JP5078062B2 - Exhaust gas purification catalyst - Google Patents
Exhaust gas purification catalyst Download PDFInfo
- Publication number
- JP5078062B2 JP5078062B2 JP2006291691A JP2006291691A JP5078062B2 JP 5078062 B2 JP5078062 B2 JP 5078062B2 JP 2006291691 A JP2006291691 A JP 2006291691A JP 2006291691 A JP2006291691 A JP 2006291691A JP 5078062 B2 JP5078062 B2 JP 5078062B2
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- gas purifying
- purifying catalyst
- noble metal
- gas purification
- 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.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 63
- 238000000746 purification Methods 0.000 title description 33
- 229910000510 noble metal Inorganic materials 0.000 claims description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000007769 metal material Substances 0.000 claims description 5
- 239000006104 solid solution Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 description 74
- 239000010410 layer Substances 0.000 description 17
- 239000002002 slurry Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 10
- 239000011247 coating layer Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910016066 BaSi Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910004709 CaSi Inorganic materials 0.000 description 1
- 229910004122 SrSi Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
本発明は、排ガス浄化用触媒に関し、より詳しくは、低温活性が高く、耐熱性に優れ、安定した排ガス浄化性能を得ることができる触媒、例えば、自動車等の内燃機関から排出される排ガスに含まれる有害成分を浄化する触媒に関する。 The present invention relates to an exhaust gas purification catalyst. More specifically, the present invention includes a catalyst having high low-temperature activity, excellent heat resistance, and stable exhaust gas purification performance, such as exhaust gas discharged from an internal combustion engine such as an automobile. The present invention relates to a catalyst that purifies harmful components.
自動車等の内燃機関から排出される排ガス中には、炭化水素（ＨＣ）、一酸化炭素（ＣＯ）、窒素酸化物（ＮＯｘ）等の有害成分が含まれている。それで、従来から、これら有害成分を浄化して無害化する三元触媒が用いられている。 The exhaust gas discharged from an internal combustion engine such as an automobile contains harmful components such as hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx). Therefore, conventionally, a three-way catalyst for purifying and detoxifying these harmful components has been used.
このような三元触媒として、複合酸化物及び貴金属からなる種々の排ガス浄化用触媒が提案されており、例えば、アパタイト型構造を有する複合酸化物を含む排ガス浄化用触媒が提案されている（例えば、特許文献１及び２参照）。 As such a three-way catalyst, various exhaust gas purification catalysts composed of a composite oxide and a noble metal have been proposed. For example, an exhaust gas purification catalyst containing a composite oxide having an apatite type structure has been proposed (for example, Patent Documents 1 and 2).
しかしながら、従来の三元触媒では、一般的に、比較的高温にならないと排ガス中の有害成分の浄化が開始されないため、低温側では有害成分を十分に浄化できないという問題がある。例えば、自動車等のエンジン始動直後は、比較的低温状態であるので、排ガス中の有害成分を十分に浄化仕切れないという問題がある。 However, the conventional three-way catalyst generally has a problem that the harmful components cannot be sufficiently purified on the low temperature side because the purification of harmful components in the exhaust gas is not started unless the temperature is relatively high. For example, immediately after the engine of a car or the like is started, there is a problem that the harmful components in the exhaust gas cannot be sufficiently purified because the temperature is relatively low.
また、従来の三元触媒においては、一般的に、比較的高温域での使用で劣化して排ガス浄化性能が低下するという場合もあり、低温域から高温域に亘って安定した排ガス浄化性能が得られないという問題もある。 In addition, in the conventional three-way catalyst, in general, there is a case where the exhaust gas purification performance deteriorates due to use in a relatively high temperature range, and a stable exhaust gas purification performance from a low temperature range to a high temperature range may be achieved. There is also a problem that it cannot be obtained.
本発明は上述した事情に鑑み、低温活性が高く、且つ耐熱性に優れ、安定した排ガス浄化性能を得ることができる排ガス浄化用触媒を提供することを目的とする。 In view of the circumstances described above, an object of the present invention is to provide an exhaust gas purification catalyst that has high low-temperature activity, excellent heat resistance, and can obtain stable exhaust gas purification performance.
本発明者等は上記目的を達成するために鋭意検討した結果、一般式（Ｌａa-xＭx）（Ｓｉ6-yＮy）Ｏ27-zで示される複合酸化物と貴金属成分とを用いることにより上記目的が達成されることを見いだし、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors use a composite oxide represented by the general formula (La ax M x ) (Si 6-y N y ) O 27-z and a noble metal component. As a result, the present inventors have found that the above object can be achieved and completed the present invention.
即ち、本発明の排ガス浄化用触媒は、一般式（Ｌａa-xＭx）（Ｓｉ6-yＮy）Ｏ27-z（式中、ＭはＢａの陽イオンを表し、ＮはＦｅの陽イオンを表し、８≦ａ≦１０であり、０．０１≦ｘ≦５であり、０≦ｙ≦３であり、０≦ｚ≦２である）で示される複合酸化物と、前記複合酸化物に固溶体化しているか又は担持されている貴金属成分とからなることを特徴とする。 That is, the exhaust gas purifying catalyst of the present invention has a general formula (La ax M x ) (Si 6-y N y ) O 27-z (wherein M represents a cation of Ba and N represents a cation of Fe ). 8 ≦ a ≦ 10, 0.01 ≦ x ≦ 5, 0 ≦ y ≦ 3, and 0 ≦ z ≦ 2), and the composite oxide It consists of a noble metal component which is in solid solution or is supported.
また、他の形態の本発明の排ガス浄化用触媒は、セラミックス又は金属材料からなる担体と、前記担体上に担持されている上記の排ガス浄化用触媒の層とからなることを特徴とする。 Another embodiment of the exhaust gas purifying catalyst of the present invention is characterized by comprising a carrier made of ceramics or a metal material, and a layer of the above exhaust gas purifying catalyst supported on the carrier.
また、本発明の排ガス浄化用触媒においては、前記貴金属成分が白金又はパラジウムであることが好ましい。 In the exhaust gas purifying catalyst of the present invention, the noble metal component is preferably platinum or palladium.
本発明の排ガス浄化用触媒は、低温活性が高く、且つ耐熱性に優れているので、安定した排ガス浄化性能を得ることができるという効果を奏する。 Since the exhaust gas purifying catalyst of the present invention has high low-temperature activity and excellent heat resistance, there is an effect that stable exhaust gas purifying performance can be obtained.
以下に、本発明の実施形態を詳細に説明する。
本発明の排ガス浄化用触媒は、一般式（Ｌａa-xＭx）（Ｓｉ6-yＮy）Ｏ27-z（式中、Ｍは１〜３価の陽イオンを表し、Ｎは３〜７価の陽イオンを表し、８≦ａ≦１０であり、０≦ｘ≦５であり、０≦ｙ≦３であり、０≦ｚ≦２である）で示されるアパタイト構造の複合酸化物と、複合酸化物に固溶体化しているか又は担持されている貴金属成分とからなるものである。このような本発明の排ガス浄化用触媒は、低温活性が高く、高温域において優れた耐熱性を有するため、安定した排ガス浄化性能を発揮するものである。
Hereinafter, embodiments of the present invention will be described in detail.
The exhaust gas purifying catalyst of the present invention has a general formula (La ax M x ) (Si 6-y N y ) O 27-z (wherein M represents a 1 to 3 valent cation, and N represents 3 to 7). A composite oxide having an apatite structure represented by a cation having a valence of 8 ≦ a ≦ 10, 0 ≦ x ≦ 5, 0 ≦ y ≦ 3, and 0 ≦ z ≦ 2. It consists of a noble metal component that is solid solution or supported on the composite oxide. Such an exhaust gas purifying catalyst of the present invention has a high low temperature activity and excellent heat resistance in a high temperature range, and therefore exhibits a stable exhaust gas purifying performance.
一般式（Ｌａa-xＭx）（Ｓｉ6-yＮy）Ｏ27-zで示されるアパタイト構造の複合酸化物が化学量論組成を持つ場合にはａ＝１０であり、非化学量論組成を持つ場合にはａ＜１０である。非化学量論組成を持つ上記一般式の複合酸化物については現実的に容易に入手できる複合酸化物のａの範囲は８≦ａ＜１０である。従って、本発明においては８≦ａ≦１０とする。 When the composite oxide having an apatite structure represented by the general formula (La ax M x ) (Si 6-y N y ) O 27-z has a stoichiometric composition, a = 10, and the non-stoichiometric composition A <10 in the case of Regarding the complex oxide of the above general formula having a non-stoichiometric composition, the range of a of the complex oxide that can be easily obtained in reality is 8 ≦ a <10. Therefore, in the present invention, 8 ≦ a ≦ 10.
本発明の排ガス浄化用触媒は、上記一般式（Ｌａa-xＭx）（Ｓｉ6-yＮy）Ｏ27-zにおいて、ＡサイトであるＬａサイト及びＢサイトであるＳｉサイトの両方について他の元素で置換されていない、即ち、ｘ＝０、ｙ＝０及びｚ＝１で特定の元素の陽イオン（Ｍ又はＮ）で置換されていない一般式ＬａaＳｉ6Ｏ26（現実的には、ａ＝９．３３の複合酸化物が容易に得られる）で示される複合酸化物に貴金属成分を固溶体化したものか又は担持させたものでもよい。 The exhaust gas purifying catalyst of the present invention is different from the above general formula (La ax M x ) (Si 6-y N y ) O 27-z for both the La site as the A site and the Si site as the B site. A general formula La a Si 6 O 26 (practically not substituted with a cation (M or N) of a particular element at x = 0, y = 0 and z = 1 , A composite oxide of a = 9.33 can be easily obtained), and a solid oxide of a noble metal component or a support on which it is supported.
また、本発明の排ガス浄化用触媒は、上記一般式（Ｌａa-xＭx）（Ｓｉ6-yＮy）Ｏ27-zにおいて、Ｌａサイトの一部をＢａの陽イオンで置換するか、あるいはＳｉサイトの一部をＦｅの陽イオンで置換するか、或いはその両サイトの各々の一部を上記のように置換して得られた複合酸化物に貴金属成分を固溶体化したものか又は担持させたものでもよい。この場合には、０．０１≦ｘ≦５、好ましくは０．１≦ｘ≦４、より好ましくは０．５≦ｘ≦３．５であり且つ（又は）０．０１≦ｙ≦３、好ましくは０．１≦ｙ≦２．５、より好ましくは０．５≦ｙ≦２であり、０≦ｚ≦２である複合酸化物を用いる。Further, the exhaust gas purifying catalyst of the present invention is the above general formula (La ax M x ) (Si 6-y N y ) O 27-z, wherein a part of the La site is substituted with a Ba cation, or Either a part of the Si site is substituted with a cation of Fe , or a part of each of the two sites is substituted as described above, or a noble metal component is solidified or supported on the composite oxide obtained. May be good. In this case, 0.01 ≦ x ≦ 5, preferably 0.1 ≦ x ≦ 4, more preferably 0.5 ≦ x ≦ 3.5 and / or 0.01 ≦ y ≦ 3, preferably Is a composite oxide in which 0.1 ≦ y ≦ 2.5, more preferably 0.5 ≦ y ≦ 2, and 0 ≦ z ≦ 2.
本発明の排ガス浄化用触媒は、自動車等のエンジン始動直後の比較的低温状態においても触媒活性が充分に高く、低温域において優れた排ガス浄化性能が得られると共に、高温域において優れた耐熱性を有するため、低温域から高温域に亘って安定した排ガス浄化性能が得られるものである。従って、本発明の排ガス浄化用触媒は、例えば、自動車等の内燃機関において排出される排ガスの浄化に好適に用いられる。 The exhaust gas purifying catalyst of the present invention has sufficiently high catalytic activity even in a relatively low temperature state immediately after starting an engine such as an automobile, and has excellent exhaust gas purifying performance in a low temperature region and excellent heat resistance in a high temperature region. Therefore, stable exhaust gas purification performance can be obtained from the low temperature range to the high temperature range. Therefore, the exhaust gas purifying catalyst of the present invention is suitably used for purifying exhaust gas discharged from an internal combustion engine such as an automobile.
このような本発明の排ガス浄化用触媒の貴金属成分としては、例えば、ロジウム、パラジウム又は白金であることが好ましく、特に白金又はパラジウムであることがより好ましい。 As such a noble metal component of the exhaust gas purifying catalyst of the present invention, for example, rhodium, palladium or platinum is preferable, and platinum or palladium is more preferable.
本発明の排ガス浄化用触媒中の貴金属成分は、排ガス浄化用触媒を構成する複合酸化物中に固溶体化して存在していても担持されて存在していてもよい。複合酸化物中への貴金属成分の導入は、例えば、粉末又はスラリー状態の複合酸化物を貴金属含有溶液（塩基性又は酸性の貴金属塩の溶液）に浸漬又は混合して貴金属成分を複合酸化物に吸着させ、得られたものを焼成することで行ってもよく、上述の複合酸化物の製造過程において複合酸化物のスラリーに貴金属成分を混入して得られたものを焼成することで行ってもよく、あるいは貴金属成分を酸化物等に担持させて得られる貴金属担持体と上述の複合酸化物とを混合して得られたものを焼成等することで行ってもよい。 The noble metal component in the exhaust gas purifying catalyst of the present invention may be present in the form of a solid solution or supported on the composite oxide constituting the exhaust gas purifying catalyst. The noble metal component is introduced into the composite oxide by, for example, immersing or mixing the composite oxide in a powder or slurry state in a noble metal-containing solution (basic or acidic noble metal salt solution) to convert the noble metal component into the composite oxide. It may be performed by adsorbing and firing the obtained product, or by firing a product obtained by mixing a noble metal component in the composite oxide slurry in the above-described composite oxide manufacturing process. Alternatively, it may be carried out by firing or the like obtained by mixing a noble metal carrier obtained by carrying a noble metal component on an oxide or the like and the above-mentioned composite oxide.
また、本発明の排ガス浄化用触媒は、上述したような複合酸化物と貴金属成分とからなるものであってもよいが、一般的には、セラミックス又は金属材料からなる担体と、担体上に担持されている排ガス浄化用触媒の層とからなるものである。 Further, the exhaust gas purifying catalyst of the present invention may be composed of the composite oxide and the noble metal component as described above, but in general, a carrier made of ceramics or a metal material and a carrier supported on the carrier. And an exhaust gas purifying catalyst layer.
なお、上記のような排気ガス浄化用触媒においては、セラミックス又は金属材料からなる担体の形状は、特に限定されるものではないが、一般的にはハニカム、板、ペレット等の形状であり、好ましくはハニカム形状である。また、このような担体の材質としては、例えば、アルミナ（Ａｌ2Ｏ3）、ムライト（３Ａｌ2Ｏ3−２ＳｉＯ2）、コージェライト（２ＭｇＯ−２Ａｌ2Ｏ3−５ＳｉＯ2）等のセラミックスや、ステンレス等の金属材料が挙げられる。 In the exhaust gas purification catalyst as described above, the shape of the carrier made of ceramics or a metal material is not particularly limited, but is generally in the shape of a honeycomb, a plate, a pellet, etc. Is a honeycomb shape. The material of such carriers, for example, alumina (Al 2 O 3), mullite (3Al 2 O 3 -2SiO 2) , cordierite (2MgO-2Al 2 O 3 -5SiO 2) ceramics or the like, Examples thereof include metal materials such as stainless steel.
このような担体上に排ガス浄化用触媒の層を形成したものである排ガス浄化用触媒は、例えば、貴金属成分が固溶体化しているか又は担持されている複合酸化物のスラリーを担体に塗布して排ガス浄化用触媒の前駆体層を形成し、これを焼成して製造してもよく、複合酸化物のスラリーを担体に塗布して複合酸化物の層を形成した後、これを貴金属含有溶液に浸漬して複合酸化物の層に貴金属成分を吸着させてこれを焼成して製造してもよく、あるいは貴金属成分を酸化物に担持させた貴金属担持体と上述の複合酸化物とを混合して得られるスラリーを担体に塗布して排ガス浄化用触媒の前駆体層を形成し、これを焼成して製造してもよい。 An exhaust gas purifying catalyst in which a layer of an exhaust gas purifying catalyst is formed on such a carrier is, for example, an exhaust gas obtained by applying a composite oxide slurry in which a noble metal component is solid solution or supported on a carrier. It may be produced by forming a precursor layer of a purification catalyst and calcining it. After forming a composite oxide layer by applying a composite oxide slurry to a support, it is immersed in a noble metal-containing solution. The noble metal component may be adsorbed on the composite oxide layer and fired, or may be produced by mixing the noble metal carrier having the noble metal component supported on the oxide and the above-mentioned composite oxide. The resulting slurry may be applied to a carrier to form a precursor layer of an exhaust gas purifying catalyst, and this may be fired for production.
以下に、本発明を下記参考例、実施例及び比較例に基づいて説明する。
参考例１
室温でオルト珪酸テトラエチル（Tetraethyl orthosilicate、ＴＥＯＳ）にエタノールと純水、さらに酢酸を加えて溶解し、これに硝酸ランタンを加えて攪拌を行うことで透明溶液（ゾル）を得た。この溶液を８０℃で６時間攪拌した後、９０℃で１２時間乾燥してキセロゲルを得た。そして、このキセロゲルを６００℃で７時間仮焼した後、８００℃で６時間焼成することによりＬａ9.33Ｓｉ6Ｏ26を得た。次に、このＬａ9.33Ｓｉ6Ｏ26に対して１質量％Ｐｔとなるようにテトラジニトリロジアミン白金を含浸させた後に蒸発乾固させて６００℃で３時間焼成することにより１質量％Ｐｔ／Ｌａ9.33Ｓｉ6Ｏ26からなる参考例１の排ガス浄化用触媒を得た。
Below, this invention is demonstrated based on the following reference example, an Example, and a comparative example.
Reference example 1
Ethanol, pure water and acetic acid were added and dissolved in tetraethyl orthosilicate (TEOS) at room temperature, and lanthanum nitrate was added thereto and stirred to obtain a transparent solution (sol). This solution was stirred at 80 ° C. for 6 hours and then dried at 90 ° C. for 12 hours to obtain a xerogel. The xerogel was calcined at 600 ° C. for 7 hours and then calcined at 800 ° C. for 6 hours to obtain La 9.33 Si 6 O 26 . Next, after impregnating tetradinitrilodiamineplatinum to 1 mass% Pt with respect to this La 9.33 Si 6 O 26 , it was evaporated to dryness and baked at 600 ° C. for 3 hours to obtain 1 mass% Pt / An exhaust gas purifying catalyst of Reference Example 1 consisting of La 9.33 Si 6 O 26 was obtained.
実施例１
室温でＴＥＯＳにエタノールと純水、さらに酢酸を加えて溶解し、これに硝酸ランタンを加えて攪拌を行うことで透明溶液（ゾル）を得た。この溶液に硝酸バリウムを添加して８０℃で６時間攪拌を行った後、９０℃で１２時間乾燥してキセロゲルを得た。そして、このキセロゲルを６００℃で７時間仮焼した後、８００℃で６時間焼成することによりＬａ8.33ＢａＳｉ6Ｏ26を得た。次に、このＬａ8.33ＢａＳｉ6Ｏ26に対して１質量％Ｐｔとなるようにテトラジニトリロジアミン白金を含浸させた後に蒸発乾固させて６００℃で３時間焼成することにより１質量％Ｐｔ／Ｌａ8.33ＢａＳｉ6Ｏ26からなる実施例１の排ガス浄化用触媒を得た。
Example 1
Ethanol, pure water, and acetic acid were added to TEOS at room temperature to dissolve, and lanthanum nitrate was added thereto and stirred to obtain a transparent solution (sol). After adding barium nitrate to this solution and stirring at 80 ° C. for 6 hours, it was dried at 90 ° C. for 12 hours to obtain a xerogel. The xerogel was calcined at 600 ° C. for 7 hours and then calcined at 800 ° C. for 6 hours to obtain La 8.33 BaSi 6 O 26 . Next, after impregnating tetradinitrilodiamineplatinum to 1 mass% Pt with respect to this La 8.33 BaSi 6 O 26 , it was evaporated to dryness and baked at 600 ° C. for 3 hours to obtain 1 mass% Pt / An exhaust gas purifying catalyst of Example 1 made of La 8.33 BaSi 6 O 26 was obtained.
参考例２
硝酸バリウムを炭酸カルシウムに変更した以外は実施例１と同様にして１質量％Ｐｔ／Ｌａ8.33ＣａＳｉ6Ｏ26からなる参考例２の排ガス浄化用触媒を得た。
Reference example 2
Exhaust gas purification catalyst of Reference Example 2 consisting of 1% by mass Pt / La 8.33 CaSi 6 O 26 was obtained in the same manner as in Example 1 except that barium nitrate was changed to calcium carbonate.
参考例３
硝酸バリウムを炭酸ストロンチウムに変更した以外は実施例１と同様にして１質量％Ｐｔ／Ｌａ8.33ＳｒＳｉ6Ｏ26からなる参考例３の排ガス浄化用触媒を得た。
Reference example 3
Exhaust gas purification catalyst of Reference Example 3 consisting of 1% by mass Pt / La 8.33 SrSi 6 O 26 was obtained in the same manner as in Example 1 except that barium nitrate was changed to strontium carbonate.
実施例２
室温でＴＥＯＳにエタノールと純水、さらに酢酸を加えて溶解し、これに硝酸ランタンを加えて攪拌を行うことで透明溶液（ゾル）を得た。この溶液に硝酸バリウムと硝酸鉄９水和物とを添加して８０℃で６時間攪拌を行った後、９０℃で１２時間乾燥してキセロゲルを得た。そして、このキセロゲルを９００℃で１２時間焼成することによりＬａ8.33ＢａＳｉ4.5Ｆｅ1.5Ｏ26を得た。次に、このＬａ8.33ＢａＳｉ4.5Ｆｅ1.5Ｏ26に対して１質量％Ｐｔとなるようにテトラジニトリロジアミン白金を含浸させた後に蒸発乾固させ、６００℃で３時間焼成することにより１質量％Ｐｔ／Ｌａ8.33ＢａＳｉ4.5Ｆｅ1.5Ｏ26からなる実施例２の排ガス浄化用触媒を得た。
Example 2
Ethanol, pure water, and acetic acid were added to TEOS at room temperature to dissolve, and lanthanum nitrate was added thereto and stirred to obtain a transparent solution (sol). Barium nitrate and iron nitrate nonahydrate were added to this solution and stirred at 80 ° C. for 6 hours, followed by drying at 90 ° C. for 12 hours to obtain a xerogel. Then, to obtain a La 8.33 BaSi 4.5 Fe 1.5 O 26 by the xerogel calcined 12 hours at 900 ° C.. Next, tetradinitrilodiamine platinum was impregnated to 1 mass% Pt with respect to La 8.33 BaSi 4.5 Fe 1.5 O 26 , evaporated to dryness, and calcined at 600 ° C. for 3 hours to obtain 1 mass%. An exhaust gas purifying catalyst of Example 2 made of Pt / La 8.33 BaSi 4.5 Fe 1.5 O 26 was obtained.
参考例４
硝酸バリウムを硝酸プラセオジウムに変更した以外は実施例２と同様にして１質量％Ｐｔ／Ｌａ6.83Ｐｒ3Ｓｉ4.5Ｆｅ1.5Ｏ27からなる参考例４の排ガス浄化用触媒を得た。
Reference example 4
Exhaust gas purification catalyst of Reference Example 4 consisting of 1% by mass Pt / La 6.83 Pr 3 Si 4.5 Fe 1.5 O 27 was obtained in the same manner as in Example 2 except that barium nitrate was changed to praseodymium nitrate.
参考例５
Ｌａ9.33Ｓｉ6Ｏ26に対して１質量％Ｐｄとなるように硝酸パラジウムを含浸させた以外は参考例１と同様にして１質量％Ｐｄ／Ｌａ9.33Ｓｉ6Ｏ26からなる参考例５の排ガス浄化用触媒を得た。
Reference Example 5
La 9.33 Si 6 except that impregnated with palladium nitrate as a 1 wt% Pd with respect to O 26 consists of 1 wt% Pd / La 9.33 Si 6 O 26 in the same manner as in Reference Example 1 Reference Example 5 of the exhaust gas A purification catalyst was obtained.
比較例１
活性化アルミナに対して１質量％Ｐｔとなるようにテトラジニトロジアミン白金を含浸させた後に蒸発乾固させ、６００℃で３時間焼成することにより１質量％Ｐｔ／Ａｌ2Ｏ3からなる比較例１の排ガス浄化用触媒を得た。
Comparative Example 1
Comparative example consisting of 1% by mass Pt / Al 2 O 3 by impregnating tetradinitrodiamine platinum so as to be 1% by mass Pt with respect to activated alumina, evaporating to dryness and baking at 600 ° C. for 3 hours. No. 1 exhaust gas-purifying catalyst was obtained.
比較例２
活性化アルミナに対して１質量％Ｐｄとなるように硝酸パラジウムを含浸させた以外は比較例１と同様にして１質量％Ｐｄ／Ａｌ2Ｏ3からなる比較例２の排ガス浄化用触媒を得た。
Comparative Example 2
Exhaust gas purification catalyst of Comparative Example 2 made of 1% by mass Pd / Al 2 O 3 was obtained in the same manner as Comparative Example 1 except that palladium nitrate was impregnated so as to be 1% by mass Pd with respect to activated alumina. It was.
排ガス浄化性能試験
実施例１、２、参考例１〜５及び比較例１、２の各々の排ガス浄化用触媒をそれぞれ２０〜６０メッシュにふるい分けした後、各々の０．１ｇをそれぞれ固定床流通反応装置の反応器に充填し、下記第１表に示す組成のモデルガスを０．５Ｌ／ｍｉｎで流通させ、２００〜６００℃の温度条件下での排ガス浄化性能を評価した。その結果は下記の第２表、第３表及び第４表に示す通りであった。
Exhaust gas purification performance test Each exhaust gas purification catalyst of Examples 1 , 2, Reference Examples 1 to 5 and Comparative Examples 1 and 2 was screened to 20 to 60 mesh, and 0.1 g of each was then fixed bed flow reaction. The reactor of the apparatus was filled, and a model gas having the composition shown in Table 1 below was circulated at 0.5 L / min, and the exhaust gas purification performance under a temperature condition of 200 to 600 ° C. was evaluated. The results were as shown in Tables 2, 3 and 4 below.
第２表及び第３表に示すデータから明らかなように、実施例１、２、参考例１〜４の本発明の排ガス浄化用触媒は、比較例１の排ガス浄化用触媒と比較して、約４００℃以下の低温域側でＣ3Ｈ6及びＮＯの浄化性能が共に優れており、特に、実施例１及び２の排ガス浄化用触媒は３００℃以下の低温域において非常に優れたＣ3Ｈ6及びＮＯの浄化性能が得られている。また、実施例１、２、参考例１〜４の排ガス浄化用触媒は、高温域において耐熱性に優れ、且つ安定したＣ3Ｈ6及びＮＯの浄化性能が得られている。さらに、第４表に示すように、参考例５の本発明の排ガス浄化用触媒は、比較例２の排ガス浄化用触媒と比べて、約３５０℃以下の低温域においてＮＯの浄化性能が優れている。 As is clear from the data shown in Tables 2 and 3 , the exhaust gas purification catalysts of Examples 1 and 2 and Reference Examples 1 to 4 of the present invention are compared with the exhaust gas purification catalyst of Comparative Example 1, The C 3 H 6 and NO purification performances are both excellent at a low temperature range of about 400 ° C. or less. In particular, the exhaust gas purification catalysts of Examples 1 and 2 are very excellent C 3 at a low temperature range of 300 ° C. or less. H 6 and NO purification performance is obtained. Further, the exhaust gas purifying catalysts of Examples 1 and 2 and Reference Examples 1 to 4 are excellent in heat resistance in a high temperature range and have stable C 3 H 6 and NO purifying performance. Furthermore, as shown in Table 4, the exhaust gas purifying catalyst of the present invention of Reference Example 5 is superior in NO purifying performance in a low temperature range of about 350 ° C. or less as compared with the exhaust gas purifying catalyst of Comparative Example 2. Yes.
実施例３：担体に担持させた排ガス浄化用触媒の製造
実施例２と同様に処理して製造したＬａ8.33ＢａＳｉ4.5Ｆｅ1.5Ｏ26４５部（質量部、以下同じ）、活性化アルミナ４５部、アルミナゾル１０部及び水１８５部をボールミルで混合してスラリーＡを得た。また、活性化アルミナ３０部、ＣｅＺｒＯ2６０部、アルミナゾル１０部及び水１００部をボールミルで混合してスラリーＢを得た。
Example 3 Production of Exhaust Gas Purifying Catalyst Supported on Support 45. La 8.33 BaSi 4.5 Fe 1.5 O 26 45 parts (parts by mass, the same shall apply hereinafter) produced by the same treatment as in Example 2 , activated alumina 45 parts, A slurry A was obtained by mixing 10 parts of alumina sol and 185 parts of water with a ball mill. Further, 30 parts of activated alumina, 60 parts of CeZrO 2 , 10 parts of alumina sol and 100 parts of water were mixed with a ball mill to obtain slurry B.
コージェライト製のハニカム基材をスラリーＡ中に浸漬し、引き上げて過剰なスラリーを吹き払った後、９０℃で１０分間乾燥させ、６００℃で３時間焼成してコート層を形成させた。このコート層の量はハニカム基材１Ｌ当り１００ｇであった。得られたコート層付きハニカム基材を所定濃度のジニトロジアミンＰｔ水溶液中に浸漬し、引き上げて余分な液滴を吹き払った後、９０℃で１０分間乾燥させ、６００℃で３時間焼成して、コート層の量１００ｇ（ハニカム基材１Ｌ）当り０．６ｇのＰｔを担持させて第一貴金属担持層を形成させた。 A cordierite honeycomb substrate was dipped in slurry A, pulled up to blow off excess slurry, dried at 90 ° C. for 10 minutes, and fired at 600 ° C. for 3 hours to form a coat layer. The amount of this coating layer was 100 g per liter of honeycomb substrate. The obtained honeycomb substrate with a coating layer was dipped in a dinitrodiamine Pt aqueous solution having a predetermined concentration, pulled up to blow off excess droplets, dried at 90 ° C. for 10 minutes, and fired at 600 ° C. for 3 hours. Then, 0.6 g of Pt was supported per 100 g of the coating layer (1 L of honeycomb substrate) to form a first noble metal supporting layer.
次いで、上記の第一貴金属担持層の形成されたハニカム基材をスラリーＢ中に浸漬し、引き上げて過剰なスラリーを吹き払った後、９０℃で１０分間乾燥させ、６００℃で３時間焼成してコート層を形成させた。このコート層の量はハニカム基材１Ｌ当り１００ｇであった。得られたハニカム基材を所定濃度の硝酸Ｒｈ水溶液中に浸漬し、引き上げて余分な液滴を吹き払った後、９０℃で１０分間乾燥させ、６００℃で３時間焼成して、コート層の量１００ｇ（ハニカム基材１Ｌ）当り０．２ｇのＲｈを担持させて第二貴金属担持層を形成させて、担体上に担持された排ガス浄化用触媒の層からなる本発明の排ガス浄化用触媒を得た。 Next, the honeycomb base material on which the first noble metal support layer is formed is dipped in the slurry B, pulled up to blow off excess slurry, dried at 90 ° C. for 10 minutes, and fired at 600 ° C. for 3 hours. Thus, a coating layer was formed. The amount of this coating layer was 100 g per liter of honeycomb substrate. The obtained honeycomb substrate was immersed in an aqueous solution of Rh nitric acid having a predetermined concentration, pulled up and blown off excess droplets, dried at 90 ° C. for 10 minutes, and fired at 600 ° C. for 3 hours. An exhaust gas purifying catalyst of the present invention comprising an exhaust gas purifying catalyst layer supported on a carrier by supporting 0.2 g of Rh per 100 g (honeycomb substrate 1 L) to form a second noble metal supporting layer. Obtained.
比較例３
活性化アルミナ４５部、ＣｅＺｒＯ2４５部、アルミナゾル１０部及び水１００部をボールミルで混合してスラリーＣを得た。
Comparative Example 3
A slurry C was obtained by mixing 45 parts of activated alumina, 45 parts of CeZrO 2 , 10 parts of alumina sol and 100 parts of water with a ball mill.
コージェライト製のハニカム基材をスラリーＣ中に浸漬し、引き上げて過剰なスラリーを吹き払った後、９０℃で１０分間乾燥させ、６００℃で３時間焼成してコート層を形成させた。このコート層の量はハニカム基材１Ｌ当り１００ｇであった。得られたコート層付きハニカム基材を所定濃度のジニトロジアミンＰｔ水溶液中に浸漬し、引き上げて余分な液滴を吹き払った後、９０℃で１０分間乾燥させ、６００℃で３時間焼成して、コート層の量１００ｇ（ハニカム基材１Ｌ）当り０．６ｇのＰｔを担持させて第一貴金属担持層を形成させた。 A cordierite honeycomb substrate was dipped in slurry C, pulled up to blow off excess slurry, dried at 90 ° C. for 10 minutes, and fired at 600 ° C. for 3 hours to form a coat layer. The amount of this coating layer was 100 g per liter of honeycomb substrate. The obtained honeycomb substrate with a coating layer was dipped in a dinitrodiamine Pt aqueous solution having a predetermined concentration, pulled up to blow off excess droplets, dried at 90 ° C. for 10 minutes, and fired at 600 ° C. for 3 hours. Then, 0.6 g of Pt was supported per 100 g of the coating layer (1 L of honeycomb substrate) to form a first noble metal supporting layer.
次いで、上記の第一貴金属担持層の形成されたハニカム基材を、活性化アルミナ３０部、ＣｅＺｒＯ2６０部、アルミナゾル１０部及び水１００部をボールミルで混合して得たスラリーＢ中に浸漬し、引き上げて過剰なスラリーを吹き払った後、９０℃で１０分間乾燥させ、６００℃で３時間焼成してコート層を形成させた。このコート層の量はハニカム基材１Ｌ当り１００ｇであった。得られたハニカム基材を所定濃度の硝酸Ｒｈ水溶液中に浸漬し、引き上げて余分な液滴を吹き払った後、９０℃で１０分間乾燥させ、６００℃で３時間焼成して、コート層の量１００ｇ（ハニカム基材１Ｌ）当り０．２ｇのＲｈを担持させて第二貴金属担持層を形成させて、担体上に担持された排ガス浄化用触媒の層からなる排ガス浄化用触媒を得た。 Next, the honeycomb base material on which the first noble metal supporting layer is formed is immersed in a slurry B obtained by mixing 30 parts of activated alumina, 60 parts of CeZrO 2 , 10 parts of alumina sol and 100 parts of water with a ball mill. Then, the slurry was pulled up and the excess slurry was blown off, followed by drying at 90 ° C. for 10 minutes and baking at 600 ° C. for 3 hours to form a coating layer. The amount of this coating layer was 100 g per liter of honeycomb substrate. The obtained honeycomb substrate was immersed in an aqueous solution of Rh nitric acid having a predetermined concentration, pulled up and blown off excess droplets, dried at 90 ° C. for 10 minutes, and fired at 600 ° C. for 3 hours. A second noble metal support layer was formed by supporting 0.2 g of Rh per 100 g (honeycomb substrate 1 L) to obtain an exhaust gas purifying catalyst comprising an exhaust gas purifying catalyst layer supported on a carrier.
排ガス浄化性能試験
実施例３及び比較例３の各々の排ガス浄化用触媒について、１０容量％の水蒸気を含有する大気中、電気炉で９００℃で２５時間の耐久処理を行った。その後、それらの排ガス浄化用触媒１５ｃｃをそれぞれ別個に評価装置に充填し、下記の第５表に示す組成の排気モデルガスを空間速度１０００００／ｈで流通させながら、２０℃／分の昇温速度で４００℃まで昇温し、ＣＯ、ＨＣ、ＮＯxの浄化率を連続的に測定した。モデルガスが５０％浄化される温度（Ｔ５０）（℃）及び４００℃におけるモデルガスの浄化率（η４００）（％）は第６表に示す通りであった。
Exhaust gas purification performance test Each of the exhaust gas purification catalysts of Example 3 and Comparative Example 3 was subjected to an endurance treatment at 900 ° C. for 25 hours in an atmosphere containing 10% by volume of water vapor. Thereafter, 15 cc of each of these exhaust gas purification catalysts was separately filled in the evaluation apparatus, and while raising the exhaust model gas having the composition shown in Table 5 below at a space velocity of 100,000 / h, the temperature rising rate was 20 ° C./min. The temperature was raised to 400 ° C., and the purification rates of CO, HC and NOx were continuously measured. The temperature at which the model gas was purified by 50% (T50) (° C.) and the model gas purification rate (η400) (%) at 400 ° C. were as shown in Table 6.
第６表に示すデータから明らかなように、ＣＯ、ＨＣ及びＮＯxについてのＴ５０（排ガスを５０％浄化する時の温度であり、温度が低いほど低温活性に優れた排ガス浄化用触媒といえる）及びη４００（排ガス温度４００℃における浄化率である）の何れにおいても本発明の実施例３の排ガス浄化用触媒は比較例３の排ガス浄化用触媒よりも優れており、本発明の排ガス浄化用触媒は低温活性が高く、耐熱性に優れ、安定した排ガス浄化性能を得ることができるものである。
As is apparent from the data shown in Table 6, CO, T50 for the HC and NO x (a temperature at which the purifying 50% of the exhaust gas, it can be said that excellent exhaust gas purifying catalyst in low-temperature activity as the temperature is low) and η400 also example 3 of the exhaust gas purifying catalyst of the present invention in any of (a purification rate of the exhaust gas temperature 400 ° C.) is superior to the exhaust gas purifying catalyst of Comparative example 3, the exhaust gas purifying catalyst of the present invention Has high low-temperature activity, excellent heat resistance, and stable exhaust gas purification performance.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006291691A JP5078062B2 (en) | 2005-10-26 | 2006-10-26 | Exhaust gas purification catalyst |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005311865 | 2005-10-26 | ||
| JP2005311865 | 2005-10-26 | ||
| JP2006291691A JP5078062B2 (en) | 2005-10-26 | 2006-10-26 | Exhaust gas purification catalyst |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012147965A Division JP5641585B2 (en) | 2005-10-26 | 2012-06-29 | Exhaust gas purification catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007144412A JP2007144412A (en) | 2007-06-14 |
| JP5078062B2 true JP5078062B2 (en) | 2012-11-21 |
Family
ID=38206444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006291691A Expired - Fee Related JP5078062B2 (en) | 2005-10-26 | 2006-10-26 | Exhaust gas purification catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5078062B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5227363B2 (en) * | 2009-06-08 | 2013-07-03 | 三井金属鉱業株式会社 | Exhaust gas purification catalyst |
| JP5873731B2 (en) * | 2012-02-07 | 2016-03-01 | 本田技研工業株式会社 | Exhaust gas treatment catalyst structure |
| JP5502953B2 (en) * | 2012-08-31 | 2014-05-28 | 三井金属鉱業株式会社 | Catalyst carrier and exhaust gas purification catalyst |
| WO2014104181A1 (en) | 2012-12-27 | 2014-07-03 | 三井金属鉱業株式会社 | Catalyst carrier and exhaust gas purifying catalyst |
| CN105050712B (en) | 2013-03-29 | 2017-12-19 | 三井金属矿业株式会社 | Exhaust-gas treatment catalytic structure body |
| WO2016002344A1 (en) | 2014-07-02 | 2016-01-07 | 三井金属鉱業株式会社 | Catalyst carrier and exhaust gas purifying catalyst |
| JP6714989B2 (en) | 2015-01-19 | 2020-07-01 | 国立大学法人秋田大学 | Exhaust gas purification catalyst carrier and exhaust gas purification catalyst |
| WO2016117240A1 (en) * | 2015-01-19 | 2016-07-28 | 三井金属鉱業株式会社 | Carrier for exhaust gas purifying catalysts, and exhaust gas purifying catalyst |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03186346A (en) * | 1989-12-15 | 1991-08-14 | Daihatsu Motor Co Ltd | Catalyst for purifying exhaust gas and catalyst structure |
| JPH06210174A (en) * | 1993-01-20 | 1994-08-02 | Daihatsu Motor Co Ltd | Catalyst for purification of exhaust gas and its production |
| JPH07112121A (en) * | 1993-06-25 | 1995-05-02 | Tosoh Corp | Method for removing nox |
| JPH08224446A (en) * | 1995-02-22 | 1996-09-03 | Daihatsu Motor Co Ltd | Device for purifying automobile exhaust gas |
| JPH11197507A (en) * | 1998-01-19 | 1999-07-27 | Yasuyuki Murofushi | Catalyst for purification of exhaust gas |
| JP4179573B2 (en) * | 1999-03-17 | 2008-11-12 | フィガロ技研株式会社 | Solid electrolyte carbon dioxide sensor element |
| JP4546046B2 (en) * | 2002-10-11 | 2010-09-15 | ダイハツ工業株式会社 | Exhaust gas purification catalyst |
| JP4325648B2 (en) * | 2005-10-24 | 2009-09-02 | トヨタ自動車株式会社 | Catalyst carrier and exhaust gas purification catalyst |
-
2006
- 2006-10-26 JP JP2006291691A patent/JP5078062B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007144412A (en) | 2007-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5078062B2 (en) | Exhaust gas purification catalyst | |
| JP5607131B2 (en) | Exhaust gas purification catalyst | |
| JP5305904B2 (en) | Exhaust gas purification catalyst | |
| JP6567168B2 (en) | Exhaust gas purification catalyst, method for producing the same, and exhaust gas purification apparatus using the same | |
| JP6438384B2 (en) | Exhaust gas purification catalyst carrier and exhaust gas purification catalyst | |
| JP5897047B2 (en) | Catalyst carrier and exhaust gas purification catalyst | |
| JP5802087B2 (en) | Exhaust gas purification catalyst | |
| JPH11276907A (en) | Catalyst for purifying exhaust gas and its production | |
| JP5071840B2 (en) | Exhaust gas purification catalyst | |
| JP6339013B2 (en) | Exhaust gas purification catalyst carrier, exhaust gas purification catalyst, and exhaust gas purification catalyst structure | |
| JPH0312936B2 (en) | ||
| JP5094049B2 (en) | Exhaust gas purification catalyst | |
| JP5641585B2 (en) | Exhaust gas purification catalyst | |
| JPH0824843B2 (en) | Heat resistant catalyst and method of using the same | |
| JP6807447B2 (en) | Exhaust gas purification catalyst carrier and exhaust gas purification catalyst | |
| JPH1076159A (en) | Exhaust gas purification catalyst and its production | |
| JPH0582258B2 (en) | ||
| JP5502953B2 (en) | Catalyst carrier and exhaust gas purification catalyst | |
| WO2002055194A1 (en) | Catalyst for clarification of nitrogen oxides | |
| JPH08155302A (en) | Catalyst for purifying exhaust gas and its production | |
| JPH04180835A (en) | Production of catalyst for purifying exhaust gas | |
| JPH1176819A (en) | Catalyst for cleaning of exhaust gas | |
| JP2009274031A (en) | Catalyst for purification of exhaust gas and manufacturing method of catalyst for purification of exhaust gas | |
| JP2003170046A (en) | Catalyst for cleaning exhaust gas and exhaust gas cleaning method | |
| KR20050028941A (en) | Method for manufacturing double layer coated pd only three way catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090729 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110427 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120502 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120629 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120808 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120824 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150907 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5078062 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |