zirconium and / or yttrium and / or gadolinium and / or lanthanum a surfactant and solvents such as water, ethanol and ammonia; ii) Soaking a substrate in the soil prepared in step i);
- step iv) Calcining the gelled composite material of step iii) at a temperature typically between 500 ° C and 1000 ° C in air.
- the substrate used in this first process for preparing the catalytic ceramic support is of dense alumina.
- the second method of preparing the catalytic ceramic support comprises the following steps:
- a sol comprising salts of nitrates and / or carbonates of aluminum and / or magnesium and / or cerium and / or zirconium and / or yttrium and / or gadolinium and / or lanthanum a surfactant and solvents such as water, ethanol and ammonia; ii) Atomising the soil in contact with a hot air stream so as to evaporate the solvent and form a micron powder;
- the soil prepared in the two processes for preparing the catalytic ceramic support preferably comprises four main constituents:
- Inorganic precursors for reasons of cost limitation, we have chosen to use nitrates of magnesium and aluminum, cerium, zirconium, yttrium or a mixture of these nitrate salts. Other inorganic precursors can be used (carbonates, sulfonates, chlorides, ...) alone or mixed in the process.
- the surfactant otherwise called surfactant.
- the solvent absolute ethanol
- the surfactant is solubilized in an ammoniacal solution which makes it possible to create hydrogen bonds between the hydrophilic blocks and the inorganic species.
- the first step is to solubilize the surfactant (0.9g) in absolute ethanol (23 mL) and in an ammoniacal solution (4.5 mL). The mixture is then refluxed for 1 hour. Then, the nitrate solution previously prepared (20 mL) is added dropwise to the mixture. The whole is refluxed for 1 h and then cooled to room temperature. The soil thus synthesized is aged in a ventilated oven whose ambient temperature (20 ° C) is precisely controlled.
- soaking consists in immersing a substrate in the soil and removing it at a constant speed.
- This invention applies to substrates of various architectures such as honeycomb structures, barrels, monoliths, honeycomb structures, spheres, multi-scale structured reactors-reactors (reactors), etc. of ceramic or metallic nature, or ceramic coated metal, and on which said support is removable (wash coat).
- the movement of the substrate causes the liquid forming a surface layer.
- This layer divides in two, the inner part moves with the substrate while the outer part falls into the container.
- the progressive evaporation of the solvent leads to the formation of a film on the surface of the substrate.
- Equation 1 e ⁇ ⁇ v 2/3
- the quenched substrates are then baked at 30 ° C to 70 ° C for a few hours. A gel is then formed. Calcination of substrates under air eliminates nitrates but also decomposes the surfactant and thus release porosity.
- the atomization technique makes it possible to transform a sol into a solid dry form (powder) by the use of a hot intermediate (FIG. 3).
- the principle is based on the spraying of fine droplets soil 3, in a chamber 4 in contact with a hot air stream 2 in order to evaporate the solvent.
- the powder obtained is entrained by the heat flow 5 to a cyclone 6 which will separate the air 7 from the powder 8.
- the apparatus that can be used in the context of the present invention is a reference commercial model "190 Mini Spray Dryer” brand Buchi.
- the powder recovered after the atomization is dried in an oven at 70 ° C and then calcined.
- These support particles of active phase (s) with a size of the order of ten nanometers display a very narrow granulometric distribution centered around 12 nm.
- the average spinel crystallite size in this example is 12 nm (measured by small angle X-ray diffraction, Figure 5). This size corresponds to that of the elementary particles observed in scanning electron microscopy indicating that the elementary particles are monocrystalline.
- D is the size of the crystallites (nm)
- ⁇ is the wavelength of the Cu Ka line (1.5406 ⁇ )
- ⁇ corresponds to the width at mid-height of the line (in rad)
- ⁇ corresponds to the diffraction angle
- the catalytic ceramic support is then impregnated with a solution of precursor Rh, and / or Pt, and / or Pd and / or Ni.
- the catalyst studied is the 3-way catalyst for use in catalytic converters.
- Rh (N0 3 ) 3 , 2H 2 O) nitrate was retained as the inorganic precursor of Rh.
- the concentration of Rh in the nitrate solution was set at 0.1 g / L.
- the catalyst is calcined under air at 500 ° C. for 4 hours.
- the reduction of the active phase is carried out under Ar-H 2 (3% vol) at 300 ° C. for 1 h.
- FIG. 6a In order to observe the size and the metallic dispersion at the surface of the support, observations by transmission electron microscopy were carried out (FIG. 6a). The latter reveal the presence of particles of Rh in the elemental state of a size of the order of a nanometer. These small particles are concentrated around the spinel particles of the support.
- Rh particles coalesce to a size of 5 nm (FIG. 6b).
- a Rh particle is stabilized on a spinel support particle, which greatly reduces the possibility of future coalescence of the metal particles during catalyst operation.
- the impregnation of the support is carried out with a solution of Ni nitrate (Ni (NO 3 ) 2 , 6H 2 0).
- Ni concentration in this solution can be set at 5g / L.
- the catalyst can be calcined in air at 500 ° C. for 4 hours and then reduced under Ar-H 2 (3% vol) at 700 ° C. for 2 hours.
- the AlMg + Rh catalyst was aged for 20 days while being subjected to a temperature of the order of 650 ° C. and another sample was subjected to a temperature of the order of 850 ° C.
- the ultra-divided spinel phase support (catalytic ceramic support) is preserved after aging and the magnification of the spinel particles is very limited.
- the size of the metal particles after aging remains generally less than or equal to the size of the elemental crystallites of the spinel support.
- reaction concerns the pollution control of exhaust gases.
- This invention can be extended to various applications in heterogeneous catalysis by adapting (s) phase (s) active (s) to the desired catalytic reaction (SMR, chemical reactions, petrochemical, environmental, ...) on a catalytic ceramic support ultra-divided spinel base, alumina, ceria, zirconia (stabilized with yttrium or not) or a mixture of these compounds.
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112013033508A BR112013033508A2 (en) | 2011-06-27 | 2012-06-08 | combustion engine exhaust gas purification device comprising a ceramic support and an active phase mechanically coupled to the support |
US14/128,483 US20140130482A1 (en) | 2011-06-27 | 2012-06-08 | Device for the Purification of Exhaust Gases from a Heat Engine, Comprising a Ceramic Carrier and an Active Phase Mechanically Anchored in the Carrier |
JP2014517561A JP2014518152A (en) | 2011-06-27 | 2012-06-08 | Device for purifying exhaust gas from a heat engine comprising a ceramic carrier and an active phase mechanically fixed in the carrier |
CA2838360A CA2838360A1 (en) | 2011-06-27 | 2012-06-08 | Device for the purification of exhaust gases from a heat engine, comprising a ceramic carrier and an active phase mechanically anchored in the carrier |
CN201280031118.XA CN103702759A (en) | 2011-06-27 | 2012-06-08 | Device for the purification of exhaust gases from a heat engine, comprising a ceramic carrier and an active phase mechanically anchored in the carrier |
KR1020147001791A KR20140082632A (en) | 2011-06-27 | 2012-06-08 | Device for the purification of exhaust gases from a heat engine, comprising a ceramic carrier and an active phase mechanically anchored in the carrier |
EP12730415.2A EP2723496A1 (en) | 2011-06-27 | 2012-06-08 | Device for the purification of exhaust gases from a heat engine, comprising a ceramic carrier and an active phase mechanically anchored in the carrier |
MX2013015110A MX2013015110A (en) | 2011-06-27 | 2012-06-08 | Device for the purification of exhaust gases from a heat engine, comprising a ceramic carrier and an active phase mechanically anchored in the carrier. |
RU2014102340/04A RU2014102340A (en) | 2011-06-27 | 2012-06-08 | DEVICE FOR CLEANING EXHAUST GASES OF A HEAT ENGINE CONTAINING A CERAMIC CARRIER AND ACTIVE PHASE MECHANICALLY FIXED IN THE CARRIER |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1155688A FR2976823B1 (en) | 2011-06-27 | 2011-06-27 | EXHAUST GAS PURIFYING DEVICE OF A THERMAL MOTOR COMPRISING A CERAMIC SUPPORT AND AN ACTIVE PHASE MECHANICALLY ANCHORED IN THE SUPPORT |
FR1155688 | 2011-06-27 |
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WO2013000683A1 true WO2013000683A1 (en) | 2013-01-03 |
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PCT/EP2012/060904 WO2013000683A1 (en) | 2011-06-27 | 2012-06-08 | Device for the purification of exhaust gases from a heat engine, comprising a ceramic carrier and an active phase mechanically anchored in the carrier |
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US (1) | US20140130482A1 (en) |
EP (1) | EP2723496A1 (en) |
JP (1) | JP2014518152A (en) |
KR (1) | KR20140082632A (en) |
CN (1) | CN103702759A (en) |
BR (1) | BR112013033508A2 (en) |
CA (1) | CA2838360A1 (en) |
FR (1) | FR2976823B1 (en) |
MX (1) | MX2013015110A (en) |
RU (1) | RU2014102340A (en) |
WO (1) | WO2013000683A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013186470A1 (en) * | 2012-06-11 | 2013-12-19 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method for the purification of exhaust gases from a heat engine using a device comprising a ceramic support divided at the nanometer scale |
WO2015028738A1 (en) * | 2013-08-30 | 2015-03-05 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Material for priming a metal substrate of a ceramic catalyst material |
WO2020189779A1 (en) | 2019-03-20 | 2020-09-24 | 千葉県 | Agent targeting double-membrane organelle dna |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102016751B1 (en) * | 2017-12-14 | 2019-10-14 | 한국에너지기술연구원 | Catalytic removal method of NOx and N2O from semiconductor exhausted gas with various pollutants |
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US20040166340A1 (en) * | 2001-08-30 | 2004-08-26 | Aktina Limited | Process for making thin film porous ceramic-metal composites and composites obtained by this process |
EP1920832A1 (en) * | 2006-11-08 | 2008-05-14 | L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | New supported noble metal catalyst and its use in synthesis gas production |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2991713A1 (en) * | 2012-06-11 | 2013-12-13 | Air Liquide | EXHAUST GAS PURIFYING DEVICE OF A THERMAL MOTOR COMPRISING A FRACTIONAL NANOMETER-SCALE CERAMIC SUPPORT |
-
2011
- 2011-06-27 FR FR1155688A patent/FR2976823B1/en not_active Expired - Fee Related
-
2012
- 2012-06-08 WO PCT/EP2012/060904 patent/WO2013000683A1/en active Application Filing
- 2012-06-08 KR KR1020147001791A patent/KR20140082632A/en not_active Application Discontinuation
- 2012-06-08 CN CN201280031118.XA patent/CN103702759A/en active Pending
- 2012-06-08 BR BR112013033508A patent/BR112013033508A2/en not_active IP Right Cessation
- 2012-06-08 EP EP12730415.2A patent/EP2723496A1/en not_active Withdrawn
- 2012-06-08 JP JP2014517561A patent/JP2014518152A/en active Pending
- 2012-06-08 RU RU2014102340/04A patent/RU2014102340A/en not_active Application Discontinuation
- 2012-06-08 CA CA2838360A patent/CA2838360A1/en not_active Abandoned
- 2012-06-08 MX MX2013015110A patent/MX2013015110A/en not_active Application Discontinuation
- 2012-06-08 US US14/128,483 patent/US20140130482A1/en not_active Abandoned
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US20040166340A1 (en) * | 2001-08-30 | 2004-08-26 | Aktina Limited | Process for making thin film porous ceramic-metal composites and composites obtained by this process |
EP1920832A1 (en) * | 2006-11-08 | 2008-05-14 | L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | New supported noble metal catalyst and its use in synthesis gas production |
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ZHANG H ET AL: "Nanocast Ordered Mesoporous CeO2 as Support for Highly Active Gold Catalyst in CO Oxidation", CHINESE JOURNAL OF CATALYSIS / DALIAN INSTITUTE OF CHEMICAL PHYSICS, ELSEVIER, AMSTERDAM, NL, vol. 30, no. 11, 1 November 2009 (2009-11-01), pages 1085 - 1090, XP026793538, ISSN: 1872-2067, [retrieved on 20091101] * |
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Cited By (5)
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---|---|---|---|---|
WO2013186470A1 (en) * | 2012-06-11 | 2013-12-19 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method for the purification of exhaust gases from a heat engine using a device comprising a ceramic support divided at the nanometer scale |
WO2015028738A1 (en) * | 2013-08-30 | 2015-03-05 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Material for priming a metal substrate of a ceramic catalyst material |
FR3009973A1 (en) * | 2013-08-30 | 2015-03-06 | Air Liquide | MATERIAL FOR PRE-COATING A METAL SUBSTRATE OF A CATALYTIC MATERIAL BASED ON CERAMIC |
WO2020189779A1 (en) | 2019-03-20 | 2020-09-24 | 千葉県 | Agent targeting double-membrane organelle dna |
EP4365590A2 (en) | 2019-03-20 | 2024-05-08 | Juntendo Educational Foundation | Agent targeting double-membrane organelle dna |
Also Published As
Publication number | Publication date |
---|---|
FR2976823A1 (en) | 2012-12-28 |
JP2014518152A (en) | 2014-07-28 |
MX2013015110A (en) | 2014-04-14 |
EP2723496A1 (en) | 2014-04-30 |
RU2014102340A (en) | 2015-08-10 |
FR2976823B1 (en) | 2015-03-27 |
CN103702759A (en) | 2014-04-02 |
CA2838360A1 (en) | 2013-01-03 |
KR20140082632A (en) | 2014-07-02 |
US20140130482A1 (en) | 2014-05-15 |
BR112013033508A2 (en) | 2017-01-24 |
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