EP2379204A1 - Purification structure including a polarised electrochemical catalysis system - Google Patents
Purification structure including a polarised electrochemical catalysis systemInfo
- Publication number
- EP2379204A1 EP2379204A1 EP09804298A EP09804298A EP2379204A1 EP 2379204 A1 EP2379204 A1 EP 2379204A1 EP 09804298 A EP09804298 A EP 09804298A EP 09804298 A EP09804298 A EP 09804298A EP 2379204 A1 EP2379204 A1 EP 2379204A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- less
- electrode
- gas
- ionic
- 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.)
- Withdrawn
Links
- 238000006555 catalytic reaction Methods 0.000 title description 7
- 238000000746 purification Methods 0.000 title description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 96
- 239000010416 ion conductor Substances 0.000 claims abstract description 47
- 239000004020 conductor Substances 0.000 claims abstract description 13
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 48
- 230000010287 polarization Effects 0.000 claims description 28
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 26
- 238000003860 storage Methods 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 230000009467 reduction Effects 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 16
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 239000000446 fuel Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000004071 soot Substances 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- -1 oxygen ions Chemical class 0.000 claims description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000012212 insulator Substances 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 239000011810 insulating material Substances 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 9
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000010948 rhodium Substances 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 5
- 239000011532 electronic conductor Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002823 nitrates Chemical group 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000007320 rich medium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 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
- F01N3/02—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
- 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
- B01D53/32—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 by electrical effects other than those provided for in group B01D61/00
- B01D53/326—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 by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
-
- 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
- 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
- B01J23/70—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
- B01J23/78—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 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
- B01J23/70—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
-
- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
- B01J23/70—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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0006—Honeycomb structures
-
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
- C04B38/0058—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity open porosity
-
- 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
- F01N3/0892—Electric or magnetic treatment, e.g. dissociation of noxious components
-
- 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
-
- 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
- B01D2255/2045—Calcium
-
- 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
- B01D2255/207—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
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20746—Cobalt
-
- 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
- B01D2255/20753—Nickel
-
- 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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- 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
- B01J37/16—Reducing
-
- 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
- F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
- F01N2240/04—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being an electric, e.g. electrostatic, device other than a heater
-
- 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
- F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
- F01N2240/28—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being a plasma reactor
-
- 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
-
- 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
- F01N2510/065—Surface coverings for exhaust purification, e.g. catalytic reaction for reducing soot ignition temperature
-
- 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
- F01N3/022—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 characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0222—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 characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
-
- 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
- F01N3/023—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 using means for regenerating the filters, e.g. by burning trapped particles
-
- 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
- F01N3/24—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
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2825—Ceramics
- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to the field of structures for purifying a gas charged with gaseous pollutants essentially of NO x type. More particularly, the invention relates to honeycomb structures, in particular used to treat the exhaust gas of a gasoline or preferably diesel engine, and incorporating an electrochemical catalyst system.
- a conventional three-way catalyst allows the joint treatment of pollutants NO x , CO and HC and their conversion into neutral and chemically harmless gases such as N 2 , CO 2 and H 2 O.
- a very good efficiency of the system is not achieved only by a continuous adjustment of the richness of the air-fuel mixture. It is thus known that the slightest deviation from the stoichiometry of said mixture causes a large increase in pollutant emissions.
- the desorption of the NOx trapped on the catalyst and their catalytic reduction in nitrogen gas N 2 can not only in the presence, at the level of the reduction catalyst, of a sufficient quantity of the reducing species, in the form of hydrocarbons or carbon monoxide CO or hydrogen H 2 , the hydrogen being able to be -Even obtained by a catalytic reaction between HC hydrocarbons and water vapor or between CO and water vapor.
- the NOx adsorbing materials are generally alkali metal or alkaline earth metal oxides, in particular barium oxide, a material currently known to be the most effective in this field.
- the efficiency of the conversion of the polluting species can also be substantially limited by the intrinsic characteristics of the materials used as the ionic and electronic conductor. More precisely, since the electrochemical system consists of small grains randomly arranged with respect to each other, its efficiency is necessarily limited, on the one hand, by the connections between the grains and, on the other hand, by the small quantity of conductors (electrons). and / or ions) available for the proper functioning of the electrochemical catalysis system.
- the object of the present invention is to provide a solution for solving the problems described above.
- one of the aims of the present invention is to provide a structure for the purification of a polluted gas, in particular a structure for filtering an exhaust gas resulting from a gasoline or preferably diesel engine loaded with pollutants. gaseous and solid particles, able to work effectively regardless of the richness of the air / fuel mixture.
- the invention relates to novel electrochemical systems, having an NO x storage ability comparable to systems using the presence of alkali or alkaline earth metals of the barium type.
- the invention relates to a NOx storage / reduction device of the particle filter type making it possible to limit the operating frequencies in rich mixture necessary for the destocking and the reduction of NO x , or even to to overcome and thus avoid overconsumption in fuel, characterizing the electrochemical systems already described.
- the invention relates in its most general form to a device for the purification of a polluted gas, for example an exhaust gas from a diesel engine or gasoline, comprising: - one and preferably a plurality monolithic honeycomb blocks, typically interconnected by a joint cement and constituting a particulate filter, said block or blocks comprising a set of adjacent channels of axes parallel to each other separated by porous walls, closed by plugs at one or the other of their ends to define inlet ducts opening on a gas inlet face and outlet ducts opening on a gas evacuation face, in such a way the gas passes through the porous walls in which at least one porous electronic conductive material forms the walls of said structure, an electrochemical system for treating said gas comprising: a layer of a material D ionic conductor by the oxygen ions and electronic insulator, the ionic conductor D comprising or consisting of a zirconium oxide partially substituted by a trivalent cation M 3+ or divalent M ' 2+ ,
- the plugs obstructing the output channels on the front face of the filter and plugs obstructing the input channels on the rear face of the filter are ionic conductors, and are electrically interconnected to constitute respectively the reference electrode W and the counter-electrode CE.
- the electronic conductive plugs may consist of SiC doped with aluminum.
- Catalyst A is preferably chosen to also be suitable for the oxidation of soot.
- Catalyst B is preferably chosen to also be suitable for the oxidation of polluting species of the HC, CO or H 2 hydrocarbon type.
- ion conductor comprising or consisting of a partially substituted zirconium oxide with a cation valence lower than that of zirconium.
- the ion conductor according to the invention can be formulated by an equation:
- x is less than 0.5.
- x is less than 0.1, and very preferably, x is less than 0.05.
- x is greater than 0.005, or even greater than 0.01. In the preceding formula, it is of course always strictly greater than 0 and strictly less than 2.
- y is generally less than or equal to 0.5.
- y is less than or equal to 0.25 and very preferably y is less than or equal to 0.1. In the preceding formula, y 'is of course strictly greater than 0 and strictly less than 1.
- y' is generally less than or equal to 0.6. Preferably, y 'is less than or equal to 0.3 and most preferably y' is less than or equal to 0.15.
- M is for example selected from the group consisting of Y 3+ , Sc 3+ or rare earths.
- M ' is for example selected from the group consisting of Ca 2+ and Sr 2+ .
- the ionic conductor D can also play a role of support material for the catalytic system and, for this purpose, preferably has a large specific surface area even after a calcination of 800 and 1000 ° C.
- the ionic conductor advantageously has a specific surface area of at least 5 m 2 / g, preferably at least 10 m 2 / g, or even at least 50 m 2 / g.
- the ionic conductor based on zirconia is an ionic conductor by oxide ions O 2 ⁇ , the conduction being obtained by substitution of certain zirconium atoms with lower valence transition metal cations as previously described.
- the trivalent or divalent substitution cations may be chosen according to the invention, in the group consisting of Y 3+ , Sc 3+ , Ca 2+ , Sr 2+ or rare earths. Good understood, this list is in no way limiting and other substitution cations, divalent or trivalent, may be considered without departing from the scope of the present invention.
- the ionic conductivity obtained by such a substitution is typically between 1 and 10 ⁇ 4 S / cm in the temperature range of 150 to 800 ° C.
- the porous inorganic material has an open porosity, conventionally measured by mercury porosimetry, greater than 10%, preferably greater than 20%, or even greater than 30%. Too little porosity of the material constituting the filtering walls leads to a too high pressure drop. Too high a porosity of the material constituting the filtering walls leads to insufficient filtration efficiency.
- the porous inorganic material is based on silicon carbide SiC, preferably recrystallized at a temperature of between 2100 and 2400 ° C.
- the inorganic material may be based on doped SiC, for example with aluminum or nitrogen, and such that its electronic resistivity is preferably lower than 20 Ohm. cm at 400 0 C, more preferably less than 15 Ohm. cm at 400 0 C and more preferably less than 10 Ohm. cm at 400 ° C.
- SiC-based is meant in the sense of the present description that the material consists of at least 25% by weight, preferably at least 45% by weight and so very preferred at least 70% by weight of SiC.
- Catalyst A most often comprises at least one precious metal selected from Pt and / or Pd and / or Rh and / or Ag and / or Au and / or transition metals, especially Cu, Fe, Ni, Co, and transition metal oxides such as Mn 2 ⁇ 3, C0 3 O 4 .
- Catalyst A used for the reaction of For example, the reduction is selected from catalysts well known in the art for their activity and preferably their selectivity to NOx reduction reactions. They can in particular be chosen from rare earths which can help to fix or trap NOx deposited in admixture with an active ingredient including precious metals or transition metals according to the known technique.
- the catalyst B most often comprises at least one precious metal selected from Pt and / or Pd and / or Rh and / or Ag and / or Au and / or transition metals, in particular Cu, Fe, Ni, Co and / or or the oxides of the transition metals.
- the catalyst B can advantageously be chosen from catalysts otherwise well known in the art for their activity and preferably their selectivity vis-à-vis the oxidation reactions of hydrocarbons .
- the reforming and steam reforming catalysts used in the field of petrochemistry and refining can be used according to the invention as catalyst B.
- Those deposited in admixture with an active ingredient including precious metals Pt, Pd, Rh, or transition metals, especially Cu, Fe, Ni, Co, can be effectively used according to the invention.
- the device as just described can be implemented according to the various methods that will now be exposed.
- the following operating modes are representative of certain preferred modes of the invention, but it is understood that other modes are also possible, without departing from the scope of the invention.
- the ionic conductor D is reduced beforehand by electrochemical activation and it imposes periodically a potential or a negative current between the electrodes W and CE, to maintain in the reduced state the ionic conductor at least at the interface between the layer D and the catalyst A during the phases of operation of the engine in which the structure honeycomb is fed by a gas mixture low in fuel.
- the ionic conductor based on zirconia is reduced beforehand by electrochemical activation.
- This electrochemical activation consists of a negative electric polarization of high amplitude, that is to say of at least -2.2
- working electrode W for example connected to catalyst A and the counter-electrode CE, for example connected to catalyst B.
- this polarization is carried out at a temperature of at least 200 ° C., and more preferably at least 400 ° C. for at least a few minutes and at most for one hour.
- Such a polarization has the effect of locally reducing the ionic conductor at least at the interface between the layer D and the catalyst A, that is to say, to bring it into a deficit state (i.e. under stoichiometric) in oxygen.
- the negative potential imposed between the electrodes W and CE corresponds to the minimum value, deduced from the ohmic drop of the system, to electrochemically reduce the ionic conductor layer D, at least on the electrode side W.
- the duration of the polarization is deliberately short (for example from 1 to 60 minutes) in order to reduce the layer D to a small thickness, preferably a few microns, for example from 1 to 100 microns, compatible with a surface adsorption mechanism .
- the inventors have observed that this polarization makes it possible to significantly and unexpectedly increase the storage capacity of the NO x of the catalyst pair A / ionic conductor D.
- the polarization of the layer D is not continuous but is triggered periodically during or immediately after an engine operating phase in which the honeycomb structure is fed with a fuel-rich mixture (air / fuel stoichiometry less than 1).
- the polarization is this time applied continuously, but is reversed periodically.
- This operating mode which can be activated unlike the previous one without the need for a fuel-rich phase, allows during a first phase to increase (unexpectedly) the NO x storage capacity by the catalyst pair.
- a / ionic conductor D is a second phase, by polarity inversion
- a / ionic conductor D is regenerated, i.e.
- NO x previously stored during the previous phase by the catalyst pair A / ionic conductor D are released in the form of NO x in particular NO 2 and / or NO and / or N 2 O.
- the NO x thus in sufficient concentration, can then be reduced essentially by means of electrochemical activation on catalyst B.
- a third embodiment according to the invention alternative to or complementary to the previous ones, alternating the two regeneration paths of the reduction catalyst A, as described previously in connection with respectively the first and second embodiments above.
- the decomposition of the nitrates is alternately obtained during certain phases by the introduction of a rich fuel mixture and in other phases by a positive electric polarization between W and CE, according to the operating modes previously described.
- the reduced state of the layer D (oxygen sub-stoichiometry) can be preserved and maintained by the operating phases during which the structure is fed with a fuel-rich mixture.
- the electrochemical activation of the layer D by application of a negative voltage or current between W and CE can be triggered in the event of a significant loss, for example of at least 30%, of the conversion to NO x by the device.
- the present invention is particularly applicable in structures used for the purification and filtration of an exhaust gas of a diesel engine.
- Such structures generally referred to as particle filters, include one and preferably a plurality of monolithic honeycomb blocks.
- the block or blocks comprising a set of adjacent ducts or channels of axes parallel to each other separated by porous walls, closed by plugs to one or the other. other of their ends to define inlet ducts opening on a gas inlet face and outlet ducts opening on a gas evacuation face, so that the gas passes through the porous walls.
- Examples of such assembled or unassembled structures are for example described in publications EP 0816065, EP 1142619, EP1306358 or EP 1591430.
- Such a system can also contribute to improving the regeneration efficiency of the filter by promoting a higher oxidation rate of the soot.
- the filter body according to the invention is thus essentially constituted of a porous silicon dioxide matrix, optionally doped, which constitutes the walls of a filtering structure. Honeycomb.
- the catalyst B is deposited for example by impregnation in the porosity of the walls of the filter body.
- the catalyst B is deposited in proportions and conditions which preferably allow the particles constituting it to be percolated between them, in the form of a film or an electronically conductive network.
- the particles may be deposited on a catalyst support consisting of an electronically conductive material.
- the ionically conductive material D is then deposited on the surface of the impregnated SiC walls and covered by the catalyst B in a layer whose thickness is preferably adjusted to remain permeable to the exhaust gases passing through the wall of the filter and to lead to a percolating ion driver network.
- the second reducing catalyst A is then deposited on the layer of the ionic conductive material, for example according to conventional impregnation techniques, such that the layer of material D electrically isolates the two catalysts.
- catalyst A is deposited in proportions and conditions permitting the percolation of the particles constituting it, in the form of a film or an electronically conductive network.
- Figure 1 is a schematic representation in section of a wall piece of a catalytic filter obtained according to the invention, incorporating in its porosity a catalyst B (step 1).
- Figure 2 is a schematic sectional representation of a wall piece of a catalytic filter obtained according to the invention, incorporating in its porosity catalyst B covered by a layer of ionic conductive material D (step 2).
- FIG. 3 is a diagrammatic representation in section of a wall piece of a catalytic filter obtained according to the invention, incorporating in its porosity catalyst B covered by a layer of an ionic conductive material D, said material D separating catalysts A and B (step 3).
- FIG. 4 is a schematic representation in section of a portion of a catalytic filter obtained according to the invention, wherein the inlet channels are blocked by plugs.
- FIG. 5 shows an elevational view of the inlet 5a and outlet 5b faces of the filtration system according to the invention.
- Figure 6 illustrates the experimental device used in the examples to demonstrate the effectiveness of a device according to the present invention.
- a longitudinal sectional view of the parallel walls 1 of a conventional honeycomb particle filter has been schematized from the front face 5 of the gas inlet. example as described in applications EP 816065 or EP 1142619.
- the constituent material of the walls 1 of the filter consists of an electronically conductive material, for example SiC doped with aluminum Al, whose open porosity is typically close to 45%.
- the filter alternately comprises input channels 2 and output channels 3, depending on the position of the plugs.
- the catalyst B is deposited by a sol-gel process and according to well-known methods, in the form of nanometric particles 4 of Rh metal. particles are thus dispersed in the porosity of the electron-conducting SiC, inside the walls 1 of the channels 2, 3.
- the impregnation can be carried out only in the lower part of the filter, for example on the first third of the length of the channels from the front face 5 of the gas inlet.
- the impregnation can, without departing from the scope of the invention, relate to a more or less important part of the walls 1, in particular to limit the losses due to the presence of the catalyst and fully retain the structure its role filtration.
- the impregnation with the catalytic solution is carried out under conditions permitting the diffusion of the catalytic solution throughout the thickness of the walls 1.
- the impregnated thickness of the walls 1 is at least of the order of 500 nm.
- the outlet channels 3, on the side of the front face 5 of the honeycomb structure of the uncapped filter are masked with a resin or a wax 6 that can be eliminated by a simple heating at a temperature typically less than or equal to 300 0 C, so as not to deteriorate the catalyst layer already present, according to masking techniques well known to those skilled in the art.
- the structure is then dried.
- a sol-gel deposition of the ionic conductor D is then performed.
- the initial sol-gel solution used for the deposition is obtained by mixing the nitrates of Yttrium Y (NO 3 ) (H 2 O) 6 and Zirconium ZrO (NO 3 ) 2 (H 2 O) 6 in respective proportions resulting in an amount of 8 mol% of Y 2 ⁇ 3 in the yttria zirconia layer 7 finally obtained after heating.
- the deposited layer may protrude beyond the portion 4 of the walls impregnated by the catalyst B.
- the porosity of this ionic conducting layer 7 is chosen to be sufficiently low to ensure good ionic conduction.
- the thickness of the ionic conducting layer 7 is also sufficiently small and porous to allow it to pass through the exhaust gases during operation.
- the resin masks 6 are then removed and the layer 7 of ionic conductor is matured, by a thermal treatment under air at 300 ° C. The treatment makes it possible to clear the outlet channels 3. It may be necessary to finely grind the surface of these channels to finish removing the resin residues.
- the filter is preferably again impregnated in the sol-gel solution of the ion conductor D so as to cover only the lower end 8 of the channels, for example to a height of about 1 mm.
- the output channels 3 are then masked again at the front face 5 of the filter, with the same resin 6 as previously described.
- a solution of catalyst A is prepared from Pt salts. According to well-known techniques, the solution is matured in the form of a sol gel and then the catalyst filter A is impregnated with this solution by simple immersion as previously under form of a film or layer 9 disposed on the surface or in the porosity of the ionic conductive layer 7. According to one possible mode, a deposition of a SiC layer can be carried out before the deposition of Pt, in order to ensure the electrical percolation and the good dispersion of the Pt. The resin masks 6 are then removed by a thermal treatment under air at 300 ° C. The treatment makes it possible to clear the outlet channels 3. It may be necessary to finely grind the surface of these channels to finish removing resin residues.
- the input channels are then masked with a resin or a suitable paper, according to techniques well known in the art.
- the outlet channels 3 of the filter which are not masked by the resin, are then closed off by electronic conductive plugs 11, as shown in FIG. 4.
- the plugs 11 are conventionally obtained by the application, on the side of the front face 5 and at the end of the outlet channels 3, of a SiC-based slip doped with aluminum to increase the electronic conduction, followed by a heat treatment of solidification at 500 ° C.
- the inlet channels are then closed by plugs 12 which are also electronically conductive.
- the method thus used then leads to a filter illustrated schematically in FIG. 4.
- FIG. 5 shows an elevational view of the inlet 5a and outlet 5b faces of a filtration system according to the invention produced from the filter shown in FIG. 4.
- the plugs 11 obstructing the output channels 3 on the input face (FIG. 5a) and obstructing the input channels 2 on the output face (FIG. 5b) are consisting of conductive SiC. On the inlet face, all plugs 11 are interconnected by metal wires 13 to constitute the reference electrode W
- the catalyst B is placed on the surface and / or in the walls of the filter in the form of particles 4.
- the catalyst particles B are thus in contact with the electron-conductive SiC walls of the monolith but electronically isolated from the catalysts A by the D-layer. solid electrolyte.
- All the plugs 12 of the output face of the filter are interconnected by metal wires 14 to form the counter-electrode CE.
- the counter CE electrode is thus obtained by the electronic contact of all layers or catalyst films B.
- the combustion gases from the engine enter the filter structure via the inlet channels 2 and are in direct contact with the layer 9 of the catalyst A.
- the gases then pass through the porous walls 1 and then come into direct contact with the catalyst. the layer 4 of the catalyst B.
- the gases, substantially free of their pollutants, are then discharged through the outlet channels 3.
- the invention is however not limited to the embodiment as previously described but must be understood as referring to any catalyzed filtering structure comprising at least a catalyst A and a catalyst B and polarized according to the above principles.
- the filtration structures in accordance with the invention comprise inlet channels and adjacent outlet channels delimited by porous walls whose ends are alternately plugged on one side and then on the other, according to conventional particle filter technology. for internal combustion engine.
- the catalyzed filter is polarized by the application of an electric current or a voltage typically from an electric generator, preferably such that the current density applied between electrode W and the counter electrode CE is greater than 0.01 mA / cm 2 , preferably greater than 0.05 mA / cm 2 and typically between 0.01 and 10 mA / cm 2 .
- the surface taken into account is the sum of the specific surfaces of the deposit A and the deposit B.
- the invention also relates to an exhaust line incorporating the combustion gas depollution device of a diesel engine preferably equipped as described above. .
- the device may comprise in particular a 0 to 10 Volts absolute voltage setting system and an associated control system according to the engine speed to other data provided by sensors, in particular one or more NO x sensors.
- the device according to the invention may also comprise additional means allowing the implementation of an onboard control of the catalytic activity of the catalyst.
- the control can consist simply of the stopping of the polarization and the measurement of the remaining potential difference between the electrode W and the counterelectrode CE. From reference values, typically established on the basis of model cells, corresponding to the potential difference measured without voltage, it is possible to estimate in a simple and fast way the efficiency of the catalyst and to apply electrochemical activation if necessary to generate the reduction of catalyst A and thus promote the catalytic efficiency of the system.
- This onboard control of the catalytic efficiency is complementary to that of the NOx sensor.
- the measurement of the voltage difference potential can induce or participate among other parameters (pressure drop, weight of the filter, etc.) in the choice of the threshold of tripping or stopping of a regeneration phase.
- the electrochemical system according to the present invention is further adapted not only to the reduction of NO x but also allows, jointly, at the level of catalysts A or B and depending on their respective electric polarization, the oxidation of soot (solid particles) present. in the walls of the particulate filter, or the oxidation of the gaseous reducing species contained in the exhaust gas such as unburnt hydrocarbons and / or carbon monoxide and / or HC + H 2 O type steam reforming reactions - ⁇ 3/2 H 2 + CO and / or reactions of gases with water of CO + H 2 O -> H 2 + CO 2 type .
- the electrons necessary for the NO x reduction reaction, or even the anions required for the combined oxidation reaction of HC and / or CO, are advantageously directly supplied by the support, which makes it possible to ensure the operation of the electrochemical system with a quantity of conductive species that is almost constant and not limited by the size of the solid electrolyte or electrolytes,
- the operation of the electrochemical catalysis system is improved since all the catalyst particles A and B are active: the electrochemical system is active regardless of the relative disposition of the particles of the catalysts A and B in the porosity of the material constituting the walls,
- Such a property allows, within the catalyzed filter according to the invention, a continuous electrochemical reduction of the NO x , whether during the operating phases of the engine in a rich mixture, corresponding according to the invention to a NO x destocking phase, or also surprisingly during the operating phases of the engine lean mixture, a sensitive portion of the NOx being directly captured and stored by the catalyst A, in contact with the ion conductor D maintained according to the invention, in a reduced state, before being reduced to the catalyst B.
- An electrochemical catalysis system 100 was carried out on the basis of a dense yttria-stabilized zirconia tube 101 (ZrO 2) o, 92 (Y 2 O 3) 0.08, 42 cm long and 3 mm thick.
- the tube constitutes the ionic conductor D (O 2 ⁇ ion conduction).
- two platinum films 102, 103 are deposited from a platinum lacquer respectively on the two outer and inner faces of the tube, over a distance d of 6 cm.
- the tube is calcined at 500 ° C. for 1 hour in air after each deposition step.
- the two films of Pt 102, 103 thus constitute respectively the reference electrode and the counter- electrode for the inner face and are connected to means 104 for applying a bias voltage.
- the reference electrode 102 is exposed on the outside face to the reaction mixture consisting of a gas comprising nitrogen monoxide and oxygen as described in Table 1 while the electrode 103 is kept in air.
- EXAMPLE 2 The same type of system is realized as above but the yttrie zirconia is reduced by a so-called "electrochemical pre-activation" step by means of a negative polarization of -4 V, ohmic drop included, for 1 hour at 400.degree. 0 C by applying a potential difference between the reference electrode and the counter-electrode for the inner face.
- Example 1 On each system of Example 1 and Example 2 several cycles were then carried out to obtain an average value representative of the storage capacity in a mixture rich in oxygen.
- the surface of the catalyst Pt is regenerated by a scanning under a current of a neutral gas (H e ) so as to achieve the destocking of all the nitrogen oxides, without reducing agent and consequently without catalytic reduction of NOx by a reducing gas is possible. In this case, only the electrochemical reduction can occur.
- Table 1 Experimental measurement data are provided in Table 1.
- Example 2 The experimental results reported in Table 2 show that the storage capacity of the system of Example 1, in which a non-prereduced zirconia is used and no NOx trap of alkali or alkaline earth metal type, is very weak or non-existent. .
- the system according to Example 2 with pre-reduced zirconia shows a significant increase in the storage capacity of the nitrogen oxides of the catalytic system despite the presence of a large amount of oxygen in the gas to be treated and a specific surface area of YSZ exposed to extremely low gas (less than 1 m 2 / g), which had never been observed until then.
- Example 3 The system described in Example 2 was subjected to polarization cycling.
- the reference electrode and the counter-electrode are connected to a generator 104 and subjected to a bias voltage of -4 volts for 5 minutes.
- the system is subjected to a positive bias of +4 V volts for about 30 seconds.
- the adsorbed NOx content in a first cycle was first measured, and so on until a tenth negative and positive polarization cycle.
- An electrochemical catalysis system 100 was made on the basis of porous tubes made of zirconia 105 stabilized with yttrium (ZrO 2) o, 92 (Y 2 O 3) 0.08, of length 42 cm and thickness 3 mm, placed in a reactor. Quartz 106.
- the tube constitutes the ionic conductor D (conduction by O 2 ⁇ ion).
- a film 102 of platinum and a film 103 of Rh are deposited from platinum and rhodium lacquers on the two inner and outer faces of the tube respectively, over a distance d of 6 cm.
- the tube is calcined at 500 ° C. for 1 hour in air after each deposition step.
- the tube porous with these two electrodes is exposed to the same reaction mixture on the inner and outer faces of the tube.
- Example 4 The same type of system is realized as previously in Example 4, but the yttrie zirconia is this time reduced by a so-called “electrochemical pre-activation" step by means of a negative bias of -4 V, including ohmic drop, during 1 hour at 400 ° C. by applying a potential difference between the working electrode and the counter-electrode for the internal face.
- Example 4 On each system of Example 4 and Example 5 several cycles were then carried out to obtain an average value representative of the storage capacity in a mixture rich in oxygen.
- the surface of the catalyst Pt and the catalyst Rh is regenerated by scanning under a current of a neutral gas (H e ) so as to achieve the destocking of all the nitrogen oxides, without reducing agent and therefore, no catalytic reduction of NOx by a reducing gas is possible. In this case of f igure, only the electrochemical reduction can occur.
- H e neutral gas
- thermocouple Temporal Location of measurement sensors: thermocouple (Temperature) placed at 3 mm (approximately) from the surface of the catalyst, gas analysis is carried out at the reactor outlet by IR + ⁇ GC analyzers.
- Example 5 shows that the storage capacity of the system of Example 4, in which a non-prereduced zirconia is used and no NOx trap of alkali or alkaline earth metal type, is very weak or non-existent. .
- the system according to Example 5 with pre-reduced zirconia shows a significant increase in the storage capacity of the nitrogen oxides of the catalytic system despite the presence of a large amount of oxygen in the gas to be treated and a specific surface area of YSZ exposed to extremely low gas (less than 5 m 2 / g), which had never been observed until then.
- Example 5 a significant electrochemical conversion of NOx to N2 during the destocking phase.
- Example 5 The system described in Example 5 was subjected to polarization cycling.
- the working electrode and the counterelectrode are connected to a generator 104 and subjected to a bias voltage of -4 volts for 5 minutes.
- the system is subjected to a positive polarization of + 4 V volts for about 30 seconds.
- the adsorbed NOx content in a first cycle was first measured, and so on until a tenth negative and positive polarization cycle.
- Experimental measurement data are provided in Table 7.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Electrochemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Engineering & Computer Science (AREA)
- Structural Engineering (AREA)
- Mechanical Engineering (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0858729A FR2939696B1 (en) | 2008-12-17 | 2008-12-17 | PURIFICATION STRUCTURE INCORPORATING A POLARIZED ELECTROCHEMICAL CATALYSIS SYSTEM |
PCT/FR2009/052575 WO2010076508A1 (en) | 2008-12-17 | 2009-12-16 | Purification structure including a polarised electrochemical catalysis system |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2379204A1 true EP2379204A1 (en) | 2011-10-26 |
Family
ID=40394185
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09804298A Withdrawn EP2379204A1 (en) | 2008-12-17 | 2009-12-16 | Purification structure including a polarised electrochemical catalysis system |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2379204A1 (en) |
FR (1) | FR2939696B1 (en) |
WO (1) | WO2010076508A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5874195B2 (en) * | 2011-05-20 | 2016-03-02 | いすゞ自動車株式会社 | Particulate matter sensor |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4253925A (en) * | 1979-10-22 | 1981-03-03 | The Board Of Trustees Of The Leland Stanford Junior University | Method and apparatus for catalytic dissociation of NO |
DE3644090A1 (en) * | 1986-12-23 | 1988-07-07 | Bbc Brown Boveri & Cie | Process and apparatus for purifying exhaust gases |
US5352337A (en) * | 1992-04-14 | 1994-10-04 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Method for reducing nitrogen oxides |
US5401372A (en) * | 1993-04-26 | 1995-03-28 | Ceramatec, Inc. | Electrochemical catalytic reduction cell for the reduction of NOx in an O2 -containing exhaust emission |
EP1382443B1 (en) | 1996-01-12 | 2013-04-24 | Ibiden Co., Ltd. | A filter for purifying exhaust gas |
US6878354B1 (en) | 1999-09-03 | 2005-04-12 | Mitsubishi Denki Kabushiki Kaisha | Catalyst and process for exhaust purification |
ES2281733T3 (en) | 1999-09-29 | 2007-10-01 | Ibiden Co., Ltd. | BEE NEST FILTER AND CERAMIC FILTER SET. |
JP3657542B2 (en) * | 2001-07-24 | 2005-06-08 | 独立行政法人産業技術総合研究所 | Chemical reactor |
JP4382367B2 (en) | 2003-01-14 | 2009-12-09 | 日本碍子株式会社 | Method for joining ceramic honeycomb structures |
KR100603008B1 (en) * | 2004-09-07 | 2006-07-24 | (주)네오포텍 | Apparatus for purifying diesel exhaust gas with coated photocatalyst layer and electrode, and manufacturing method thereof |
KR20060115939A (en) * | 2005-05-07 | 2006-11-13 | (주)네오포텍 | System for purifying exhaust gas of diesel engine and method use of the same system |
FR2895274B1 (en) * | 2005-12-23 | 2008-04-04 | Peugeot Citroen Automobiles Sa | CATALYST FOR ENGINE EXHAUST LINE, POLLUTING EMISSION REDUCTION DEVICE INCLUDING CATALYST AND USE THEREOF |
FR2899493B1 (en) * | 2006-04-10 | 2008-05-23 | Saint Gobain Ct Recherches | PURIFICATION STRUCTURE INCORPORATING AN ELECTROCHEMICAL CATALYSIS SYSTEM |
FR2921848B1 (en) * | 2007-10-08 | 2011-03-18 | Saint Gobain Ct Recherches | TEXTURED PURIFICATION STRUCTURE INCORPORATING AN ELECTROCHEMICAL CATALYSIS SYSTEM |
DE102007062249A1 (en) * | 2007-12-21 | 2009-06-25 | Robert Bosch Gmbh | Catalyst for the treatment of combustion exhaust gases |
-
2008
- 2008-12-17 FR FR0858729A patent/FR2939696B1/en not_active Expired - Fee Related
-
2009
- 2009-12-16 WO PCT/FR2009/052575 patent/WO2010076508A1/en active Application Filing
- 2009-12-16 EP EP09804298A patent/EP2379204A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
WO2010076508A1 (en) | 2010-07-08 |
FR2939696B1 (en) | 2015-12-04 |
FR2939696A1 (en) | 2010-06-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2197568B1 (en) | Purification structure incorporating a biased electrochemical catalyst system | |
CA2648397A1 (en) | Purification structure incorporating an electrochemical catalysis system | |
EP3230564B1 (en) | Exhaust gas aftertreatment device for internal combustion engine | |
EP2197567B1 (en) | Texturized purification structure incorporating an electrochemical catalyst system | |
EP3017158B1 (en) | System and process for regeneration of a nox adsorbing material | |
EP3230563B1 (en) | Exhaust gas aftertreatment device for internal combustion engine | |
EP2582449A2 (en) | Electrochemical catalysis system | |
WO2011157964A1 (en) | Use of an nox-reducing catalyst system based on a mixed cerium oxide | |
EP2379207A1 (en) | Purification structure including a catalysis system supported by a zircon in reduced state | |
FR3057020A1 (en) | DEVICE FOR POST-PROCESSING EXHAUST GASES OF A THERMAL ENGINE | |
FR2984182A1 (en) | CATALYTIC GAS TREATMENT SYSTEM | |
WO2010076508A1 (en) | Purification structure including a polarised electrochemical catalysis system | |
KR101086595B1 (en) | Exhaust gas purification device for internal combustion engine | |
EP1968741B1 (en) | Catalyst for an engine exhaust line, device for reducing polluting emissions including this catalyst, and uses of this device | |
EP2014360A1 (en) | Device for treating the gas emissions of an engine. | |
EP2990097A1 (en) | Catalytic particle filter | |
WO2020094935A1 (en) | Vehicle equipped with a spark ignition engine and a self-regenerating particulate filter, and associated control method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20110718 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: VERNOUX, PHILIPPE Inventor name: PRINCIVALLE, AGNES Inventor name: HADJAR, ABDELKADER Inventor name: GUIZARD, CHRISTIAN |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: HADJAR, ABDELKADER Inventor name: VERNOUX, PHILIPPE Inventor name: GUIZARD, CHRISTIAN Inventor name: PRINCIVALLE, AGNES |
|
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20140708 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20141119 |