JP2011515221A5 - - Google Patents
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- JP2011515221A5 JP2011515221A5 JP2011502059A JP2011502059A JP2011515221A5 JP 2011515221 A5 JP2011515221 A5 JP 2011515221A5 JP 2011502059 A JP2011502059 A JP 2011502059A JP 2011502059 A JP2011502059 A JP 2011502059A JP 2011515221 A5 JP2011515221 A5 JP 2011515221A5
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- oxidation
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- 239000003054 catalyst Substances 0.000 claims description 74
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 230000003647 oxidation Effects 0.000 claims description 36
- 238000007254 oxidation reaction Methods 0.000 claims description 36
- 230000003197 catalytic Effects 0.000 claims description 25
- 239000006104 solid solution Substances 0.000 claims description 22
- 239000010953 base metal Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000004071 soot Substances 0.000 claims description 19
- 150000001768 cations Chemical class 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- WUKWITHWXAAZEY-UHFFFAOYSA-L Calcium fluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 14
- GEIAQOFPUVMAGM-UHFFFAOYSA-N oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 12
- 239000010436 fluorite Substances 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- -1 oxygen ion Chemical class 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- OFJATJUUUCAKMK-UHFFFAOYSA-N Cerium(IV) oxide Chemical group [O-2]=[Ce+4]=[O-2] OFJATJUUUCAKMK-UHFFFAOYSA-N 0.000 claims description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- 241000894007 species Species 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910004625 Ce—Zr Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000006262 metallic foam Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 230000001747 exhibiting Effects 0.000 claims 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 150000002500 ions Chemical class 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 3
- 230000002378 acidificating Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910020203 CeO Inorganic materials 0.000 description 1
- 229910002089 NOx Inorganic materials 0.000 description 1
- 229920002397 Thermoplastic olefin Polymers 0.000 description 1
- 229910003134 ZrOx Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000024881 catalytic activity Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Description
本明細書におけるドープされたＯＳ材料は、実質的に相純粋な立方晶のフルオライト構造を含有するＺｒＯ2／ＣｅＯ2固溶体に基づくものであって、卑金属、即ち非貴金属の特定のイオン交換により生成される。適切な材料の範囲及びイオン交換の実施に関する全詳細は、米国特許出願第１２／３６３，３１０号及び第１２／３６３，３２９号に記載されている。イオン交換の様式は、化学的に塩基性の条件、即ち、高ｐＨ、即ち高ＯＨ-／低ヒドロニウム（Ｈ3Ｏ+）又はプロトン（Ｈ+）含有率の条件下での固溶体への活性金属／カチオンの導入を本質的に含む。前記方法において、酸性の金属溶液の溶液は、例えばｐＨ８．０〜９．５の高いｐＨを有するアンモニア性塩基（水酸化アンモニウムを基礎とした溶液）の添加によって化学的に塩基性の形に変換されうる。前述の研究において示されるように、得られた材料は、酸性金属、例えば金属硝酸塩の従来の含浸により実現されるいかなる促進とも対照的に高活性及び水熱耐久性を示すが、ここで結果として生じる非活性化を伴う新しい材料におけるバルク酸化物相の形成及びかかる酸化物相の急激な焼結が基準である。金属イオンによるＣｅ−ＺｒＯｘ格子内のＣｅ3+不足部位に存在するＨ+種の提案された交換は、酸化物マトリックス内で高分散での特定の一価イオン、例えばＫ+、二価イオン、例えばＣｕ2+、三価イオン、例えばＦｅ3+、より高い原子価のイオンの組み込み及び安定化を可能にする。しかるに組み込まれる卑金属の選択は、特に興味深く、触媒的に重要な反応に活性であることが知られている酸化物に基づく。特定の触媒的に重要性のある金属としては、Ａｇ、Ｃｕ、Ｃｏ、Ｍｎ、Ｆｅ、アルカリ金属、アルカリ土類金属、遷移金属、車両排出の従来の操作窓内の条件下でＮ2のその後の分解及び還元を受け得る安定した硝酸塩を形成することが知られている他の金属又は半金属が挙げられる。「遷移金属」という用語は、元素の周期律表の第３〜１２族における３８の元素を指す。 The doped OS material herein is based on a ZrO 2 / CeO 2 solid solution containing a substantially phase-pure cubic fluorite structure, which is based on specific ion exchange of base metals, ie non-noble metals. Generated. Full details regarding the scope of suitable materials and performing ion exchange are described in US patent application Ser. Nos. 12 / 363,310 and 12 / 363,329. The mode of ion exchange is the active metal to solid solution under chemically basic conditions, ie high pH, ie high OH − / low hydronium (H 3 O + ) or proton (H + ) content. / Essentially including the introduction of cations. In the above method, the solution of the acidic metal solution is converted into a chemically basic form by adding an ammoniacal base (a solution based on ammonium hydroxide) having a high pH, for example, pH 8.0-9.5. Can be done. As shown in the previous study, the resulting material exhibits high activity and hydrothermal durability in contrast to any enhancement achieved by conventional impregnation of acidic metals, such as metal nitrates, but here as a result The basis is the formation of the bulk oxide phase in the new material with the resulting deactivation and the rapid sintering of such oxide phase. The proposed exchange of H + species present at Ce 3+ deficient sites in the Ce-ZrOx lattice by metal ions is due to the specific monovalent ions, eg K + , divalent ions, highly dispersed in the oxide matrix, For example, Cu 2+ , trivalent ions such as Fe 3+ , allowing the incorporation and stabilization of higher valence ions. The selection of the base metals that are incorporated, however, is based on oxides that are particularly interesting and known to be active in catalytically important reactions. Certain catalytically important metals include Ag, Cu, Co, Mn, Fe, alkali metals, alkaline earth metals, transition metals, N 2 after the conditions in conventional operating windows of vehicle emissions. Other metals or metalloids known to form stable nitrates that can undergo decomposition and reduction of The term “transition metal” refers to the 38 elements in Groups 3-12 of the Periodic Table of Elements.
本発明の一実施態様によれば、前記触媒は、ＣＤＰＦ又はディーゼルＮＯｘ微粒子トラップの標準構成に適合しないので、交互チャネルを有する多孔質基材を含まない。むしろ、触媒の好ましい構成は、活性触媒ウォシュコートが配置される、単位面積につき高ユニットセル数の従来の「フロースルー型」モノリスとしてのものである。高内部表面積及び乱流堆積メカニズムとの活性ウォシュコートの組み合わせは、ディーゼル／圧縮点火車両の従来の作動温度及びフローの下での保持及び連続微粒子酸化を容易にするのに十分である。本発明の実施態様は、従って以下である：
本発明は、内燃エンジンのオフガス中の粒子状物質の直接触媒酸化用触媒系に関し、前記系は、前記粒子状物質の直接低温酸化のための活性酸化触媒配合物が被覆された標準的フロースルー型モノリス装置を含み、前記活性触媒が、その中に配置される活性レドックス酸化物を含有する。前記触媒系は、前記モノリスが、１平方インチにつき９００超のセルを有するフロースルー型モノリスである。前記触媒系は、前記モノリスが、１平方インチにつき６００超のセルを有するフロースルー型モノリスである。前記触媒系は、前記モノリスが、１平方インチにつき４００超のセルを有するフロースルー型モノリスである。前記モノリスが、排気流において乱流フローを導入することが可能な金属モノリスである前記触媒系。前記モノリスが、高度に蛇行する性質の流路を示す金属発泡体又はセラミック発泡体である前記触媒系。前記触媒系が耐火性酸化物である前記触媒系。前記触媒系がセリウムを含有する前記触媒系。前記酸化物が、セリウム及びジルコニウム酸化物（Ｃｅ−Ｚｒ酸化物）の固溶体の形態のセリウム酸化物である前記触媒系。前記酸化物が、酸素イオン伝導特性を有する（従来のＸＲＤ法により測定される通りの）実質的に相純粋な立方晶のフルオライトの固溶体であり、且つ、
ａ．約９５％以下のジルコニウム
ｂ．約９５％以下のセリウム
ｃ．希土類、イットリウム、及びそれらの混合物から成る群から選択される約２０％以下の安定剤
を含むＣｅ−Ｚｒ酸化物の固溶体の形態のセリウム酸化物である前記触媒系。前記触媒系が、遷移金属、アルカリ金属、アルカリ土類金属及びＩＩＩｂ族金属から成る群から選択される１種以上の卑金属ドーパント種の導入により更に改質される実質的に相純粋な立方晶のフルオライトの固溶体である前記触媒系。前記レドックス酸化物が、高ｐｈ／低ヒドロニウムイオン（Ｈ 3 Ｏ + ）／低プロトン（Ｈ + ）含有率の条件下で、溶解されたカチオンの前駆体溶液をレドックス活性材料に接触させることにより生成される立方晶のフルオライトの固溶体を含有する、卑金属をドープしたセリウムである前記触媒系。前記卑金属が、金属カチオンの水酸化アンモニウム／アンモニア錯体によりレドックス活性酸化物に導入される前記触媒系。前記卑金属が、金属カチオンの有機アミン錯体によりレドックス酸化物に導入される前記触媒系。前記卑金属が、金属カチオンの水酸化化合物によりレドックス酸化物に導入される前記触媒系。前記導入される金属種の濃度が、約０．０１質量％〜約１０質量％である前記触媒系。前記導入される金属種の濃度が、最も好ましくは０．１質量％〜約２．５質量％である前記触媒系。前記卑金属をドープした固溶体が、従来のＸＲＤ法による相解析が実質的に相純粋な立方晶のフルオライト相（９５％超）を保持するように高レベルの分散度で金属を含有し、バルク金属酸化物ドーパント相が５％未満で記録され、線幅の広がり／シェラーの式の方法により測定されるドーパント金属酸化物の粒径が約３０Ａ〜約１００Ａである前記触媒系。前記卑金属をドープした前記固溶体が、ＸＲＤによる相解析により、促進された材料が１１００℃での水熱酸化エージングの後で少なくとも９５％の立方晶のフルオライト相を維持することが明らかにされるように高レベルの分散度で金属を含有する前記触媒系。前記卑金属をドープした前記固溶体が、ＸＲＤによる相解析により、促進された材料が１１００℃での水熱酸化エージングの後で少なくとも９９％の立方晶のフルオライト相を維持することが明らかにされるように高レベルの分散度で金属を含有する前記触媒系。前記触媒系とハウジングとを含む、すすの直接触媒酸化用装置であって、連続的なすす酸化が約１００〜約６５０℃の温度で起きる前記装置。前記触媒系が白金族金属を含まない、前記すすの直接触媒酸化用触媒系。白金族金属を更に含む、前記すすの直接触媒酸化用触媒系。前記白金族金属が、白金、パラジウム、ロジウム及びそれらの混合物から成る群から選択される、前記すすの直接触媒酸化用触媒系。更なる担体又は結合剤としてＡｌ 2 Ｏ 3 、改質Ａｌ 2 Ｏ 3 、ＳｉＯ 2 、ＺｒＯ 2 又はそれらの組み合わせ或いは他の適切な耐火性酸化物を更に含有する単層のウォシュコートとして前記モノリス上に配置される触媒活性なウォシュコートを更に含む、前記すすの直接触媒酸化用触媒系。担体又は結合剤として実質的にＡｌ 2 Ｏ 3 、改質Ａｌ 2 Ｏ 3 、ＳｉＯ 2 、ＺｒＯ 2 、それらの組み合わせ或いは他の適切な耐火性酸化物を含有する第１層と、卑金属をドープした混合酸化物を含む活性酸化触媒配合物を含む第２層とを有する２つ以上の層で前記モノリス上に配置される触媒活性なウォシュコートを更に含む、前記すすの直接触媒酸化用触媒系。前記触媒系上に排出ガスを通過させる工程を含む排出ガスの処理方法。金属カチオンの水酸化アンモニウム／アンモニア錯体の化学的塩基状態下で固溶体中への活性金属／カチオンの導入によって、又は金属カチオンの有機アミン錯体によって、又は金属カチオンの水酸化化合物によって、実質的に純粋な立方晶のフルオライト構造を含むＣｅＺｅＯｘ固溶体に基づくレドックス活性材料中に卑金属を導入する工程
を含む、請求項１から２０までのいずれか１項に記載のすすの直接触媒酸化のための触媒系を製造する方法。前記方法によって得られる酸化触媒。
According to one embodiment of the present invention, the catalyst does not include a porous substrate with alternating channels because it does not meet the standard configuration of CDPF or diesel NOx particulate traps. Rather, the preferred configuration of the catalyst is as a conventional “flow-through” monolith with a high unit cell count per unit area on which the active catalyst washcoat is placed. The combination of an active washcoat with a high internal surface area and turbulent deposition mechanism is sufficient to facilitate retention under a conventional operating temperature and flow and continuous particulate oxidation of a diesel / compression ignition vehicle. Embodiments of the present invention are therefore:
The present invention relates to a catalyst system for direct catalytic oxidation of particulate matter in off-gas of an internal combustion engine, the system comprising a standard flow-through coated with an active oxidation catalyst formulation for direct low temperature oxidation of the particulate matter. Wherein the active catalyst contains an active redox oxide disposed therein. The catalyst system is a flow-through monolith where the monolith has more than 900 cells per square inch. The catalyst system is a flow-through monolith in which the monolith has more than 600 cells per square inch. The catalyst system is a flow-through monolith in which the monolith has more than 400 cells per square inch. The catalyst system, wherein the monolith is a metal monolith capable of introducing a turbulent flow in the exhaust stream. The catalyst system, wherein the monolith is a metal foam or ceramic foam showing a highly serpentine channel. The catalyst system, wherein the catalyst system is a refractory oxide. The catalyst system wherein the catalyst system contains cerium. The catalyst system, wherein the oxide is cerium oxide in the form of a solid solution of cerium and zirconium oxide (Ce-Zr oxide). The oxide is a solid solution of substantially phase pure cubic fluorite (as measured by a conventional XRD method) having oxygen ion conduction properties; and
a. Less than about 95% zirconium
b. Less than 95% cerium
c. About 20% or less of the stabilizer selected from the group consisting of rare earths, yttrium, and mixtures thereof.
Said catalyst system is a cerium oxide in the form of a solid solution of Ce-Zr oxide containing. The catalyst system is a substantially phase-pure cubic crystal that is further modified by the introduction of one or more base metal dopant species selected from the group consisting of transition metals, alkali metals, alkaline earth metals, and Group IIIb metals. The catalyst system is a solid solution of fluorite. The redox oxide is obtained by contacting a dissolved cation precursor solution with a redox active material under conditions of high ph / low hydronium ion (H 3 O + ) / low proton (H + ) content. The catalyst system comprising cerium doped with a base metal, containing a solid solution of cubic fluorite produced. The catalyst system wherein the base metal is introduced into the redox active oxide by an ammonium hydroxide / ammonia complex of a metal cation. The catalyst system wherein the base metal is introduced into the redox oxide by an organic amine complex of a metal cation. The catalyst system wherein the base metal is introduced into the redox oxide by a hydroxide compound of a metal cation. The catalyst system wherein the concentration of the metal species introduced is about 0.01% to about 10% by weight. The catalyst system wherein the concentration of the introduced metal species is most preferably from 0.1% to about 2.5% by weight. The base metal-doped solid solution contains metal at a high level of dispersion such that the conventional XRD phase analysis retains a substantially phase-pure cubic fluorite phase (> 95%), bulk The catalyst system wherein the metal oxide dopant phase is recorded at less than 5% and the particle size of the dopant metal oxide is about 30A to about 100A as measured by the line broadening / Scherrer formula method. The base solution doped solid solution reveals by XRD phase analysis that the promoted material maintains at least 95% cubic fluorite phase after hydrothermal oxidation aging at 1100 ° C. Such a catalyst system containing metal at a high level of dispersion. The solid solution doped with the base metal reveals that the promoted material maintains at least 99% cubic fluorite phase after hydrothermal aging at 1100 ° C. by phase analysis by XRD Such a catalyst system containing metal at a high level of dispersion. An apparatus for direct catalytic oxidation of soot comprising the catalyst system and a housing, wherein the continuous soot oxidation occurs at a temperature of about 100 to about 650 ° C. The catalyst system for direct catalytic oxidation of soot, wherein the catalyst system does not contain a platinum group metal. The catalyst system for direct catalytic oxidation of soot, further comprising a platinum group metal. The catalyst system for direct catalytic oxidation of soot, wherein the platinum group metal is selected from the group consisting of platinum, palladium, rhodium and mixtures thereof. On the monolith as a single-layer washcoat further containing Al 2 O 3 , modified Al 2 O 3 , SiO 2 , ZrO 2 or combinations thereof or other suitable refractory oxides as further support or binder The catalytic system for direct catalytic oxidation of soot, further comprising a catalytically active washcoat disposed in A first layer containing essentially Al 2 O 3 , modified Al 2 O 3 , SiO 2 , ZrO 2 , combinations thereof or other suitable refractory oxides as a support or binder , and base metal doped The catalytic system for direct catalytic oxidation of soot, further comprising a catalytically active washcoat disposed on the monolith in two or more layers having a second layer comprising an active oxidation catalyst formulation comprising a mixed oxide. An exhaust gas treatment method comprising a step of passing exhaust gas over the catalyst system. Substantially pure by introduction of an active metal / cation into a solid solution under the chemical base state of an ammonium hydroxide / ammonia complex of a metal cation, or by an organic amine complex of a metal cation, or by a hydroxide compound of a metal cation. Of introducing a base metal into a redox active material based on a CeZeOx solid solution containing a unique cubic fluorite structure
21. A process for producing a catalyst system for direct catalytic oxidation of soot according to any one of claims 1 to 20. An oxidation catalyst obtained by the method.
ｂ）すす蓄積の間のガス環境：図２、４、５及び６に示される通りの充填サイクル中の両方において触媒性能に対する反応性ガス化学作用の明らかな影響があり、更に、昇温反応バーンアウトプロトコルに対するＴＰＯの対照から明らかなように、ガス雰囲気の性質が再生に影響することを認めることができる（図５、８、１０、１３、１４、１６及び１８ａ／ｂ）。この影響は、熱伝達及び触媒活性の組み合わせに起因する。ある熱伝達成分は、反応性ガス混合気内の著しいレベルの燃料成分、主にＣＯ及びＨＣの燃焼から生じる活性触媒の外部加熱により生じる。このエネルギーは、ウォシュコート内で保持され、それにより、予想床温より熱くなると認められ、従って、触媒すす酸化に対する活性化エネルギー障壁の克服が促進される。第２の複合熱伝達及び触媒活性成分は、ＣＯ酸化過程への関与から生じるレドックス酸化物の活性化から生じる。ドープされたセリウム酸化物は、ＰＧＭの非存在下でも効果的な酸化触媒であり、低温でのＣＯ酸化を容易にすることができることが示されている（ＰＣＴ／ＵＳ２００９／０３８３９８）。それを行う際、触媒Ｏイオン輸送機能が活性化され、ＣＯ酸化の活性部位でエネルギーが放出される。枯渇した酸素の後続の再酸化は、すす酸化を開始するためにＯＳを更に装填する意味でＯＳの構造物全体に亘って分配される更なる発熱をもたらす。このメカニズムは、より完全な説明が明らかにされ得るＵＳ２００５／０２８２６９８Ａ１の基礎の部分を形成する。 b) Gas environment during soot accumulation: there is a clear influence of reactive gas chemistry on the catalyst performance both during the filling cycle as shown in FIGS. It can be seen that the nature of the gas atmosphere affects the regeneration, as is evident from the TPO control over the out protocol (Figures 5, 8, 10, 13, 14, 16 and 18a / b). This effect is due to a combination of heat transfer and catalytic activity. Some heat transfer components are caused by external heating of the active catalyst resulting from combustion of significant levels of fuel components in the reactive gas mixture, primarily CO and HC. This energy is retained within the washcoat, and is thereby recognized to be hotter than the expected bed temperature, thus facilitating overcoming the activation energy barrier to catalytic soot oxidation. The second combined heat transfer and catalytically active component results from redox oxide activation resulting from participation in the CO oxidation process. It has been shown that doped cerium oxide is an effective oxidation catalyst even in the absence of PGM and can facilitate CO oxidation at low temperatures ( PCT / US2009 / 038398 ). In doing so, the catalytic O ion transport function is activated and energy is released at the active site of CO oxidation. Subsequent reoxidation of the depleted oxygen results in further exotherm being distributed throughout the OS structure in the sense of further loading the OS to initiate soot oxidation. This mechanism forms the basis of US 2005/0282698 A1 where a more complete description can be revealed.
Claims (29)
ａ．約９５％以下のジルコニウム
ｂ．約９５％以下のセリウム
ｃ．希土類、イットリウム、及びそれらの混合物から成る群から選択される約２０％以下の安定剤
を含むＣｅ−Ｚｒ酸化物の固溶体の形態のセリウム酸化物である、請求項１から９までのいずれか１項に記載の触媒系。 The oxide is a solid solution of substantially phase-pure cubic fluorite (as measured by a conventional XRD method) with oxygen ion conduction properties; and
a. Up to about 95% zirconium b. About 95% or less of cerium c. Rare earth, yttrium, and cerium oxide in the form of a solid solution of Ce-Zr oxide containing about 20 percent of a stabilizer selected from the group consisting of mixtures thereof, any of claims 1 to 9 1 The catalyst system according to item.
金属カチオンの水酸化アンモニウム／アンモニア錯体の化学的塩基状態下で固溶体中への活性金属／カチオンの導入によって、又は金属カチオンの有機アミン錯体によって、又は金属カチオンの水酸化化合物によって、実質的に純粋な立方晶のフルオライト構造を含むＣｅＺｅＯｘ固溶体に基づくレドックス活性材料中に卑金属を導入する工程Substantially pure by introduction of an active metal / cation into a solid solution under the chemical base state of an ammonium hydroxide / ammonia complex of the metal cation, or by an organic amine complex of the metal cation, or by a hydroxide compound of the metal cation. Of introducing a base metal into a redox active material based on a CeZeOx solid solution containing a unique cubic fluorite structure
を含む、請求項１から２０までのいずれか１項に記載のすすの直接触媒酸化のための触媒系を製造する方法。21. A process for producing a catalyst system for direct catalytic oxidation of soot according to any one of claims 1 to 20.
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| US3987908P | 2008-03-27 | 2008-03-27 | |
| US61/039,879 | 2008-03-27 | ||
| US12/240,170 | 2008-09-29 | ||
| US12/240,170 US20090246109A1 (en) | 2008-03-27 | 2008-09-29 | Solid solutions and methods of making the same |
| US12/363,310 US9403151B2 (en) | 2009-01-30 | 2009-01-30 | Basic exchange for enhanced redox OS materials for emission control applications |
| US12/363,329 | 2009-01-30 | ||
| US12/363,310 | 2009-01-30 | ||
| US12/363,329 US20100196217A1 (en) | 2009-01-30 | 2009-01-30 | Application of basic exchange os materials for lower temperature catalytic oxidation of particulates |
| PCT/US2009/038403 WO2010002486A2 (en) | 2008-03-27 | 2009-03-26 | Continuous diesel soot control with minimal back pressure penality using conventional flow substrates and active direct soot oxidation catalyst disposed thereon |
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| JP2011501155A Withdrawn JP2011526198A (en) | 2008-03-27 | 2009-03-27 | Application of base exchange OS materials for low temperature catalytic oxidation of fine particles |
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2009
- 2009-03-26 KR KR1020107023769A patent/KR20110008190A/en active Search and Examination
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