JPS6111146A - Oxidizing catalyst - Google Patents
Oxidizing catalystInfo
- Publication number
- JPS6111146A JPS6111146A JP59134246A JP13424684A JPS6111146A JP S6111146 A JPS6111146 A JP S6111146A JP 59134246 A JP59134246 A JP 59134246A JP 13424684 A JP13424684 A JP 13424684A JP S6111146 A JPS6111146 A JP S6111146A
- Authority
- JP
- Japan
- Prior art keywords
- tungsten
- catalyst
- alumina
- silica
- resistant material
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 title abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 239000003779 heat-resistant material Substances 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 239000010937 tungsten Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims abstract 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000010970 precious metal Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000000151 deposition Methods 0.000 abstract 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 239000002184 metal Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000010718 Oxidation Activity Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- -1 platinum group metals Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は天然ガス、プロパンガス等の比較的軽質な炭化
水素ガスあるいは一酸化炭素ガスを接触酸化し、炭酸ガ
ス、水に完全酸化する触媒体に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a catalyst that catalytically oxidizes relatively light hydrocarbon gas such as natural gas, propane gas, or carbon monoxide gas to completely oxidize it into carbon dioxide gas and water. It is something.
従来例の構成とその問題点
一般に炭化水素を空気の存在下、炭酸ガスと水蒸気に完
全酸化させる酸化触媒の活性については白金、パラジウ
ム等の白金族をアルミナ、シリカ等の無機態熱材料に担
持したものが、最も活性が高いとされてきた。しかしな
がら白金族はいづれもコストが高く、資源的にも安定供
給の面で問題が残る。さらに耐熱性、１Ｉｉ１硫黄性に
ついても問題がある。特に耐熱性については、５００℃
以上の温度で使用した場合、担持白金族の金属粒子径が
増大して活性が劣化するという問題がある。この為助触
媒の添加、担体の改良等の工夫がなされているが十分な
効果を挙げていない。最近、ペロブスカイト構造を有す
る複合酸化物、特にコバルトを構成元素とするものは活
性が高く白金族の酸化活性に匹敵することが報告されて
いる。さらに耐熱性についても１０００’Ｃ以上の焼成
でも殆ど活性が落ちず非常に優れた触媒である。しかし
ながらペロブスカイト構造を有する複合酸化物の粉末の
表面積はせいぜい５ｒｎ２／ｇ以下であり、この表面積
を太きくし、活性を上げる為に担持型の触媒の開発が望
まれている。 しかし、ペロブスカイト構造を構成する
遷移金属の内、活性が高いとされる、コバルト、ニッケ
ル、鉄等はいツレモ、アルミナ、シリカ等の多孔質の無
機耐熱材料と固溶体を形成し、これらの触媒担体上で望
むペロブスカイト構造を形成することが出来ないという
問題がある。Structure of conventional examples and their problems In general, the activity of oxidation catalysts that completely oxidize hydrocarbons into carbon dioxide gas and water vapor in the presence of air is achieved by supporting platinum group metals such as platinum and palladium on inorganic thermal materials such as alumina and silica. It has been said that those with the highest activity are the most active. However, all platinum group metals are expensive, and problems remain in terms of stable supply of resources. Furthermore, there are also problems with heat resistance and 1Ii1 sulfur properties. Especially for heat resistance, 500℃
When used at temperatures above, there is a problem that the particle diameter of the supported platinum group metal increases and the activity deteriorates. For this reason, efforts have been made to add co-catalysts and improve carriers, but these efforts have not produced sufficient results. Recently, it has been reported that complex oxides having a perovskite structure, particularly those containing cobalt as a constituent element, have high oxidation activity comparable to that of platinum group metals. Furthermore, in terms of heat resistance, it is an extremely excellent catalyst with almost no loss of activity even when fired at temperatures of 1000'C or higher. However, the surface area of a composite oxide powder having a perovskite structure is at most 5rn2/g or less, and in order to increase this surface area and increase activity, it is desired to develop a supported catalyst. However, among the transition metals that make up the perovskite structure, cobalt, nickel, and iron, which are said to have high activity, form a solid solution with porous inorganic heat-resistant materials such as aluminum, alumina, and silica, and these metals form solid solutions on these catalyst supports. There is a problem that it is not possible to form the desired perovskite structure.
発明の目的
本発明の目的は比較的コストの安い遷移金属を中心とす
るペロブスカイト構造を有する高活性で血寸熱性の高い
担持型の酸化触媒を提供することにある。OBJECTS OF THE INVENTION An object of the present invention is to provide a supported oxidation catalyst which is relatively inexpensive and has a perovskite structure mainly containing transition metals, has high activity and high blood temperature.
発明の構成
この目的を達成するために本発明はシリカ、アルミナ等
の多孔質無機耐熱材料にタングステンアンモニウム等の
タングステンを含む各種塩から５〜４０％含浸法により
タングステンを担持し、８００〜９００℃の温度で１〜
３時間焼成したものの上に再度結晶構造式がＡ１ ｘＡ
’ｘＢ、ｙＢ’ｙ０３であらわされるペロブスカイト構
造を有するような量論比に調整された各種金属塩を含浸
した後８００〜９００℃で１〜１０時間焼成するという
構成を取った。但し人はランタン、ネオジウム等の希土
類元素からＡ′は銀、ストロンチウム、セリウムから選
択し、 Ｂ 、 Ｂ’はそれぞれコバルト、ニッケル、
鉄等の遷移金属元素あるいは白金、パラジウム等の貴金
属元素から選択した。株数ｘ、ｙは０〜０．９の範囲と
なるよう構成した。この結果、シリカ、アルミナ等多孔
質無機耐熱材料との間にスピネル等の固溶体を形成する
こともなく所定のベロゲスカイト構造を有する複合酸化
物を形成することが出来た。さらにシリカ、アルミナ等
の多孔質上にペロブスカイト構造を形成する結果、従来
の粉末触媒に比較し、粒子径が非常に小さくなり（５０
〜５００Ａ）、その結果、酸化活性が向上した。Structure of the Invention To achieve this object, the present invention supports tungsten on a porous inorganic heat-resistant material such as silica or alumina by impregnating 5 to 40% of various salts containing tungsten such as tungsten ammonium, and then impregnating the porous inorganic heat-resistant material such as silica or alumina at 800 to 900°C. 1~ at the temperature of
The crystal structure formula is A1 x A again on top of the one fired for 3 hours.
The structure was such that the material was impregnated with various metal salts adjusted to a stoichiometric ratio to have a perovskite structure represented by 'xB, yB'y03, and then fired at 800 to 900°C for 1 to 10 hours. However, from rare earth elements such as lanthanum and neodymium, A' should be selected from silver, strontium, and cerium, and B and B' should be selected from cobalt, nickel, and nickel, respectively.
It was selected from transition metal elements such as iron or noble metal elements such as platinum and palladium. The number of strains x and y was configured to be in the range of 0 to 0.9. As a result, a composite oxide having a predetermined vergeskite structure could be formed without forming a solid solution such as spinel with a porous inorganic heat-resistant material such as silica or alumina. Furthermore, as a result of forming a perovskite structure on porous materials such as silica and alumina, the particle size becomes extremely small (50
~500A), resulting in improved oxidation activity.
実施例の説明
以下本発明の一実施例について説明する。触媒Ａは本発
明によるものでγ−アルミナ担体（表面積１８０ｍ２／
ｇ）にタングステンアンモニウム塩を用いて酸化タング
ステン（ＷＯｓ ）重量にして２０％含浸担持後８５０
℃１２時間焼成したものに、酢酸ランタン、酢酸セリウ
ム、酢酸コバルトを用いて焼成後の量論比がＬａｏ、
ＣｅｏｌＧｏ Ｏ３となるように量論比を調整した混合
溶液に含浸２０％担持後８５０℃で５時間焼成したもの
である。触媒Ｂは従来の粉末調整法によるもので、Ｌａ
ｏ、ＣｅｏｌＣｏｏ。DESCRIPTION OF EMBODIMENTS An embodiment of the present invention will be described below. Catalyst A is according to the present invention and has a γ-alumina carrier (surface area 180 m2/
g) After impregnating and supporting tungsten oxide (WOs) at 20% by weight using tungsten ammonium salt, 850
℃ for 12 hours, the stoichiometric ratio after firing using lanthanum acetate, cerium acetate, and cobalt acetate was
It was impregnated with a mixed solution whose stoichiometric ratio was adjusted to give CeolGo O3 and loaded at 20%, and then calcined at 850° C. for 5 hours. Catalyst B was produced by conventional powder preparation method, and La
o, CeolCoo.
となるよう調整された各酢酸塩の混合溶液をロータリー
エバポレーターにより乾燥後、８５０℃で５時間焼成し
たものである。触媒Ａ、Ｂを用いてメタン完全酸化反応
を行った結果をＴａｂｌｅ １に捷とめた。空間速度（
Ｓ、Ｖ、）は１８０００ｈ−１である。A mixed solution of each acetate salt adjusted to have the following properties was dried using a rotary evaporator, and then baked at 850° C. for 5 hours. The results of a complete methane oxidation reaction using catalysts A and B are summarized in Table 1. Space velocity (
S, V,) is 18000h-1.
Ｔａｂｌｅ １
発明の効果
実施例に示したごとく本発明による所の多孔質カイト構
造を有する触媒に比較すると酸化活性をる触媒では１０
０〜２００ｍ２／ｙの多孔質担体のポアーを利用するこ
とが出来、粒子径が大巾に小さくなＩ）（５ｏ〜５００
人）活性が向上した。さらに触媒の耐熱性についても担
持型にすることによシ、劣化を小さくすることが出来た
。さらに実施例と同じ条件で反応を行ったロジウムを０
．５％アルミナに担持した触媒のメタンの完全酸化温度
が５２０’Ｃであることより、本発明による触媒の活性
は白金族担持触媒の活性を上回るものである。Table 1 Effects of the Invention As shown in the examples, compared to the catalyst having a porous kite structure according to the present invention, the catalyst with oxidation activity has an oxidation activity of 10%.
It is possible to utilize the pores of a porous carrier of 0 to 200 m2/y, and the particle size is extremely small.
Human) activity improved. Furthermore, with respect to the heat resistance of the catalyst, deterioration could be reduced by using a supported type catalyst. Furthermore, rhodium was reacted under the same conditions as in the example.
．． Since the complete methane oxidation temperature of the catalyst supported on 5% alumina is 520'C, the activity of the catalyst according to the present invention exceeds that of the platinum group supported catalyst.
一方コストについてみてみると、白金族を担持した触媒
の見〜殉のコストである。以上本発明によシ白金族以外
の金属を用いて、側熱性が高く酸化活性の高い触媒を得
ることができる。On the other hand, when looking at the cost, it is the cost of a catalyst supporting a platinum group metal. As described above, according to the present invention, a catalyst with high side heat property and high oxidation activity can be obtained using a metal other than the platinum group.
Claims (1)
ンアンモニウム等のタングステンを含む各種塩から５〜
４０％含浸法によりタングステンを担持し、８００〜９
００℃の温度で焼成した後、結晶構造式Ａ＿１＿−＿ｘ
Ａ′＿ｘＢ＿１＿−＿ｙＢ′＿ｙＯ＿３であらわされる
ペロブスカイト構造を有する複合金属酸化物で、ムはラ
ンタン、ネオジウム等の希土類元素からＡ′は銀、スト
ロンチウム、セリウムから選択し、Ｂ、Ｂ′はそれぞれ
コバルト、ニッケル、鉄等の遷移金属元素あるいは白金
、パラジウム等の貴金属元素から選択した元素を株数ｘ
、ｙが０〜０．９の範囲となるよう構成したものを５〜
４０％担持した酸化触媒。From various salts containing tungsten such as tungsten ammonium to porous inorganic heat-resistant materials such as silica and alumina.
Tungsten is supported by the 40% impregnation method, and the
After firing at a temperature of 00℃, the crystal structure formula A_1_-_x
A composite metal oxide having a perovskite structure represented by A'_xB_1_-_yB'_yO_3, where Mu is selected from rare earth elements such as lanthanum and neodymium, A' is selected from silver, strontium, and cerium, and B and B' are cobalt, respectively. x number of stocks of elements selected from transition metal elements such as nickel and iron, or precious metal elements such as platinum and palladium
, 5 to 5 configured so that y is in the range of 0 to 0.9.
40% supported oxidation catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59134246A JPS6111146A (en) | 1984-06-28 | 1984-06-28 | Oxidizing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59134246A JPS6111146A (en) | 1984-06-28 | 1984-06-28 | Oxidizing catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6111146A true JPS6111146A (en) | 1986-01-18 |
| JPH0543416B2 JPH0543416B2 (en) | 1993-07-01 |
Family
ID=15123808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59134246A Granted JPS6111146A (en) | 1984-06-28 | 1984-06-28 | Oxidizing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6111146A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02284649A (en) * | 1989-04-25 | 1990-11-22 | Yoshida Kogyo Kk <Ykk> | Production of perovskite-type oxide catalyst |
| WO2008004687A1 (en) | 2006-07-03 | 2008-01-10 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst |
| JP2012196660A (en) * | 2011-03-08 | 2012-10-18 | Denso Corp | Hydrocarbon selective oxidation catalyst and method for manufacturing the same |
-
1984
- 1984-06-28 JP JP59134246A patent/JPS6111146A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02284649A (en) * | 1989-04-25 | 1990-11-22 | Yoshida Kogyo Kk <Ykk> | Production of perovskite-type oxide catalyst |
| WO2008004687A1 (en) | 2006-07-03 | 2008-01-10 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst |
| EP2050497A1 (en) * | 2006-07-03 | 2009-04-22 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst |
| EP2050497A4 (en) * | 2006-07-03 | 2011-03-16 | Toyota Motor Co Ltd | Exhaust gas purifying catalyst |
| US8999878B2 (en) | 2006-07-03 | 2015-04-07 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst |
| JP2012196660A (en) * | 2011-03-08 | 2012-10-18 | Denso Corp | Hydrocarbon selective oxidation catalyst and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0543416B2 (en) | 1993-07-01 |
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