JPS6025544A - Catalyst for purifying exhaust gas - Google Patents
Catalyst for purifying exhaust gasInfo
- Publication number
- JPS6025544A JPS6025544A JP58133145A JP13314583A JPS6025544A JP S6025544 A JPS6025544 A JP S6025544A JP 58133145 A JP58133145 A JP 58133145A JP 13314583 A JP13314583 A JP 13314583A JP S6025544 A JPS6025544 A JP S6025544A
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- carrier
- catalyst
- slurry
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 abstract description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 abstract description 2
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 abstract description 2
- 229960001633 lanthanum carbonate Drugs 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- 239000012153 distilled water Substances 0.000 abstract 1
- 239000008188 pellet Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 230000006866 deterioration Effects 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
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000036848 Porzana carolina Species 0.000 description 1
- 235000002492 Rungia klossii Nutrition 0.000 description 1
- 244000117054 Rungia klossii Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009747 swallowing Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、自動車の排ガスを浄化対象とする排ガス浄化
用触媒に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an exhaust gas purifying catalyst for purifying automobile exhaust gas.
（従来技術）
自動車等の内燃＠ｉ；ａから排出される排ガスを浄化す
るために触媒が１史用さ瓦ているこ七は既に９４口られ
ている。従来、自動車用の排ガス浄化用触媒としては、
活・計アルミナ等からなる粒状担体また媒コージライト
等からなるハニカム状基材にアルミナを被覆したモノリ
ス担体に、白金、パラジウム、ロジウム等のノ独媒活性
を有する貴金属を単独または組合ｔて担持したものが使
用されているっ融媒において、担体Ｖま単に触媒成分を
支持する役割を果たすだけでなく、その触媒の触媒活性
、＃久性に大きく作用するうそのため、従来はより多孔
質で表面積の大きい活１生アルミナ（ｒ−アルミナ）を
用いている。(Prior Art) Catalysts have been used for a long time to purify exhaust gas emitted from internal combustion engines such as automobiles, and 94 catalysts have already been used. Conventionally, as a catalyst for purifying exhaust gas for automobiles,
A granular carrier made of active or total alumina, etc., or a monolithic carrier made of a honeycomb-shaped base material made of medium cordierite, etc. coated with alumina, supports noble metals having sole catalytic activity, such as platinum, palladium, and rhodium, singly or in combination. In the fusion medium in which the carrier V is used, the carrier V not only plays the role of supporting the catalyst components, but also has a large effect on the catalytic activity and durability of the catalyst. Live alumina (r-alumina) with a large surface area is used.
（技術釣線、１）
ところで、この種の触媒は、力Ｘなシの高温（約８００
〜１０００℃）にさらされて使用さり、ること力λら、
触媒性能が熱劣化していくものであってはならない。(Technical Fishing Line, 1) By the way, this type of catalyst can be used at extremely high temperatures (approximately 800
~1000℃)
The catalyst performance must not deteriorate due to heat.
し力＞Ｌ７ｚがら、担体と１〜て活性′γアルミナ用い
た排ガス浄化用触媒をム、少なからず上記熱劣化を起こ
す、という問題を有する。However, when using an exhaust gas purifying catalyst using activated γ alumina as a carrier, there is a problem in that the above-mentioned thermal deterioration occurs to some extent.
（発明の目的）
本発明は担体としてアルミナを使用しているにもカーか
わらず、熱劣化が少なく、ｆｌ／２ ｉｔ ｙ’こ触媒
活性および耐久性を有する排ガス堕化用ｈコ（媒を提供
することを目的とするう
本発明者等は、かかる技術的課題のノヂを決を月的とし
て種々研究ケ直ねた結果、触媒性能の熱劣化の一因が刀
口燕状況Ｆに訃りるアルミナの変態に存することを見出
し、本発明を完成した。(Objective of the Invention) The present invention provides a catalyst for exhaust gas degradation that has little thermal deterioration, fl/2 ity' catalyst activity and durability despite using alumina as a carrier. The inventors of the present invention have conducted various research to solve this technical problem, and as a result, it has been determined that the cause of thermal deterioration of catalyst performance is due to the Tsubame Toguchi situation F. The present invention was completed based on the discovery that the present invention exists in the metamorphosis of alumina.
すなわち、アルばすの変態は、 γ：３００〜８００℃ δ： ８００〜９００℃ θ：９００〜１０５０℃ α ： １０５０ ℃ の如く起こるが、ｒ→δ→θと変化する際に。In other words, Albus's transformation is γ: 300-800℃ δ: 800~900℃ θ:900~1050℃ α: 1050℃ It occurs as follows, but when changing from r → δ → θ.
触媒活性が著しく低下することを見出した。It was found that the catalytic activity was significantly reduced.
（発明の構成）
本発明の排ガス浄化用触媒は、担体の少なくとも表（ｌ
ｔｉ ）２をδ−アルミナ、θ−アルミナまたはこれら
の混合物で形成し、該担体にノ独媒成分をｊ旦持さ亡た
。ことを１与４文とする。(Structure of the Invention) The exhaust gas purifying catalyst of the present invention has at least the surface (l) of the carrier.
ti)2 was formed from δ-alumina, θ-alumina or a mixture thereof, and the carrier was freed from the solvent component. Let's say 1 and 4 sentences.
本発明において、担体の形態は特に限定されない。具体
的には、アルミナｌこよって形成された分離型担体、た
とえば粒状担体°またはベレット状２ｍ体、またはコー
ジライト等からなる担体基材にアルミナを被覆して形成
された一体屓（モノリス）指体、九とえげハニカム状担
体が挙げられる。In the present invention, the form of the carrier is not particularly limited. Specifically, a separate carrier formed of alumina, such as a granular carrier or a pellet-shaped 2M body, or a monolithic finger formed by coating alumina on a carrier base material such as cordierite, is used. body, nine-thorn honeycomb-like carrier.
触媒成分としては、通常この棟の目的に使用されるもの
が使用でき、たとえば白金、ロジウム！たはパラジウム
などの貴金属単独まｆｃは組合ビたものが挙けられる。As catalyst components, those normally used for this purpose can be used, such as platinum, rhodium! Or a precious metal such as palladium alone or a combination of fc can be mentioned.
（実施例・比較例）
以下１本発明を実施例および比較Ｈにより詳細に祝明す
るう
実施例１〜３
コージライト質モノリス担体基材（直径３０關。(Examples and Comparative Examples) The present invention will be explained in detail below with reference to Examples and Comparative H. Examples 1 to 3 Cordierite monolith carrier base material (diameter 30 mm).
長は５０ ｍ＋＋ｔ ４円筒状）紫、以−Ｆの工程で触
媒化するっ
■ γ−アルミナを、８５０℃、９００℃および１０５
０℃の各温度で焼成して、δ−アルミナ。The length is 50 m++t (4 cylindrical) purple, and it will be catalyzed in the following process.
δ-alumina by firing at various temperatures of 0°C.
θ−アルミナまたはそれらの混合物を得るっ■ アルば
ナゾル（−ｒルミブー「有半１０＜五七チン３００部、
硝酸アルξニウム６０都、蒸１ｇ水３００〜４００部、
炭酸ランタン（焼成によって約４２％の酸化ランタンに
なるもの）４０部および＋ｊｌ記■で得られたアルミナ
５３ｏ１ｆｌＸを混合してスラリーとする。このスラリ
ー中に、＃記担体基材を２分間浸漬し、引き上げて担体
基材セル内のスラリーを空気流で吹き飛ばし、１５０℃
で３時間乾燥した後、６００・℃の温度で３時間焼成し
て触媒担体を得る。To obtain θ-alumina or a mixture thereof, Albanazol (-r Lumibou 10 < 57 300 parts,
60 parts of aluminum nitrate, 1 g of steamed water, 300-400 parts,
40 parts of lanthanum carbonate (which becomes about 42% lanthanum oxide upon calcination) and the alumina 53o1flX obtained in step 2 are mixed to form a slurry. The carrier base material marked with # was immersed in this slurry for 2 minutes, then pulled out and the slurry in the carrier base material cells was blown away with an air flow, and the temperature was raised to 150°C.
After drying for 3 hours at a temperature of 600.degree. C. for 3 hours, a catalyst carrier is obtained.
■ 前記■で得られた触媒担体を、硝酸第一七リウム溶
液、白金ＰソルトＢ液そして塩化ロジウム６敢にに面す
ることにより、活性層にセリウム、白金およびロジウム
を吸着させる。(2) The catalyst carrier obtained in (1) above is exposed to a heptadium nitrate solution, platinum P salt solution B, and rhodium chloride to adsorb cerium, platinum, and rhodium onto the active layer.
そして、これを乾燥、焼成して触媒化することによって
、本発明触媒Ａ（８５０℃で焼成したもの）、Ｂ（９０
０℃で焼成したもの）、Ｃ（１０５０℃で焼成したもの
）を得る。担持量は、担体１ノあたｊ） 、 ＣｅＯ２
ｏ、 ３モル、 ｉ’ｔ Ｌ Ｏ！およびＲｈＯ，１、
Ｐである。Then, by drying and calcining this to catalyze it, the present invention catalysts A (calcined at 850°C) and B (90°C
(fired at 0°C) and C (fired at 1050°C). The supported amount is per carrier 1), CeO2
o, 3 moles, i't L O! and RhO,1,
It is P.
比較例１〜３ アルミナとして、γ−アルミナを７００℃。Comparative examples 1 to 3 As alumina, γ-alumina was heated at 700°C.
１１５０℃および１２５’Ｏ℃で焼成してなるものを用
いる以外、前記実施例と同様にして、比較触媒ａ（７０
０℃で焼成し７にもの）、ｂ （１１５０℃で焼成した
もの）、Ｃ（１２５０℃で焼成したもの）を萄・る。Comparative catalyst a (70
7), b (fired at 1150°C), and C (fired at 1250°C).
（試験例）
次に、実施例および比較１＋ｌＪの触媒を耐久試験に洪
し２耐久試験後の触媒について、ノ弦媒粘性（浄化率）
を比較したう
ＣＩ）＃久試験
各触媒を金属−容器に装契し、とｉｌを自動車のエンジ
ン排気系に取付け、実鑵にＪノｔガスを流す仁とによシ
行なう。この場・−・において、試験条件は次のように
設定した。(Test example) Next, the catalysts of Example and Comparison 1 + lJ were subjected to a durability test.
Compare CI) #long test Load each catalyst in a metal container, attach it to the engine exhaust system of a car, and run the J-not gas through it. In this case, the test conditions were set as follows.
空ソ然比（Ａ／Ｆ） ：朽１６ 試験時間（時間）：５０ 触媒床Ｑ度（１：：） ：ＦＪｓｏ。Sora ratio (A/F): 16 Exam time (hours): 50 Catalyst bed Q degree (1::): FJso.
空間速度（１／時）二約６万
（２） 活性評価
耐久試験後の谷触媒に、次の条件で笈ツｂガスを通じて
、 ｌ−ＩＣ，ＣＯをば〆化さビるとともにＮＯｘを環
元させ、ＨＣ，ＣＯおよびＮＯｘの浄化率を測定する。Space velocity (1/hour): Approximately 60,000 (2) After the activity evaluation durability test, the Tani catalyst was passed under the following conditions to oxidize l-IC and CO and to ring NOx. The purification rate of HC, CO and NOx is measured.
加熱１１犠度 ＩＣ） 二 ３００ 空間速υｔ（１／時）：約８万 この場合において、変動ガス１ｊｃｏ：０．８％。Heating 11 sacrifice IC) 2 300 Space velocity υt (1/hour): Approximately 80,000 In this case, variable gas 1jco: 0.8%.
心ＪＯｘ ： ２２００ｐｐｍ 、’ ＨＣとしてＣ３
Ｈ６： ２２００ｐｐｍ、 ０２ ： ０．８％、、
Ｈ２： ０．２７％、Ｈ２Ｏ： ＃１０係、Ｃｏ２：１
０褒、Ｎ２：残シのモデルガスに。Mind JOx: 2200ppm,'C3 as HC
H6: 2200ppm, 02: 0.8%,,
H2: 0.27%, H2O: #10, Co2: 1
0 reward, N2: For remaining model gas.
過剰の０２、Ｃ０２を各々２多、０．５ ）１２で交互
に心入したもので、ちる。Excess 02 and C02 are added alternately by 2 and 0.5)12, respectively, and it is removed.
測定詰呆を、図に示す。The measurement packing is shown in the figure.
仁の結果から明ら〃）なように、実施列に係る触媒Ａ、
１３．Ｃは、比較例ａ、ｂ、ｃに比して。As is clear from the results of Jin), catalyst A according to the practical sequence,
13. C is compared to Comparative Examples a, b, and c.
高ｒ品１１吋久住に１２れる。。High quality item 11 inches long and 12 times tall. .
（発明の効果）
以−Ｈの如く、本発明によれば、使用中におけるアルば
すの燕夕ご悪が抑制されるので、ｄη述した技術的課、
小ケ屏消Ｃさる、という効果を突する。(Effects of the Invention) As shown in I-H, according to the present invention, the problem of swallowing of Albus during use is suppressed, so that the technical issues mentioned above,
It uses the effect of ``Small Screening C Saru''.
徒だ、ノｇ発明に係るノ独媒ば、（γ−アルミナのもの
に比して）アル（”す細孔径が大きい範囲に分布してい
るので、燐、硫黄等ｐ被舟物質によって細孔が閉塞され
にくく、したがつて、耐被梼性にも浸れる、という効果
を萎する。It's a waste, because the pore size of Al (compared to that of γ-alumina) is distributed over a large range, so the pore diameters of the pores of the invention are distributed over a large range, so phosphorus, sulfur, etc. The pores are less likely to be clogged, thus reducing the effect of providing water resistance.
図ｔｉ、芙施例に係る揖媒Ａ 、 Ｂ 、 ＣＪ−よび
比較・詞に係る触媒ａ、ｂ、ｃについて、＋：ｉｌｊ久
試ｌ倹後の触媒活性を示したグラフ、を表わすっ特許出
願人 トヨタ自動車株式会社
（（２′ｔか１名ンFigure 1 represents a graph showing the catalytic activity of catalysts A, B, and CJ- according to Example 3 and catalysts a, b, and c according to comparative examples. Applicant: Toyota Motor Corporation ((2't or 1 person)
Claims (1)
はこれらの混合物で形成した担体に触媒成分をづ旦コ苛
さ亡てなる。排ガス浄化用触媒。The catalyst components are then impregnated onto a support formed of δ-alumina, θ-alumina, or a mixture thereof, at least on the surface. Catalyst for exhaust gas purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58133145A JPS6025544A (en) | 1983-07-21 | 1983-07-21 | Catalyst for purifying exhaust gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58133145A JPS6025544A (en) | 1983-07-21 | 1983-07-21 | Catalyst for purifying exhaust gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6025544A true JPS6025544A (en) | 1985-02-08 |
Family
ID=15097780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58133145A Pending JPS6025544A (en) | 1983-07-21 | 1983-07-21 | Catalyst for purifying exhaust gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6025544A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5439865A (en) * | 1992-07-30 | 1995-08-08 | Ngk Insulators, Ltd. | Catalyst for exhaust gas purification and process for production thereof |
| KR100388030B1 (en) * | 1998-12-21 | 2003-09-19 | 주식회사 포스코 | Method for preparing lanthanum-containing thermal stabilized alumina by electrodeposition precipitation |
| WO2004004899A1 (en) * | 2002-07-09 | 2004-01-15 | Daihatsu Motor Co., Ltd. | Method for producing catalyst for clarifying exhaust gas |
| JP2004243305A (en) * | 2002-10-11 | 2004-09-02 | Daihatsu Motor Co Ltd | Exhaust gas purifying catalyst |
| JP2004243306A (en) * | 2002-10-11 | 2004-09-02 | Daihatsu Motor Co Ltd | Method for producing exhaust gas purifying catalyst |
| US7381394B2 (en) | 2002-07-09 | 2008-06-03 | Daihatsu Motor Co., Ltd. | Method for producing perovskite-type composite oxide |
-
1983
- 1983-07-21 JP JP58133145A patent/JPS6025544A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5439865A (en) * | 1992-07-30 | 1995-08-08 | Ngk Insulators, Ltd. | Catalyst for exhaust gas purification and process for production thereof |
| KR100388030B1 (en) * | 1998-12-21 | 2003-09-19 | 주식회사 포스코 | Method for preparing lanthanum-containing thermal stabilized alumina by electrodeposition precipitation |
| WO2004004899A1 (en) * | 2002-07-09 | 2004-01-15 | Daihatsu Motor Co., Ltd. | Method for producing catalyst for clarifying exhaust gas |
| WO2004004898A1 (en) * | 2002-07-09 | 2004-01-15 | Daihatsu Motor Co., Ltd. | Catalyst for clarifying exhaust gas |
| US7205257B2 (en) | 2002-07-09 | 2007-04-17 | Daihatsu Motor Co., Ltd. | Catalyst for clarifying exhaust gas |
| US7381394B2 (en) | 2002-07-09 | 2008-06-03 | Daihatsu Motor Co., Ltd. | Method for producing perovskite-type composite oxide |
| US7622418B2 (en) | 2002-07-09 | 2009-11-24 | Daihatsu Motor Company, Ltd. | Method for producing exhaust gas purifying catalyst |
| JP2004243305A (en) * | 2002-10-11 | 2004-09-02 | Daihatsu Motor Co Ltd | Exhaust gas purifying catalyst |
| JP2004243306A (en) * | 2002-10-11 | 2004-09-02 | Daihatsu Motor Co Ltd | Method for producing exhaust gas purifying catalyst |
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