JPH05168926A - Catalyst excellent in heat resistance for purifying exhaust gas of internal combustion engine and production thereof - Google Patents
Catalyst excellent in heat resistance for purifying exhaust gas of internal combustion engine and production thereofInfo
- Publication number
- JPH05168926A JPH05168926A JP4148025A JP14802592A JPH05168926A JP H05168926 A JPH05168926 A JP H05168926A JP 4148025 A JP4148025 A JP 4148025A JP 14802592 A JP14802592 A JP 14802592A JP H05168926 A JPH05168926 A JP H05168926A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- barium
- compound
- cerium oxide
- exhaust gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の利用分野】本発明は自動車等の内燃機関から排
出される排気ガスの浄化用触媒及びその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for purifying exhaust gas discharged from an internal combustion engine such as an automobile and a method for producing the same.
【０００２】詳しくは、例えばマニホールド直下の高温
(９００〜１１００℃)に長時間さらされた後において
も、従来の触媒に較べ優れた排ガス浄化性能を示す触媒
及びその製造方法に関するものである。More specifically, for example, high temperature just below the manifold
The present invention relates to a catalyst showing excellent exhaust gas purification performance even after being exposed to (900 to 1100 ° C.) for a long time as compared with a conventional catalyst, and a method for producing the same.
【０００３】[0003]
【従来の技術】自動車等の内燃機関から排出される排気
ガス中の炭化水素、一酸化炭素及び窒素酸化物を同時に
除去する三元触媒では、現在主として白金またはロジウ
ム等の白金族元素、及び低温活性向上のために酸素貯蔵
効果を持つ酸化セリウムが用いられている。2. Description of the Related Art At present, a three-way catalyst for simultaneously removing hydrocarbons, carbon monoxide and nitrogen oxides in exhaust gas discharged from an internal combustion engine of an automobile or the like is currently mainly composed of platinum or a platinum group element such as rhodium and low temperature. Cerium oxide, which has an oxygen storage effect, is used to improve the activity.
【０００４】最近の触媒に要求される性能の一つとして
９００〜１１００℃の高温における耐熱性がある。これ
は、触媒の設置場所がよりエンジンに近いマニホールド
直下とされる傾向があることや高速運転時における排ガ
ス温度の上昇等による。One of the performances required of recent catalysts is heat resistance at a high temperature of 900 to 1100 ° C. This is because the location of the catalyst tends to be directly below the manifold closer to the engine and the exhaust gas temperature rises during high-speed operation.
【０００５】しかし、白金族元素や酸化セリウムを含む
触媒はこの様な高温においては劣化され易い。この為、
従来から、触媒の耐熱性を向上させるために、希土類金
属及びアルカリ土類金属の酸化物を添加する方法が知ら
れている。(例えば、特開昭第５０−９９９８８号、特
開昭第５２−３１９９４号)。また、酸化セリウムの高
温における熱劣化を抑制させるためにランタン、カルシ
ウム等を添加することにより触媒の耐熱性を向上できる
としている。(例えば、特開昭第５７−６３１３３号、
特開昭第６１−４６２４７号)。However, a catalyst containing a platinum group element or cerium oxide is easily deteriorated at such a high temperature. Therefore,
Conventionally, in order to improve the heat resistance of the catalyst, a method of adding oxides of rare earth metals and alkaline earth metals is known. (For example, JP-A-50-99988 and JP-A-52-31994). In addition, it is said that the heat resistance of the catalyst can be improved by adding lanthanum, calcium or the like in order to suppress thermal deterioration of cerium oxide at high temperatures. (For example, JP-A-57-63133,
JP-A-61-46247).
【０００６】しかしながら、最近の自動車エンジンの高
速運転による排ガス温度の上昇傾向から、上記公報のい
ずれかに記載された触媒においても高温で使用した後の
活性は充分ではなく、高温で使用した後でも活性が従来
の触媒ほど低下しない優れた触媒の開発が望まれてい
る。However, due to the tendency of exhaust gas temperature to rise due to the recent high-speed operation of automobile engines, even the catalysts described in any of the above publications are not sufficiently active after being used at high temperature, and even after being used at high temperature. It is desired to develop an excellent catalyst whose activity does not decrease as much as that of a conventional catalyst.
【０００７】[0007]
【発明の目的】本発明は、上記従来技術の問題点を解決
し、９００〜１１００℃の高温に長時間さらされた後に
おいても、優れた排気ガス浄化性能を示す触媒を提供す
ることを目的とする。It is an object of the present invention to solve the above-mentioned problems of the prior art and to provide a catalyst exhibiting excellent exhaust gas purification performance even after being exposed to a high temperature of 900 to 1100 ° C. for a long time. And
【０００８】[0008]
【問題点を解決するための手段】本発明者らは、前記問
題点を解決すべく鋭意研究の結果、排気ガス浄化用触媒
を９００〜１１００℃の高温にさらした後でも優れた触
媒活性を維持するために、少なくとも１種類の白金族元
素、活性アルミナ、酸化セリウム、バリウム化合物及び
ジルコニウム化合物を組み合わせることが極めて有効で
あることを見いだし本発明を完成させた。[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have found that the catalyst for purifying exhaust gas exhibits excellent catalytic activity even after being exposed to a high temperature of 900 to 1100 ° C. It has been found that it is extremely effective to combine at least one platinum group element, activated alumina, cerium oxide, a barium compound and a zirconium compound for maintaining the present invention, and completed the present invention.
【０００９】上記目的は、本発明に従い、一体構造を有
する支持体上に、少なくとも１種類の白金族元素、活性
アルミナ、酸化セリウム、バリウム化合物及びジルコニ
ウム化合物からなる活性層を有することを特徴とする排
気ガス浄化用触媒及びその製造方法により解決される。According to the present invention, the above object is characterized in that an active layer comprising at least one platinum group element, activated alumina, cerium oxide, barium compound and zirconium compound is provided on a support having an integral structure. This is solved by an exhaust gas purifying catalyst and a method for manufacturing the same.
【００１０】以下本発明について詳細に説明する。The present invention will be described in detail below.
【００１１】本発明においては、各種バリウム化合物及
びジルコニウム化合物の添加が、白金族元素及び酸化セ
リウムのシンタリング抑制効果を示し、酸化セリウムの
酸素貯蔵効果を保持し、９００〜１１００℃の高温での
使用後の触媒活性の維持に好ましい結果を示す。In the present invention, the addition of various barium compounds and zirconium compounds exhibits the sintering inhibiting effect of platinum group elements and cerium oxide, retains the oxygen storage effect of cerium oxide, and is maintained at a high temperature of 900 to 1100 ° C. It shows favorable results in maintaining the catalytic activity after use.
【００１２】[Ａ] 先ず最初に本発明の触媒について説
明する。[A] First, the catalyst of the present invention will be described.
【００１３】本発明の排気ガス浄化用触媒は、一体構造
を有する支持体上に、触媒成分として少なくとも１種類
の白金族元素、活性アルミナ、酸化セリウム、バリウム
化合物及びジルコニウム化合物を含んでなる排気ガス浄
化触媒である。The catalyst for purifying exhaust gas of the present invention is an exhaust gas containing at least one platinum group element, activated alumina, cerium oxide, barium compound and zirconium compound as catalyst components on a support having an integral structure. It is a purification catalyst.
【００１４】該一体構造を有する支持体は耐火性金属酸
化物または耐火性金属から構成されたものであり、その
構造は例えばハニカム状または三次元網状構造である。
該一体構造を有する支持体は発泡体であることもでき
る。The support having the integral structure is made of a refractory metal oxide or a refractory metal, and its structure is, for example, a honeycomb structure or a three-dimensional network structure.
The support having the integral structure may be a foam.
【００１５】耐火性金属酸化物としては、コージエライ
ト、ムライト、α−アルミナ、シリマナイト、珪酸マグ
ネシウム、ジルコン、ペンタライト、スポジユメン、ア
ルミノ珪酸塩などが挙げられる。また、耐火性金属とし
ては、耐火性鉄基合金、耐火性ニツケル基合金、耐火性
クロム基合金などを挙げることができる。Examples of the refractory metal oxide include cordierite, mullite, α-alumina, sillimanite, magnesium silicate, zircon, pentalite, spodiumene, and aluminosilicate. Examples of the refractory metal include a refractory iron-based alloy, a refractory nickel-based alloy, and a refractory chrome-based alloy.
【００１６】これら一体構造を有する支持体のうち、コ
ージエライトから構成されたハニカム状支持体が最も好
ましく用いられる。Among these supports having an integral structure, the honeycomb support made of cordierite is most preferably used.
【００１７】該白金族元素としては、ＣＯ、ＨＣ、ＮＯ
xを同時に浄化させる目的から、白金及びロジウムを含
むことが望ましい。白金の重量は、必要な触媒活性が得
られる限り如何なる量でも良いが、通常触媒１リツター
当り０.１〜１０g、好ましくは０.１〜３gである。ま
た、ロジウムの重量は、必要な触媒活性が得られる限り
如何なる量でも良いが、通常触媒１リツター当り０.０
２〜２g、好ましくは０.０２〜０.７gである。The platinum group element includes CO, HC and NO.
For the purpose of purifying x at the same time, it is desirable to contain platinum and rhodium. The weight of platinum may be any amount as long as the required catalytic activity can be obtained, but it is usually 0.1 to 10 g, preferably 0.1 to 3 g per 1 litter of the catalyst. The weight of rhodium may be any amount as long as the required catalytic activity is obtained, but it is usually 0.0 per 1 litter of the catalyst.
2 to 2 g, preferably 0.02 to 0.7 g.
【００１８】該活性アルミナは、たとえばγ−アルミナ
が好ましく、その比表面積は１０〜３００m2／gである
ことが望ましく、その重量は通常触媒１リツター当り３
０〜２００g、好ましくは４０〜１２０gである。The activated alumina is preferably, for example, γ-alumina, its specific surface area is preferably 10 to 300 m 2 / g, and its weight is usually 3 per 1 litter of the catalyst.
It is 0 to 200 g, preferably 40 to 120 g.
【００１９】該酸化セリウムは酸素貯蔵効果があり、白
金族元素の使用量を減少し、かつ同一浄化性能を保たせ
るに好ましく、その重量は通常触媒１リツター当り１０
〜１５０g、好ましくは１０〜５０gである。酸化セリウ
ムの比表面積は１０〜３００m2／gであることが望まし
い。The cerium oxide has an oxygen storage effect and is preferable for reducing the amount of platinum group element used and maintaining the same purifying performance, and the weight thereof is usually 10 per 1 litter of the catalyst.
~ 150 g, preferably 10-50 g. The specific surface area of cerium oxide is preferably 10 to 300 m 2 / g.
【００２０】該バリウム化合物としては、水酸化バリウ
ム、酸化バリウムおよび炭酸バリウムが好ましく、その
重量は、該触媒１リツター当り、酸化バリウムに換算
し、０.１〜２０g、好ましくは３〜１５g、更に好まし
くは５〜１０gである。As the barium compound, barium hydroxide, barium oxide and barium carbonate are preferable, and the weight thereof is 0.1 to 20 g, preferably 3 to 15 g, further converted to barium oxide, per 1 litter of the catalyst. It is preferably 5 to 10 g.
【００２１】該ジルコニウム化合物としては、酸化ジル
コニウムが好ましく、その重量は、該触媒１リツター当
り、０.１〜３０g、好ましくは５〜２５g、更に好まし
くは７〜２０gである。The zirconium compound is preferably zirconium oxide, and the weight thereof is 0.1 to 30 g, preferably 5 to 25 g, and more preferably 7 to 20 g per 1 litter of the catalyst.
【００２２】[Ｂ] 次に、本発明の排気ガス浄化用触媒
の製造方法について説明する。[B] Next, a method for producing the exhaust gas purifying catalyst of the present invention will be described.
【００２３】白金族元素を含んでなる活性アルミナの調
製 活性アルミナ(例えば、γ−アルミナ)をミキサーに入れ
る。この活性アルミナの粒径は、１〜１００ミクロン
(μ)、好ましくは１〜５０μ、更に好ましくは１〜３０
μである。ここで、活性アルミナ中に酸化セリウムの一
部を混合させておいても良い。Preparation of activated alumina containing platinum group elements
Make activated alumina (eg, γ-alumina) into a mixer. The particle size of this activated alumina is 1-100 microns
(μ), preferably 1 to 50 μ, more preferably 1 to 30
is μ. Here, a part of cerium oxide may be mixed in the activated alumina.
【００２４】活性アルミナに、白金化合物(例えば、水
酸化白金酸アミン溶液、塩化白金酸)を加える。白金化
合物は、γ−アルミナをミキサーで撹拌しながら、少量
づつ添加することもできるし、一度に添加することもで
きる。白金化合物は溶液(例えば、水溶液)、または懸濁
液(例えば水性懸濁液)として添加することができる。添
加する白金化合物の重量は、活性アルミナ１kg当り、白
金に換算し、１〜１００gであつてよく、白金化合物の
溶液として１００〜５００mlであつてよい。A platinum compound (eg amine hydroxide platinate solution, chloroplatinic acid) is added to activated alumina. The platinum compound can be added little by little while stirring γ-alumina with a mixer, or can be added all at once. The platinum compound can be added as a solution (eg an aqueous solution) or a suspension (eg an aqueous suspension). The weight of the platinum compound added may be 1 to 100 g in terms of platinum per 1 kg of activated alumina, and may be 100 to 500 ml as a platinum compound solution.
【００２５】ついで、ロジウム化合物(例えば、硝酸ロ
ジウム、塩化ロジウム)は、上記活性アルミナと白金化
合物を含有する混合物に、少量づつ添加することもでき
るし、一度に添加することもできる。ロジウム化合物は
溶液または懸濁液として添加することができる。添加す
るロジウム化合物の重量は、活性アルミナ１kg当り、ロ
ジウムに換算し、０.２〜５０gであつてよく、ロジウム
化合物の溶液として１００〜５００mlであつてよい。Then, the rhodium compound (for example, rhodium nitrate or rhodium chloride) can be added to the mixture containing the activated alumina and the platinum compound little by little, or can be added all at once. The rhodium compound can be added as a solution or suspension. The weight of the rhodium compound added may be 0.2 to 50 g in terms of rhodium per 1 kg of activated alumina, and may be 100 to 500 ml as a solution of the rhodium compound.
【００２６】続いて、酢酸の溶液、好ましくは１０〜４
０重量％の酢酸水溶液を、上記白金族化合物と活性アル
ミナを含有する混合物に加える。酢酸溶液は、この混合
物をミキサーで撹拌しながら少量づつ加えることが好ま
しい。加える酢酸の量は、活性アルミナ１kg当り、１０
０〜３００mlであることができる。Subsequently, a solution of acetic acid, preferably 10-4
A 0% by weight aqueous acetic acid solution is added to the mixture containing the platinum group compound and activated alumina. The acetic acid solution is preferably added little by little while stirring this mixture with a mixer. The amount of acetic acid added is 10 per 1 kg of activated alumina.
It can be 0-300 ml.
【００２７】スラリーの調製 上記の方法で得た白金族元素を含む活性アルミナ、酸化
セリウム、バリウム化合物、ジルコニウム化合物、酢酸
及び純水をミルに導入して粉砕しスラリーを生成させ
る。酸化セリウムの重量は、活性アルミナ１kg当り、５
０〜５００g、好ましくは１５０〜４００gである。 Preparation of Slurry Activated alumina containing platinum group element obtained by the above method, cerium oxide, barium compound, zirconium compound, acetic acid and pure water are introduced into a mill and pulverized to form a slurry. The weight of cerium oxide is 5 per 1 kg of activated alumina.
It is 0 to 500 g, preferably 150 to 400 g.
【００２８】該バリウム化合物としては、水酸化バリウ
ム、酢酸バリウムおよび酸化バリウムが好ましく、その
重量は、活性アルミナ１kg当り、酸化バリウムに換算
し、１.０〜３１０g、好ましくは４５〜２２５g、更に
好ましくは６０〜１５０gであることができる。As the barium compound, barium hydroxide, barium acetate and barium oxide are preferable, and the weight thereof is 1.0 to 310 g, preferably 45 to 225 g, more preferably converted to barium oxide per 1 kg of activated alumina. Can be from 60 to 150 g.
【００２９】該ジルコニウム化合物としては、酢酸ジル
コニルおよび水酸化ジルコニルが好ましく、その重量
は、活性アルミナ１kg当り、酸化ジルコニウムに換算
し、１.０から４３０g、好ましくは７０〜３５０g、更
に好ましくは１００〜２９０gである。As the zirconium compound, zirconyl acetate and zirconyl hydroxide are preferable, and the weight thereof is 1.0 to 430 g, preferably 70 to 350 g, more preferably 100 to 100 g, calculated as zirconium oxide per 1 kg of activated alumina. It is 290 g.
【００３０】酢酸は、好ましくは６０〜９０重量％の水
溶液として、活性アルミナ１kg当り、５０〜３００mlで
あることができ、純水の量は、活性アルミナ１kg当り、
５０〜１０００mlであることができる。The acetic acid can be present in an amount of 50 to 300 ml per kg of activated alumina, preferably as an aqueous solution of 60 to 90% by weight, and the amount of pure water per kg of activated alumina is
It can be 50 to 1000 ml.
【００３１】ミルによる上記粉砕により、スラリー中の
混合物の平均粒子径は０.１〜１０μ、好ましくは１〜
５μにすることができる。The average particle size of the mixture in the slurry is 0.1-10 μm, preferably 1-μm by the above pulverization by a mill.
It can be 5μ.
【００３２】生成したスラリーを容器に移し、純水を加
えて所定の比重を有するスラリーとする。この比重は、
例えば１.２０〜１.８５g／mlとすることができる。The produced slurry is transferred to a container, and pure water is added to obtain a slurry having a predetermined specific gravity. This specific gravity is
For example, it can be 1.20 to 1.85 g / ml.
【００３３】スラリーの一体構造を有する支持体への付
着 上記スラリーを一体構造を有する支持体に付着させる。
この支持体は上記[Ａ]で説明したものである。Application of slurry to a support having an integral structure
It is attached to a support having an integral structure wearing the slurry.
This support is the same as described in [A] above.
【００３４】スラリーは、一体構造を有する支持体に、
例えば１〜６０秒間、好ましくは３〜１０秒間付着させ
た後、セル内の余分なスラリーを空気流で取り除く。つ
ぎに、スラリーを付着させた支持体を例えば熱風で、好
ましくは２０〜１００℃の熱風で、少なくとも５０％の
水分、好ましくは９０％の水分を除く。この様にして水
分を除去した後、２００〜９００℃、好ましくは３００
〜８００℃の温度で、１０分〜１０時間、好ましくは１
５〜６０分間、例えば空気中で焼成しても良い。焼成に
当り支持体の温度を徐々に上げる時には、上記乾燥(水
分の除去)を省略しても良い。The slurry is applied to a support having an integral structure,
For example, after depositing for 1 to 60 seconds, preferably 3 to 10 seconds, excess slurry in the cell is removed by air flow. Next, the support to which the slurry is attached is removed with, for example, hot air, preferably hot air at 20 to 100 ° C. to remove at least 50% of water, preferably 90% of water. After removing the water in this way, the temperature is 200 to 900 ° C., preferably 300.
At a temperature of ~ 800 ° C, for 10 minutes to 10 hours, preferably 1
You may bake in the air for 5 to 60 minutes, for example. When gradually raising the temperature of the support during firing, the drying (removal of water) may be omitted.
【００３５】上記のスラリー付着工程により、一体構造
を有する支持体１リツター当り、白金及びロジウムを含
む活性アルミナを、例えば３０〜２００g、酸化セリウ
ムを１０〜１５０g、バリウム化合物を酸化バリウムに
換算し０.１〜２０g、ジルコニウム化合物を酸化ジルコ
ニウムに換算し０.１〜３０g付着させることができる。By the above slurry deposition step, for example, 30 to 200 g of activated alumina containing platinum and rhodium, 10 to 150 g of cerium oxide, and barium compound are converted to barium oxide per 1 litter of the support having an integral structure. .1 to 20 g, zirconium compound can be converted to zirconium oxide to deposit 0.1 to 30 g.
【００３６】[0036]
【実施例】以下、本発明を実施例により詳細に説明す
る。EXAMPLES The present invention will be described in detail below with reference to examples.
【００３７】実施例−１ (a) ＢＥＴ表面積が１５０m2／g及び平均粒子径が３０
μの活性アルミナ１.２kgをミキサーにいれ、この活性
アルミナを撹拌させながら、白金２０.４gを含む水酸化
白金酸のアミン水溶液３００mlを少量づつ滴下し、均一
に分散させた。続いて、ロジウム４.１gを含む硝酸ロジ
ウム水溶液１５０mlを少量づつ滴下し、均一に分散させ
た。 Example-1 (a) BET surface area of 150 m 2 / g and average particle size of 30
1.2 kg of activated alumina of μ was placed in a mixer, and 300 ml of an amine aqueous solution of hydroxidized platinic acid containing 20.4 g of platinum was dropped little by little while stirring the activated alumina to uniformly disperse. Then, 150 ml of an aqueous rhodium nitrate solution containing 4.1 g of rhodium was added dropwise little by little and dispersed uniformly.
【００３８】最後に、２５重量％の酢酸１００mlを少量
づつ滴下し、均一に分散させ、白金及びロジウムを含有
する(Ｐt／Ｒh＝５／１)アルミナ粉末を調製した。Finally, 100 ml of 25% by weight acetic acid was dropped little by little and uniformly dispersed to prepare an alumina powder containing platinum and rhodium (Pt / Rh = 5/1).
【００３９】(b) (a)の工程で得られた白金及びロジウ
ムを含む活性アルミナを乾燥重量にて５３２g、平均粒
子径が１５μの酸化セリウムを３０４g、水酸化バリウ
ム８水和物を１１７g(酸化バリウム換算;５７g)、酢酸
ジルコニルを５３５g(酸化ジルコニウム換算;１０７
g)、９０重量％酢酸を７１ml及び純水１００mlをミルに
導入し混合粉砕した後に、アルミナスラリーを得る。粉
砕時間はスラリー中の粒子径の９０％以上が９.０μ以
下となるまでとした。(B) 532 g of dry activated alumina containing platinum and rhodium obtained in the step (a), 304 g of cerium oxide having an average particle diameter of 15μ and 117 g of barium hydroxide octahydrate ( Barium oxide conversion; 57 g), zirconyl acetate 535 g (zirconium oxide conversion; 107
g), 71 ml of 90 wt% acetic acid and 100 ml of pure water were introduced into a mill and mixed and pulverized to obtain an alumina slurry. The crushing time was until 90% or more of the particle diameter in the slurry became 9.0 μ or less.
【００４０】(c) (b)の工程で得られたスラリーに純水
を加え比重を１.６６g／mlに調製し、希釈スラリーを得
た。この希釈スラリー中に、直径９３mmφ、長さ１４
７.５mmＬの円筒形のコージエライト製モノリス担体(体
積１.０リツター、３００セル／in2)を５秒間浸漬し、
これを希釈スラリーから引き上げた後、空気流にて余分
なスラリーを取り除いた。更に、３０〜６０℃にて乾燥
後、５００℃にて３０分間焼成し、触媒Ａを得た。(C) Pure water was added to the slurry obtained in the steps (b) to adjust the specific gravity to 1.66 g / ml to obtain a diluted slurry. In this diluted slurry, diameter 93mmφ, length 14
A 7.5 mmL cylindrical cordierite monolithic carrier (volume 1.0 litter, 300 cells / in 2 ) was immersed for 5 seconds,
After this was pulled up from the diluted slurry, excess slurry was removed by air flow. Further, after drying at 30 to 60 ° C., it was calcined at 500 ° C. for 30 minutes to obtain a catalyst A.
【００４１】この(a)(b)(c)の一連の工程において得ら
れた触媒Ａは、完成触媒１リツター当り、白金及びロジ
ウム１.４g、アルミナ７０g、酸化セリウム４０g、酸化
バリウムに換算して７.５gのバリウム化合物及び酸化ジ
ルコニウム１４gを含んでいた。The catalyst A obtained in the series of steps (a) (b) (c) was converted into 1.4 g of platinum and rhodium, 70 g of alumina, 40 g of cerium oxide, 40 g of barium oxide per 1 litter of the finished catalyst. It contained 7.5 g of barium compound and 14 g of zirconium oxide.
【００４２】比較例−１ 実施例−１の(b)の工程において、水酸化バリウム及び
酢酸ジルコニルを添加しなかつたこと以外は同様の方法
にて、触媒Ｂを得た。 Comparative Example-1 A catalyst B was obtained by the same method except that barium hydroxide and zirconyl acetate were not added in the step (b) of Example-1.
【００４３】比較例−２ 実施例−１の(b)の工程において、酢酸ジルコニルを添
加しなかつたこと以外は同様の方法にて、触媒Ｃを得
た。 Comparative Example-2 A catalyst C was obtained by the same method except that zirconyl acetate was not added in the step (b) of Example-1.
【００４４】比較例−３ 実施例−１の(b)の工程において、水酸化バリウムを添
加しなかつたこと以外は同様の方法にて、触媒Ｄを得
た。 Comparative Example-3 A catalyst D was obtained by the same method except that barium hydroxide was not added in the step (b) of Example-1.
【００４５】比較例−４ 実施例−１の(b)の工程において、酸化セリウムを添加
しなかつたこと以外は同様の方法にて、触媒Ｅを得た。 Comparative Example-4 A catalyst E was obtained by the same method except that cerium oxide was not added in the step (b) of Example-1.
【００４６】実施例−２ 実施例−１の(b)の工程において、水酸化バリウムの代
わりに、酸化バリウム換算としては同量の酸化バリウム
を用いたこと以外は同様の方法にて、触媒Ｆを得た。 Example-2 In the step (b) of Example-1, the catalyst F was prepared in the same manner except that the same amount of barium oxide as barium oxide was used instead of barium hydroxide. Got
【００４７】実施例−３ 実施例−１の(b)の工程において、水酸化バリウムの添
加量を１１７gの代わりに８３gとしたこと以外は同様の
方法にて、完成触媒１リツター当り、酸化バリウムに換
算して５.３gのバリウム化合物を含む触媒Ｇを得た。 Example-3 In the step (b) of Example-1, barium oxide was added per 1 litter of the finished catalyst in the same manner except that the amount of barium hydroxide added was 83 g instead of 117 g. As a result, a catalyst G containing 5.3 g of barium compound was obtained.
【００４８】実施例−４ 実施例−１の(b)の工程において、水酸化バリウムの添
加量を１１７gの代わりに１５６gとしたこと以外は同様
の方法にて、完成触媒１リツター当り、酸化バリウムに
換算して１０gのバリウム化合物を含む触媒Ｈを得た。 Example-4 In the step (b) of Example-1, barium oxide was added per 1 litter of the finished catalyst in the same manner except that the amount of barium hydroxide added was 156 g instead of 117 g. As a result, a catalyst H containing 10 g of a barium compound was obtained.
【００４９】実施例−５ 実施例−１の(b)の工程において、水酸化バリウムの添
加量を１１７gの代わりに５５gとしたこと以外は同様の
方法にて、完成触媒１リツター当り、酸化バリウムに換
算して３.５gのバリウム化合物を含む触媒Ｉを得た。 Example-5 In the step (b) of Example-1, barium oxide was added per 1 litter of the finished catalyst in the same manner except that the amount of barium hydroxide added was 55 g instead of 117 g. The catalyst I containing 3.5 g of barium compound was obtained.
【００５０】実施例−６ 実施例−１の(b)の工程において、酢酸ジルコニルの代
わりに、酸化ジルコニウム換算としては同量の水酸化ジ
ルコニルを用いたこと以外は同様の方法にて、触媒Ｊを
得た。 Example 6 Catalyst J was prepared in the same manner as in Example 1 except that the same amount of zirconyl hydroxide as zirconium oxide was used instead of zirconyl acetate. Got
【００５１】実施例−７ 実施例−１の(b)の工程において、酢酸ジルコニルの添
加量を５３５gの代わりに７６４gとしたこと以外は同様
の方法にて、完成触媒１リツター当り、酸化ジルコニウ
ム２０gを含む触媒Ｋを得た。実施例−８ 実施例−１の(b)の工程において、酢酸ジルコニルの添
加量を５３５gの代わりに２６８gとしたこと以外は同様
の方法にて、完成触媒１リツター当り、酸化ジルコニウ
ム７gを含む触媒Ｌを得た。 Example 7 In the step (b) of Example-1, 20 g of zirconium oxide was added per 1 litter of the finished catalyst by the same method except that the amount of zirconyl acetate added was 764 g instead of 535 g. A catalyst K containing was obtained. Example-8 A catalyst containing 7 g of zirconium oxide per 1 litter of the finished catalyst was prepared in the same manner as in the step (b) of Example-1, except that the amount of zirconyl acetate added was 268 g instead of 535 g. L was obtained.
【００５２】実施例−９ 実施例−１の(b)の工程において、酸化セリウムの添加
量を３０４gの代わりに１９０gとしたこと以外は同様の
方法にて、完成触媒１リツター当り、酸化セリウム２５
gを含む触媒Ｍを得た。 Example-9 In the same manner as in the step (b) of Example-1, except that the amount of cerium oxide added was 190 g instead of 304 g, cerium oxide 25 per liter of finished catalyst was used.
A catalyst M containing g was obtained.
【００５３】実施例−１０ 実施例−１の(b)の工程において、酸化セリウムの添加
量を３０４gの代わりに４１８gとしたこと以外は同様の
方法にて、完成触媒１リツター当り、酸化セリウム５５
gを含む触媒Ｎを得た。 Example-10 In the step (b) of Example-1, except that the amount of cerium oxide added was 418 g instead of 304 g, cerium oxide 55 was added per 1 litter of the finished catalyst.
A catalyst N containing g was obtained.
【００５４】試験例−１ 実施例−１〜１０および比較例−１〜４で得られた各々
の触媒(サンプル記号ＡからＮ)は、以下の方法にて耐久
試験を行った後、その触媒性能を評価した。 Test Example-1 Each of the catalysts (Sample Codes A to N) obtained in Examples-1 to 10 and Comparative Examples-1 to 4 was subjected to a durability test by the following method, and then the catalyst was used. The performance was evaluated.
【００５５】耐久試験 各触媒をステンレス製のマルチコンバーターに充填し、
以下の条件にて、このマルチコンバーターに実際の排ガ
スと同様な排ガスを５０時間流すことによつて行った。 Durability test Each catalyst was filled in a stainless multi-converter,
Exhaust gas similar to actual exhaust gas was caused to flow through this multi-converter for 50 hours under the following conditions.
【００５６】空然比 ; Ａ／Ｆ＝１６.２ 触媒床温度 ; ９５０℃ 燃料 ; ガソリン(無鉛)触媒性能評価試験 触媒の性能評価は、各触媒をサンブリング管を取り付け
た上記同様のマルチコンバーターに充填し、各触媒の入
口及び出口ガス成分を堀場製作所ＭＥＸＡ８１２０で分
析することにより行った。この場合、排ガスとしては、
実際の排ガスと同様なガスを使用し、以下の条件にて触
媒性能評価試験を行った。A / F ratio: A / F = 16.2 Catalyst bed temperature: 950 ° C. Fuel: Gasoline (lead-free) catalyst performance evaluation test The performance evaluation of the catalyst was carried out by the same multi-converter as described above in which each catalyst was fitted with a tumbling pipe. And gas components of the inlet and outlet of each catalyst were analyzed by Horiba MEXA8120. In this case, as exhaust gas,
Using the same gas as the actual exhaust gas, a catalyst performance evaluation test was conducted under the following conditions.
【００５７】空燃比 ;１４.５５、１４.７、１
４.８５(△Ａ／Ｆ＝±０.５) 空間速度(ＳＶ);１３３,０００／Ｈr 触媒入口温度 ;５００℃ 変動周期 ;２.０Ｈz 尚、各成分(ＣＯ、ＨＣ、ＮＯx)の浄化率は上記各Ａ／
Ｆにおける浄化率の平均値にて示した。Air-fuel ratio: 14.55, 14.7, 1
4.85 (△ A / F = ± 0.5) Space velocity (SV); 133,000 / Hr Catalyst inlet temperature; 500 ° C Fluctuation cycle; 2.0Hz Purification of each component (CO, HC, NOx) The rate is each A /
The average value of the purification rate in F is shown.
【００５８】この結果を第１表〜第６表に示した。The results are shown in Tables 1 to 6.
【００５９】第１表からわかるように、酸化セリウム、
バリウム化合物及びジルコニウム化合物を同時に含む触
媒(サンプル記号;Ａ)は、９５０℃における高温耐久試
験後においても優れた浄化性能を示した。しかし、これ
らの添加物の内、少なくとも一つ以上の添加物がない場
合においては、９５０℃における高温耐久試験後の浄化
性能は、著しく低下した。As can be seen from Table 1, cerium oxide,
The catalyst containing the barium compound and the zirconium compound at the same time (sample symbol: A) showed excellent purification performance even after the high temperature durability test at 950 ° C. However, when at least one of these additives was not present, the purification performance after the high temperature endurance test at 950 ° C. was significantly reduced.
【００６０】第２表からわかるように、バリウム化合物
の種類に依らず、バリウム化合物が他の添加物(酸化セ
リウム、ジルコニウム化合物)と共存すると、高温耐久
試験後に優れた浄化性能を示した。As can be seen from Table 2, when the barium compound coexists with other additives (cerium oxide, zirconium compound), regardless of the kind of barium compound, excellent purification performance was shown after the high temperature durability test.
【００６１】第３表からわかるように、バリウム化合物
の添加効果は少量にても認められるが、添加量の最適範
囲は、酸化バリウムに換算し、０.１〜２０g／l、好ま
しくは３.０〜１５.０g／l、更に好ましくは５.０〜１
０g／lである。As can be seen from Table 3, the addition effect of the barium compound is recognized even in a small amount, but the optimum range of the addition amount is 0.1 to 20 g / l in terms of barium oxide, preferably 3. 0 to 15.0 g / l, more preferably 5.0 to 1
It is 0 g / l.
【００６２】第４表からわかるように、ジルコニウム化
合物の種類に依らず、ジルコニウム化合物が他の添加物
(酸化セリウム、バリウム化合物)と共存すると、高温耐
久試験後に優れた浄化性能を示した。As can be seen from Table 4, the zirconium compound is used as another additive regardless of the kind of the zirconium compound.
When coexisting with (cerium oxide and barium compound), excellent purification performance was exhibited after the high temperature durability test.
【００６３】第５表からわかるように、ジルコニウム化
合物の添加効果は少量にても認められるが、添加量の最
適範囲は、酸化ジルコニウムに換算し、０.１〜３０g／
l、好ましくは５.０〜２５.０g／l、更に好ましくは７.
０〜２０g／lである。As can be seen from Table 5, the effect of adding the zirconium compound is recognized even in a small amount, but the optimum range of the adding amount is 0.1 to 30 g / z in terms of zirconium oxide.
1, preferably 5.0 to 25.0 g / l, more preferably 7.
It is 0 to 20 g / l.
【００６４】第６表からわかるように、酸化セリウムの
添加量の最適範囲は、１０〜１５０g／l、好ましくは１
０〜５０g／lである。As can be seen from Table 6, the optimum range of the amount of cerium oxide added is 10 to 150 g / l, preferably 1
It is 0 to 50 g / l.
【００６５】試験例−２ 各触媒の耐久試験後の酸化セリウムの結晶子径をＸ線回
折装置(理学電機製ＲＡＤ−ＩＩＶＢ)を用いて求め、酸
化セリウムの熱劣化の度合を評価した。熱劣化が進行す
ると、酸化セリウムの結晶子径は次第に大きくなり、そ
の酸素貯蔵効果は小さくなる為、触媒の活性は低下す
る。 Test Example-2 The crystallite size of cerium oxide after the durability test of each catalyst was determined by using an X-ray diffractometer (RAD-IIVB manufactured by Rigaku Denki Co., Ltd.), and the degree of thermal deterioration of cerium oxide was evaluated. As the thermal deterioration progresses, the crystallite size of cerium oxide gradually increases and its oxygen storage effect decreases, so that the activity of the catalyst decreases.
【００６６】第７表からわかるように、酸化セリウムの
熱劣化の度合は、バリウム化合物及びジルコニウム化合
物を同時に添加した触媒において、著しく抑制された。As can be seen from Table 7, the degree of thermal deterioration of cerium oxide was significantly suppressed in the catalyst to which the barium compound and the zirconium compound were added at the same time.
【００６７】[0067]
【発明の効果】以上説明したように、本発明の触媒は、
一体構造を有する支持体上に活性成分として、白金族元
素、活性アルミナ、酸化セリウム、バリウム化合物及び
ジルコニウム化合物を含むことにより、従来の触媒に比
べ、触媒中の酸化セリウムの熱劣化は著しく抑制され
た。本発明の触媒により、９５０℃における高温耐久試
験後の活性を常用温度(５００℃)における各規制物質の
浄化率にて評価すると、一酸化炭素の浄化率を１０〜１
５％、炭化水素の浄化率を３〜７％、窒素酸化物の浄化
率を１０〜１５％上げることが可能となつた。As described above, the catalyst of the present invention is
By including platinum group element, activated alumina, cerium oxide, barium compound and zirconium compound as an active component on the support having a monolithic structure, thermal deterioration of cerium oxide in the catalyst is significantly suppressed as compared with the conventional catalyst. It was When the activity of the catalyst of the present invention after a high temperature durability test at 950 ° C. is evaluated by the purification rate of each regulated substance at a normal temperature (500 ° C.), the purification rate of carbon monoxide is 10 to 1
It is possible to increase the purification rate of hydrocarbons by 5%, the purification rate of hydrocarbons by 3 to 7%, and the purification rate of nitrogen oxides by 10 to 15%.
【００６８】表の説明 第１表;９５０℃高温耐久試験後の各触媒において、浄
化性能に対する添加物の効果についての比較。Explanation of Tables Table 1; Comparison of effect of additives on purification performance of each catalyst after 950 ° C. high temperature durability test.
【００６９】第２表;９５０℃高温耐久試験後の各触媒
において、添加したバリウム化合物の種類の浄化性能に
対する効果についての比較。Table 2 is a comparison of the effect of the type of barium compound added on the purification performance of each catalyst after the 950 ° C. high temperature durability test.
【００７０】第３表;９５０℃高温耐久試験後の各触媒
において、添加したバリウム化合物の添加量の浄化性能
に対する効果についての比較。Table 3 is a comparison of the effect of the added amount of the added barium compound on the purification performance in each catalyst after the 950 ° C. high temperature durability test.
【００７１】第４表;９５０℃高温耐久試験後の各触媒
において、添加したジルコニウム化合物の種類の浄化性
能に対する効果についての比較。Table 4 is a comparison of the effect of the type of the added zirconium compound on the purification performance of each catalyst after the 950 ° C. high temperature durability test.
【００７２】第５表;９５０℃高温耐久試験後の各触媒
において、添加したジルコニウム化合物の添加量の浄化
性能に対する効果についての比較。Table 5: Comparison of the effect of the added amount of the added zirconium compound on the purification performance in each catalyst after the 950 ° C high temperature durability test.
【００７３】第６表;９５０℃高温耐久試験後の各触媒
において、添加した酸化セリウムの添加量の浄化性能に
対する効果についての比較。Table 6: Comparison of the effect of the added amount of cerium oxide added on the purification performance in each catalyst after the 950 ° C. high temperature durability test.
【００７４】第７表;９５０℃高温耐久試験後の各触媒
において、添加物による酸化セリウムの熱劣化の抑制に
対する効果について酸化セリウムの結晶子径を比較。Table 7: Comparison of cerium oxide crystallite diameters with respect to the effect of additives on suppressing thermal deterioration of cerium oxide in each catalyst after the 950 ° C. high temperature durability test.
【００７５】[0075]
【表１】 [Table 1]
【００７６】[0076]
【表２】 [Table 2]
【００７７】[0077]
【表３】 [Table 3]
【００７８】[0078]
【表４】 [Table 4]
【００７９】[0079]
【表５】 [Table 5]
【００８０】[0080]
【表６】 [Table 6]
【００８１】[0081]
【表７】 [Table 7]
Claims (3)
素、活性アルミナ、酸化セリウム、バリウム化合物およ
びジルコニウム化合物を含む排気ガス浄化用触媒であっ
て、白金族元素が白金、パラジウムおよびロジウムであ
ることを特徴とする排気ガス浄化用触媒。1. An exhaust gas purifying catalyst containing a platinum group element, activated alumina, cerium oxide, a barium compound and a zirconium compound on a support having an integral structure, wherein the platinum group element is platinum, palladium and rhodium. An exhaust gas purifying catalyst characterized by being present.
素、活性アルミナ、酸化セリウム、バリウム化合物およ
びジルコニウム化合物を含む排気ガス浄化用触媒であっ
て、白金族元素がパラジウムおよびロジウムであること
を特徴とする排気ガス浄化用触媒。2. An exhaust gas purifying catalyst containing a platinum group element, activated alumina, cerium oxide, a barium compound and a zirconium compound on a support having an integral structure, wherein the platinum group element is palladium and rhodium. An exhaust gas purification catalyst characterized by.
素、活性アルミナ、酸化セリウム、バリウム化合物およ
びジルコニウム化合物を含む排気ガス浄化用触媒であっ
て、白金族元素がパラジウムであることを特徴とする排
気ガス浄化用触媒。3. An exhaust gas purifying catalyst containing a platinum group element, activated alumina, cerium oxide, a barium compound and a zirconium compound on a support having an integral structure, wherein the platinum group element is palladium. Exhaust gas purification catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4148025A JP2581872B2 (en) | 1992-05-15 | 1992-05-15 | Exhaust gas purification catalyst for internal combustion engine excellent in heat resistance and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4148025A JP2581872B2 (en) | 1992-05-15 | 1992-05-15 | Exhaust gas purification catalyst for internal combustion engine excellent in heat resistance and method for producing the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62213159A Division JP2537239B2 (en) | 1987-08-28 | 1987-08-28 | Exhaust gas purification catalyst for internal combustion engine excellent in heat resistance and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05168926A true JPH05168926A (en) | 1993-07-02 |
| JP2581872B2 JP2581872B2 (en) | 1997-02-12 |
Family
ID=15443429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4148025A Expired - Lifetime JP2581872B2 (en) | 1992-05-15 | 1992-05-15 | Exhaust gas purification catalyst for internal combustion engine excellent in heat resistance and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2581872B2 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0766474A (en) * | 1993-08-31 | 1995-03-10 | Jgc Corp | Carbon dioxide laser device |
| JPH11207183A (en) * | 1997-11-20 | 1999-08-03 | Daihatsu Motor Co Ltd | Catalyst for purification of exhaust gas |
| JP2001062295A (en) * | 1999-08-30 | 2001-03-13 | Daihatsu Motor Co Ltd | Exhaust gas cleaning catalyst |
| JP2001070792A (en) * | 1999-09-03 | 2001-03-21 | Daihatsu Motor Co Ltd | Catalyst for cleaning exhaust gas |
| JP2002011350A (en) * | 1999-05-24 | 2002-01-15 | Daihatsu Motor Co Ltd | Exhaust gas cleaning catalyst |
| US6500392B2 (en) | 1996-12-20 | 2002-12-31 | Ngk Insulators, Ltd. | Catalyst for exhaust gas purification and system for exhaust gas purification |
| WO2007122917A1 (en) | 2006-03-30 | 2007-11-01 | Cataler Corporation | Exhaust gas purifying catalyst and method for producing same |
| WO2008004390A1 (en) | 2006-07-05 | 2008-01-10 | Cataler Corporation | Catalyst for purifying exhaust gas and process for producing the same |
| JP2008296111A (en) * | 2007-05-30 | 2008-12-11 | Toyota Motor Corp | Manufacturing method of exhaust gas purifying catalyst and exhaust gas purifying catalyst |
| US7759278B2 (en) | 2004-11-08 | 2010-07-20 | Cataler Corporation | Exhaust gas-purifying catalyst |
| US7956005B2 (en) | 2005-12-22 | 2011-06-07 | Cataler Corporation | Exhaust gas-purifying catalyst |
| US8133839B2 (en) | 2005-06-16 | 2012-03-13 | Cataler Corporation | Exhaust gas-purifying catalyst |
| US11110396B2 (en) | 2015-04-07 | 2021-09-07 | Umicore Shokubai Japan Co., Ltd. | Catalyst for purification of exhaust gas from internal combustion engine and exhaust gas purifying method using the catalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4990295A (en) * | 1972-12-15 | 1974-08-28 | ||
| JPS5976548A (en) * | 1982-07-26 | 1984-05-01 | ソシエテ・フランセ−ズ・デ・ブロデユイ・プ−ル・カタリ−ズ「い」プロ−カタリ−ズ | Production of catalyst for treating exhaust gas from internal combustion engine |
| JPS59156434A (en) * | 1983-02-25 | 1984-09-05 | Toyota Motor Corp | Catalyst for purifying exhaust gas |
| JPS60190236A (en) * | 1984-03-12 | 1985-09-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Preparation of catalyst having high temperature heat resistance |
| JPS6111147A (en) * | 1984-06-14 | 1986-01-18 | エンゲルハード・コーポレーシヨン | Catalyst |
| JPS6214338A (en) * | 1985-07-11 | 1987-01-22 | Ricoh Co Ltd | Tracking device |
| JPS6458347A (en) * | 1987-08-28 | 1989-03-06 | Engelhard Nippon | Catalyst of superior heat resistance for purifying internal combustion engine exhaust gas and its preparation |
-
1992
- 1992-05-15 JP JP4148025A patent/JP2581872B2/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4990295A (en) * | 1972-12-15 | 1974-08-28 | ||
| JPS5976548A (en) * | 1982-07-26 | 1984-05-01 | ソシエテ・フランセ−ズ・デ・ブロデユイ・プ−ル・カタリ−ズ「い」プロ−カタリ−ズ | Production of catalyst for treating exhaust gas from internal combustion engine |
| JPS59156434A (en) * | 1983-02-25 | 1984-09-05 | Toyota Motor Corp | Catalyst for purifying exhaust gas |
| JPS60190236A (en) * | 1984-03-12 | 1985-09-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Preparation of catalyst having high temperature heat resistance |
| JPS6111147A (en) * | 1984-06-14 | 1986-01-18 | エンゲルハード・コーポレーシヨン | Catalyst |
| JPS6214338A (en) * | 1985-07-11 | 1987-01-22 | Ricoh Co Ltd | Tracking device |
| JPS6458347A (en) * | 1987-08-28 | 1989-03-06 | Engelhard Nippon | Catalyst of superior heat resistance for purifying internal combustion engine exhaust gas and its preparation |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0766474A (en) * | 1993-08-31 | 1995-03-10 | Jgc Corp | Carbon dioxide laser device |
| US6500392B2 (en) | 1996-12-20 | 2002-12-31 | Ngk Insulators, Ltd. | Catalyst for exhaust gas purification and system for exhaust gas purification |
| JPH11207183A (en) * | 1997-11-20 | 1999-08-03 | Daihatsu Motor Co Ltd | Catalyst for purification of exhaust gas |
| JP2002011350A (en) * | 1999-05-24 | 2002-01-15 | Daihatsu Motor Co Ltd | Exhaust gas cleaning catalyst |
| JP2001062295A (en) * | 1999-08-30 | 2001-03-13 | Daihatsu Motor Co Ltd | Exhaust gas cleaning catalyst |
| JP2001070792A (en) * | 1999-09-03 | 2001-03-21 | Daihatsu Motor Co Ltd | Catalyst for cleaning exhaust gas |
| US7759278B2 (en) | 2004-11-08 | 2010-07-20 | Cataler Corporation | Exhaust gas-purifying catalyst |
| US8133839B2 (en) | 2005-06-16 | 2012-03-13 | Cataler Corporation | Exhaust gas-purifying catalyst |
| EP2698197A1 (en) | 2005-06-16 | 2014-02-19 | Cataler Corporation | Exhaust gas-purifying catalyst |
| US7956005B2 (en) | 2005-12-22 | 2011-06-07 | Cataler Corporation | Exhaust gas-purifying catalyst |
| US8187996B2 (en) | 2005-12-22 | 2012-05-29 | Cataler Corporation | Exhaust gas-purifying catalyst |
| US8097556B2 (en) | 2006-03-30 | 2012-01-17 | Cataler Corporation | Exhaust gas-purifying catalyst and method of manufacturing the same |
| WO2007122917A1 (en) | 2006-03-30 | 2007-11-01 | Cataler Corporation | Exhaust gas purifying catalyst and method for producing same |
| WO2008004390A1 (en) | 2006-07-05 | 2008-01-10 | Cataler Corporation | Catalyst for purifying exhaust gas and process for producing the same |
| US9073048B2 (en) | 2006-07-05 | 2015-07-07 | Cataler Corporation | Exhaust gas-purifying catalyst and method of manufacturing the same |
| JP2008296111A (en) * | 2007-05-30 | 2008-12-11 | Toyota Motor Corp | Manufacturing method of exhaust gas purifying catalyst and exhaust gas purifying catalyst |
| US11110396B2 (en) | 2015-04-07 | 2021-09-07 | Umicore Shokubai Japan Co., Ltd. | Catalyst for purification of exhaust gas from internal combustion engine and exhaust gas purifying method using the catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2581872B2 (en) | 1997-02-12 |
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