JPS6377544A - Catalyst for purifying exhaust gas - Google Patents
Catalyst for purifying exhaust gasInfo
- Publication number
- JPS6377544A JPS6377544A JP61219808A JP21980886A JPS6377544A JP S6377544 A JPS6377544 A JP S6377544A JP 61219808 A JP61219808 A JP 61219808A JP 21980886 A JP21980886 A JP 21980886A JP S6377544 A JPS6377544 A JP S6377544A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- catalyst
- rare earth
- oxide
- activated alumina
- 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 42
- 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 32
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 53
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 26
- 229910052763 palladium Inorganic materials 0.000 claims description 24
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 17
- 239000010948 rhodium Substances 0.000 claims description 16
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052703 rhodium Inorganic materials 0.000 claims description 15
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 7
- -1 rare earth salt Chemical class 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 17
- 229910052697 platinum Inorganic materials 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical group [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 3
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical class [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical class [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical class [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical class [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、車両の内燃機関等、特に自動車の内燃機関
から排出される排気ガス中の窒素酸化物（ＮＯｘ）、炭
化水素（ＩＣ）および−酸化炭素（ＣＯ）を効率よく低
減させる排気ガス浄化用触媒に関する。Detailed Description of the Invention (Industrial Application Field) This invention is directed to the treatment of nitrogen oxides (NOx), hydrocarbons (IC) and -Regarding an exhaust gas purification catalyst that efficiently reduces carbon oxide (CO).
（従来の技術）
従来、車両の機関等から排出される排気ガス中のＮＯｘ
、 ｌ（Ｃ，Ｃｏを浄化する排気ガス浄化用触媒は種々
提案されている。一方希土類酸化物を触媒として又担体
に用いることも研究され、なかでもセリウムは活性アル
ミナに適当量添加されると耐熱性が著しく向上すること
からあらかじめ酸化セリウムを含有させた活性アルミナ
粉末をモノリス担体基材の表面に付着させた後、白金、
ロジウム、パラジウム等の触媒金属をそれぞれ単独ある
いは組合わせて担持した触媒等が提案されており、例え
ば特開昭５２−１１６７７９号、特開昭５４−１５９３
９２号公報などに開示されている。(Conventional technology) Conventionally, NOx in exhaust gas emitted from vehicle engines, etc.
Various exhaust gas purification catalysts have been proposed to purify C and Co. On the other hand, research has also been conducted on the use of rare earth oxides as catalysts and as supports. Platinum,
Catalysts supporting catalytic metals such as rhodium and palladium, either singly or in combination, have been proposed; for example, JP-A-52-116779 and JP-A-54-1593
This is disclosed in Publication No. 92, etc.
（発明が解決しようとする問題点）
しかしながら、このような従来の排気ガス浄化用触媒に
あっては、白金、ロジウム、パラジウム等の貴金属がウ
オツシュコーテイング層中に均一に担持されていたため
、特に被毒に弱いパラジウムについてはウオツシュコー
テイング層表面近くに担持された部分は劣化しやすいと
いう問題があった。(Problems to be Solved by the Invention) However, in such conventional exhaust gas purification catalysts, noble metals such as platinum, rhodium, palladium, etc. are uniformly supported in the wash coating layer. Palladium, which is susceptible to poisoning, has a problem in that the portion supported near the surface of the wash coating layer is susceptible to deterioration.
（問題点を解決するための手段）
この発明は活性アルミナに酸化ランタンを生成分とする
希土類酸化物とパラジウムを担持せしめて得た粉末を内
側のコーティング層に用い、ウォッシュコート表面近く
の被毒物質からパラジウムを遠ざけることにより上記問
題点を解決し得ることを知見したことに基づくものであ
る。(Means for Solving the Problems) This invention uses a powder obtained by supporting a rare earth oxide and palladium containing lanthanum oxide on activated alumina for the inner coating layer, and prevents poisoning near the washcoat surface. This is based on the discovery that the above problems can be solved by keeping palladium away from the substance.
従ってこの発明の排気ガス浄化用触媒は酸化ランタンを
主成分とする希土類酸化物とパラジウムを担持する活性
アルミナを含む第１のウオ・７シユコ一ト層と、この第
１のウォッシュコート層上に酸化セリウムを主成分とす
る希±１ａ化物を担持する活性アルミナと酸化ジルコニ
ウムを含む第２のウォッシュコート層を備えた触媒担体
にロジウムが担持されていることを特徴とする。尚、本
発明の触媒には、浄化性能向上のため、第１のウォッシ
ュコート層及び／または第２のウォッシュコート層に白
金を担持させてもよい。Therefore, the exhaust gas purifying catalyst of the present invention has a first wash coat layer containing a rare earth oxide mainly composed of lanthanum oxide and activated alumina supporting palladium, and a first wash coat layer on the first wash coat layer. The present invention is characterized in that rhodium is supported on a catalyst carrier having a second wash coat layer containing activated alumina and zirconium oxide, which supports a diluted 1a compound containing cerium oxide as a main component. In addition, in the catalyst of the present invention, platinum may be supported on the first washcoat layer and/or the second washcoat layer in order to improve the purification performance.
次にこの発明の触媒の製造方法を説明する。Next, a method for producing the catalyst of the present invention will be explained.
先ず活性アルミナをランタンを主成分とする希土類塩水
溶液に含浸後乾燥し、例えば６００℃で１時間、空気中
で焼成し、アルミナに対して希土類酸化物を金属換算で
３〜１０重量％含む担体を得る。First, activated alumina is impregnated with a rare earth salt aqueous solution containing lanthanum as a main component, dried, and calcined in air at, for example, 600°C for 1 hour to form a carrier containing 3 to 10% by weight of rare earth oxides based on the alumina in terms of metal. get.
ランタンを主成分とする希土類塩は９０重呈％以上がラ
ンタン塩であり、残部はプラセオジウム、ネオジウム、
サマリウム、ユーロピウム、ジスプロシウム、イッテリ
ビウム等の塩である。この内特にプラセオジウム、ネオ
ジウムはアルミナおよびセリウムの熱安定性を高めるの
に有効であり、含まれていると望ましい。この担体を塩
化パラジウム水溶液に含浸後、乾燥し、例えば４００〜
６００°Ｃで１時間空気中で焼成し、アルミナに対して
パラジウムを０．１〜１重量％含む担体を得る。次にこ
の担体とアルミナゾル（ベーマイトアルミナ懸濁液に硝
酸を添加して得られるゾル）を混合、粉砕した後、触媒
担体、例えばモノリス担体基材に付着させ、例えば４０
０〜６５０℃の温度で焼成し、第１層のウォッシュコー
トを得る。More than 90% of the rare earth salts whose main component is lanthanum are lanthanum salts, and the remainder is praseodymium, neodymium,
Salts of samarium, europium, dysprosium, ytterbium, etc. Among these, praseodymium and neodymium are particularly effective in increasing the thermal stability of alumina and cerium, and are preferably included. After impregnating this carrier with an aqueous palladium chloride solution, it is dried and
Calcination is performed in air at 600° C. for 1 hour to obtain a carrier containing 0.1 to 1% by weight of palladium based on alumina. Next, this carrier and alumina sol (a sol obtained by adding nitric acid to a boehmite alumina suspension) are mixed and pulverized, and then attached to a catalyst carrier, for example, a monolithic carrier base material.
Firing at a temperature of 0 to 650°C yields a first layer washcoat.
次に活性アルミナをセリウムを主成分とする希土類塩（
セリウム９０％以上、残部はプラセオジウム、ネオジウ
ム、サマリウム、ユーロピウム、ジスプロシウム、イフ
テリビウム等）水溶液に含浸後乾燥し、例えば６００℃
、１時間で空気中で焼成し、アルミナに対して希土類酸
化物を金属換算で１〜５重量％含む担体を得る。この担
体とアルミナゾルと酸化ジルコニウム粉末を混合粉砕し
た後、前記の第１のウォッシュコート層上に付着させ、
例えば４００〜６５０℃の温度で焼成した。しかる後白
金及び／またはロジウムの塩酸酸性混合溶液を用い特定
条件下で含浸し、所定量の貴金属を所定比率で担持し、
乾燥した後、空気雰囲気中で５５０〜６００°Ｃで０．
５時間以上焼成して排気ガス浄化用触媒を得る。Next, activated alumina is added to a rare earth salt containing cerium as the main component (
After impregnating in an aqueous solution (90% or more of cerium, the remainder being praseodymium, neodymium, samarium, europium, dysprosium, ifteribium, etc.), dry at 600°C.
, in air for 1 hour to obtain a carrier containing 1 to 5% by weight of rare earth oxide based on alumina in terms of metal. After mixing and pulverizing this carrier, alumina sol, and zirconium oxide powder, depositing it on the first wash coat layer,
For example, it was fired at a temperature of 400 to 650°C. After that, it is impregnated with an acidic mixed solution of platinum and/or rhodium in hydrochloric acid under specific conditions to support a predetermined amount of precious metals in a predetermined ratio.
After drying, heat at 550-600°C in an air atmosphere to 0.
The mixture is fired for 5 hours or more to obtain an exhaust gas purifying catalyst.
（作 用）
−ａにパラジウムは白金と同様酸化触媒として働き、特
にＣＯの酸化に有効であるが、被毒（特に鉛被前）に対
して弱い傾向にある。したがってコート層表面から、被
毒物質が浸透したところまでの部分に担持されたパラジ
ウムは被毒されて活性を失なってしまう。またパラジウ
ムは高温にさらされるとシンクリングし易く活性が低下
してしまう。本発明ではパラジウムの被毒を防止する目
的で、あらかじめパラジウムを担持したアルミナで第１
のウォッシュコート層を形成し、この層上に第２のウォ
ッシュコート層を形成する。この結果、被毒物質がパラ
ジウムの担持位置まで浸透せず、触媒の被毒に対する耐
久性が向上する。さらにパラジウムおよびロジウムの熱
安定性を向上させる目的でパラジウムを含むコート層に
は酸化ランタンを、ロジウムを含むコート層には酸化ジ
ルコニウムを添加する。これらの酸化物には金属と化合
物を形成し安定化させる働きがある。例えばパラジウム
は酸化セリウムとは化合物をつくらないが、酸化ランタ
ンとはしａ−０−Ｐｄなる表面化合物を形成するので触
媒の耐熱性能を高めるために第１層に用いる活性アルミ
ナにはあらかじめランタンを担持させる。(Function) Palladium (a) works as an oxidation catalyst like platinum, and is particularly effective in oxidizing CO, but tends to be weak against poisoning (particularly when exposed to lead). Therefore, the palladium supported in the area from the surface of the coating layer to the point where the poisonous substance has permeated is poisoned and loses its activity. Furthermore, when palladium is exposed to high temperatures, it tends to sink and its activity decreases. In the present invention, in order to prevent palladium from being poisoned, alumina pre-supported with palladium is used as the first material.
A washcoat layer is formed, and a second washcoat layer is formed on this layer. As a result, the poisoning substance does not penetrate to the palladium supported position, and the durability of the catalyst against poisoning is improved. Further, in order to improve the thermal stability of palladium and rhodium, lanthanum oxide is added to the coat layer containing palladium, and zirconium oxide is added to the coat layer containing rhodium. These oxides have the function of forming and stabilizing compounds with metals. For example, palladium does not form a compound with cerium oxide, but it forms a surface compound called a-0-Pd with lanthanum oxide, so in order to improve the heat resistance of the catalyst, lanthanum is added to the activated alumina used in the first layer in advance. carry it.
（実施例） 次に実施例、比較例および試験例により説明する。(Example) Next, examples, comparative examples, and test examples will be explained.
ス新ｌ生１
粒状活性アルミナ担体を、ランタンを主成分とする希土
類硝酸塩水溶液に含浸した後、乾燥し、６００℃１時間
空気中で焼成し、アルミナに対して希土類酸化物を金属
換算で５重量％含む担体を得た。希土類酸化物中７０〜
９５％が酸化ランタンであり、残りは酸化セリウム、酸
化プラセオジウム、酸化ネオジウムを含む。この担体を
塩化パラジウム水溶液に含浸後乾燥し、６００℃１時間
空気中で焼成しアルミナに対してパラジウムを０．２重
量％含む担体を得た。この担体１５００ ｇと硝酸酸性
アルミナゾル２５００ ｇをボールミルに混ぜ込み６時
間粉砕したのち、このアルミナを含む液（以下コーテイ
ング液Ａと呼ぶ）をモノリス担体基材（１，１４００セ
ル）に付着させ焼成（６００℃×２時間）した。After impregnating a granular activated alumina carrier with a rare earth nitrate aqueous solution containing lanthanum as the main component, it was dried and calcined in air at 600°C for 1 hour, and the amount of rare earth oxide was 5% in terms of metal compared to the alumina. A carrier containing % by weight was obtained. 70~ in rare earth oxides
95% is lanthanum oxide, and the remainder includes cerium oxide, praseodymium oxide, and neodymium oxide. This carrier was impregnated with an aqueous palladium chloride solution, dried, and calcined in air at 600°C for 1 hour to obtain a carrier containing 0.2% by weight of palladium based on alumina. 1,500 g of this carrier and 2,500 g of nitric acidic alumina sol were mixed in a ball mill and pulverized for 6 hours, and then this alumina-containing liquid (hereinafter referred to as coating liquid A) was adhered to a monolithic carrier base material (1,1400 cells) and baked ( 600°C x 2 hours).
この時の付着量は２２０ ｇ ／個に設定した。これが
第１のウォッシュコート層である。The amount of adhesion at this time was set at 220 g/piece. This is the first washcoat layer.
次に粒状活性アルミナ担体を、セリウムを主成分とする
希土類硝酸塩水溶液に含浸後乾燥し、６００℃で１時間
空気中で焼成し、アルミナに対して希土類酸化物を金属
換算で３重量％含む担体を得た。Next, the granular activated alumina support was impregnated with a rare earth nitrate aqueous solution containing cerium as a main component, dried, and calcined in air at 600°C for 1 hour. I got it.
希土類酸化物中７０〜９５％が酸化セリウムであり、残
りは酸化ランタン、酸化プラセオジウム、酸化ネオジウ
ムを含む。この担体１５００ ｇ 、 Ｆ、ｆ化ジルコ
ニウム１００ ｇ、硝酸酸性アルミナゾル２５００ ｇ
をボールミルに混ぜ込み６時間粉砕した後、この液（コ
ーテイング液Ｂ）を前記の第１のウォッシュコート層の
上に付着させ焼成（６００°ＣＸ２時間）した。70 to 95% of the rare earth oxide is cerium oxide, and the remainder includes lanthanum oxide, praseodymium oxide, and neodymium oxide. 1500 g of this carrier, 100 g of F, zirconium fluoride, 2500 g of nitric acid acidic alumina sol
After mixing in a ball mill and pulverizing for 6 hours, this liquid (coating liquid B) was deposited on the first wash coat layer and baked (at 600° C. for 2 hours).
この時の付着量は２００ ｇ ／個に設定した。さらに
この付着した担体に白金０．４０ｇ、ロジウム０．１５
ｇになるように担持した後焼成（６００℃×２時間）し
、触媒１を得た。The amount of adhesion at this time was set at 200 g/piece. Furthermore, 0.40 g of platinum and 0.15 g of rhodium were added to the adhered carrier.
After supporting the catalyst so as to give a weight of 1.5 g, the catalyst was calcined (600° C. for 2 hours) to obtain catalyst 1.
尖施±１
実施例１においてアルミナに対して酸化ランタンを主成
分とする希土類酸化物を金属換算で３重量％にした以外
同様にして触媒２を得た。1. Catalyst 2 was obtained in the same manner as in Example 1 except that the amount of rare earth oxide mainly composed of lanthanum oxide was 3% by weight in terms of metal relative to the alumina.
大侮桝主
実施例１においてアルミナに対して酸化ランタンを主成
分とする希土類酸化物を金属換算で１０重量％にした以
外同様にして触媒３を得た。Catalyst 3 was obtained in the same manner as in Example 1 except that the rare earth oxide containing lanthanum oxide as the main component was changed to 10% by weight in terms of metal relative to the alumina.
去庭開↓
実施例１において酸化ジルコニウムを５０ｇに変えた以
外同様にして触媒４を得た。Kai Shiba ↓ Catalyst 4 was obtained in the same manner as in Example 1 except that zirconium oxide was changed to 50 g.
実隻炭工
実施例１において酸化ジルコニウムを１５０ｇに変えた
以外同様にして触媒５を得た。Catalyst 5 was obtained in the same manner as in Example 1 except that the amount of zirconium oxide was changed to 150 g.
尖ル拠ｉ
実施例１においてパラジウム０．１５重世％、白金０．
３０ｇ、ロジウム０．１０ ｇに変えた以外同様にして
触媒６を得た。In Example 1, 0.15% palladium and 0.15% platinum were used.
Catalyst 6 was obtained in the same manner except that the amount of rhodium was changed to 30 g and 0.10 g of rhodium.
尖立開ユ
実施例１においてパラジウムの担持量を２倍にし、白金
を担持させるのをやめた以外同様にして触媒７を得た。Catalyst 7 was obtained in the same manner as in Example 1 except that the amount of palladium supported was doubled and platinum was not supported.
大侮開主
実施例１においてパラジウム０．２重量％を０．４重量
％に、白金０．４０ｇをパラジウム０．８０ｇに、ロジ
ウム０．１５ｇを０．３０ｇに変える以外同様にして触
媒８を得た。Catalyst 8 was prepared in the same manner as in Example 1 except that 0.2% by weight of palladium was changed to 0.4% by weight, 0.40g of platinum was changed to 0.80g of palladium, and 0.15g of rhodium was changed to 0.30g. Obtained.
ル較■土
実施例１において酸化ランタンを主成分とする希土類酸
化物を含まないものに変えた以外同様にして触媒Ａを得
た。Comparative Example 2 Catalyst A was obtained in the same manner as in Example 1 except that the catalyst was changed to one containing no rare earth oxide containing lanthanum oxide as the main component.
止較貞１
実施例１において酸化ジルコニウムを含まないものに変
えた以外同様にして触媒Ｂを得た。Stop Calibration 1 Catalyst B was obtained in the same manner as in Example 1 except that the catalyst did not contain zirconium oxide.
ル較貫ユ
実施例１において酸化ランタンを主成分とする希土類酸
化物を含まず、かつ酸化ジルコニウムを含まないものに
変えた以外同様にして触媒Ｃを得た。Catalyst C was obtained in the same manner as in Example 1, except that it did not contain a rare earth oxide containing lanthanum oxide as a main component and did not contain zirconium oxide.
此１シボ土
実施例１に記すコーテイング液Ａとコーテイング液Ｂを
同重量混合しこの混合液をモノリス担体基材Ｃ１，１１
，４００セル）に付着させ、焼成（６００’ｃ×２時間
）した。この時の付着量は４２０ ｇ ／個に設定した
。さらにこの付着した担体に白金０．４０ ｇ、ロジウ
ム０．１５ ｇになるように担持した後、焼成（６００
℃×２時間）し、触媒りを得た。This 1 Grained soil Mix the coating liquid A and the coating liquid B described in Example 1 by the same weight, and apply this mixed liquid to the monolithic carrier base material C1, 11.
, 400 cells) and fired (600'c x 2 hours). The amount of adhesion at this time was set at 420 g/piece. Furthermore, 0.40 g of platinum and 0.15 g of rhodium were supported on the adhered carrier, and then fired (600 g).
℃ x 2 hours) to obtain a catalyst.
ル鮫阻ｌ
実施例１に記すコーテイング液Ｂをモノリス担体基材（
１，７β、４００セル）に付着させ乾燥した。Coating liquid B described in Example 1 was applied to a monolithic carrier base (
1,7β, 400 cells) and dried.
この時の付着量は２００ ｇ ／個に設定した。この付
着した担体の上にコーティング液入を付着させ、焼成（
６００℃×２時間）した。この時の付着量は２２０ｇ／
個に設定した。さらにこの付着した担体に白金０．４０
ｇ、ロジウム０．１５ ｇになるように担持した後、６
００℃で２時間焼成し、触媒Ｅを得た。The amount of adhesion at this time was set at 200 g/piece. A coating liquid container is applied onto this adhered carrier and baked (
600°C x 2 hours). The amount of adhesion at this time is 220g/
It was set to 1. Furthermore, 0.40% platinum was added to this adhered carrier.
g, after supporting rhodium to 0.15 g, 6
Catalyst E was obtained by calcining at 00°C for 2 hours.
成」（炭
実施例１〜８から得た触媒１〜８、比較例１〜５から得
た触媒Ａ−Ｅについて、下記の条件で有鉛耐久を行ない
１０モードエミツシヨンの浄化率を評価し、得た結果を
表１に示した。Catalysts 1 to 8 obtained from Charcoal Examples 1 to 8 and Catalysts A to E obtained from Comparative Examples 1 to 5 were subjected to leaded durability under the following conditions and the purification rate of 10 mode emission was evaluated. The results obtained are shown in Table 1.
而 １ −
触 媒 モノリス型貴金属触媒エンジン
排気量 ２２００ ｃｃガソリン中ｐｂ含有ｆｆ
ｉ ５０ ｍｇ／ＩＩｓガロン触媒入ロガス温度
７５０℃
空間速度 約７万Ｈ−１
耐久時間 １００時間
入ロエミッション Ｇｏ ０．４〜０．６％０
ｆｆｉ ｏ、ｓ ±０．１ ％ＮＯ１５００
ｐｐｍ
ＨＣ１０００ｐｐｍ
Ｃ０ｚ １４．９±０．１ ％
−表一一」一
本ランタンを主成分とする希土類酸化物。1-Catalyst Monolithic precious metal catalyst Engine displacement 2200 cc PB content in gasoline ff
i 50 mg/IIs gallon Catalyst log gas temperature
750℃ Space velocity Approximately 70,000H-1 Durability time 100 hours Low emission Go 0.4~0.6%0
ffi o,s ±0.1%NO1500
ppm HC1000ppm C0z 14.9±0.1 % -Table 11 Rare earth oxide whose main component is lanthanum.
（発明の効果）
以上説明してきたように、この発明によれば、その構成
を酸化ランタンを主成分とする希土類酸化物とパラジウ
ムを担持する活性アルミナを含む第１のウォッシュコー
トｉを形成し、その面上に酸化セリウムを主成分とする
希土類酸化物を担持する活性アルミナと酸化ジルコニウ
ムを含む第２のウォッシュコート層を設けた触媒担体上
にロジウムを担持させて構成したことにより、パラジウ
ムが被毒物質より遠ざけられ、またパラジウムが酸化ラ
ンタンと、ロジウムが酸化ジルコニウムと化合物を形成
し安定化する働きによりパラジウムおよびロジウムの耐
熱性を向上でき、長期に亘り触媒活性化の低下が生じな
いという効果が得られる。(Effects of the Invention) As explained above, according to the present invention, the first washcoat i is formed which includes a rare earth oxide mainly composed of lanthanum oxide and activated alumina supporting palladium, By having rhodium supported on a catalyst carrier having a second wash coat layer containing activated alumina and zirconium oxide supporting a rare earth oxide mainly composed of cerium oxide, palladium is covered. It is kept away from poisonous substances, and the heat resistance of palladium and rhodium can be improved by forming compounds with palladium and lanthanum oxide and rhodium and zirconium oxide to stabilize them, and the effect is that catalyst activation does not decrease over a long period of time. is obtained.
Claims (1)
ウムを担持する活性アルミナを含む第１のウォッシュコ
ート層と、この第１のウォッシュコート層上に酸化セリ
ウムを主成分とする希土類酸化物を担持する活性アルミ
ナと酸化ジルコニウムとを含む第２のウォッシュコート
層を備えた触媒担体にロジウムが担持されている排気ガ
ス浄化用触媒。1. A first washcoat layer containing a rare earth oxide mainly composed of lanthanum oxide and activated alumina supporting palladium, and a rare earth oxide mainly composed of cerium oxide supported on this first washcoat layer. An exhaust gas purifying catalyst in which rhodium is supported on a catalyst carrier having a second washcoat layer containing activated alumina and zirconium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61219808A JPS6377544A (en) | 1986-09-19 | 1986-09-19 | Catalyst for purifying exhaust gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61219808A JPS6377544A (en) | 1986-09-19 | 1986-09-19 | Catalyst for purifying exhaust gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6377544A true JPS6377544A (en) | 1988-04-07 |
Family
ID=16741358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61219808A Pending JPS6377544A (en) | 1986-09-19 | 1986-09-19 | Catalyst for purifying exhaust gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6377544A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5019546A (en) * | 1989-02-16 | 1991-05-28 | Mazda Motor Corporation | Catalyst for purifying exhaust gas and method of manufacturing the same |
| US5147842A (en) * | 1989-06-09 | 1992-09-15 | N.E. Chemcat Corporation | Exhaust gas-purifying catalyst and process for preparation thereof |
| US5212142A (en) * | 1991-11-04 | 1993-05-18 | Engelhard Corporation | High performance thermally stable catalyst |
| US5318757A (en) * | 1990-12-21 | 1994-06-07 | Ngk Insulators, Ltd. | Honeycomb heater and catalytic converter |
| US5702675A (en) * | 1994-12-16 | 1997-12-30 | Toyota Jidosha Kabushiki Kaisha | Catalyst for purifying exhaust gases and process for producing the same |
| US5898014A (en) * | 1996-09-27 | 1999-04-27 | Engelhard Corporation | Catalyst composition containing oxygen storage components |
| US5948723A (en) * | 1996-09-04 | 1999-09-07 | Engelhard Corporation | Layered catalyst composite |
| US5948377A (en) * | 1996-09-04 | 1999-09-07 | Engelhard Corporation | Catalyst composition |
| US5981427A (en) * | 1996-09-04 | 1999-11-09 | Engelhard Corporation | Catalyst composition |
| US6044644A (en) * | 1994-12-06 | 2000-04-04 | Engelhard Corporation | Close coupled catalyst |
| US6087298A (en) * | 1996-05-14 | 2000-07-11 | Engelhard Corporation | Exhaust gas treatment system |
| US6110862A (en) * | 1998-05-07 | 2000-08-29 | Engelhard Corporation | Catalytic material having improved conversion performance |
| US6248688B1 (en) | 1996-09-27 | 2001-06-19 | Engelhard Corporation | Catalyst composition containing oxygen storage components |
| US6261989B1 (en) | 1999-05-19 | 2001-07-17 | Daihatsu Motor Co., Ltd. | Catalytic converter for cleaning exhaust gas |
| US6464946B1 (en) | 1999-05-07 | 2002-10-15 | Daihatsu Motor Co., Ltd. | Catalytic converter for cleaning exhaust gas |
| US6576200B1 (en) | 1998-08-28 | 2003-06-10 | Daihatsu Motor Co., Ltd. | Catalytic converter for automotive pollution control, and oxygen-storing complex oxide used therefor |
| US6682706B1 (en) | 1998-12-09 | 2004-01-27 | Daihatsu Motor Co., Ltd. | Catalytic converter for automotive pollution control, and process for making catalytic converter |
| US6921738B2 (en) * | 1996-12-06 | 2005-07-26 | Engelhard Corporation | Catalytic metal plate |
| EP1977819A2 (en) | 1996-12-06 | 2008-10-08 | Basf Catalysts Llc | Catalytic metal plate |
| US7678347B2 (en) | 2005-07-15 | 2010-03-16 | Basf Catalysts Llc | High phosphorous poisoning resistant catalysts for treating automobile exhaust |
| US7749472B2 (en) | 2006-08-14 | 2010-07-06 | Basf Corporation | Phosgard, a new way to improve poison resistance in three-way catalyst applications |
-
1986
- 1986-09-19 JP JP61219808A patent/JPS6377544A/en active Pending
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5019546A (en) * | 1989-02-16 | 1991-05-28 | Mazda Motor Corporation | Catalyst for purifying exhaust gas and method of manufacturing the same |
| US5147842A (en) * | 1989-06-09 | 1992-09-15 | N.E. Chemcat Corporation | Exhaust gas-purifying catalyst and process for preparation thereof |
| US5318757A (en) * | 1990-12-21 | 1994-06-07 | Ngk Insulators, Ltd. | Honeycomb heater and catalytic converter |
| US5212142A (en) * | 1991-11-04 | 1993-05-18 | Engelhard Corporation | High performance thermally stable catalyst |
| US6044644A (en) * | 1994-12-06 | 2000-04-04 | Engelhard Corporation | Close coupled catalyst |
| US6254842B1 (en) | 1994-12-06 | 2001-07-03 | Engelhard Corporation | Method for using a close coupled catalyst |
| US5702675A (en) * | 1994-12-16 | 1997-12-30 | Toyota Jidosha Kabushiki Kaisha | Catalyst for purifying exhaust gases and process for producing the same |
| US6087298A (en) * | 1996-05-14 | 2000-07-11 | Engelhard Corporation | Exhaust gas treatment system |
| US5948377A (en) * | 1996-09-04 | 1999-09-07 | Engelhard Corporation | Catalyst composition |
| US5981427A (en) * | 1996-09-04 | 1999-11-09 | Engelhard Corporation | Catalyst composition |
| US5989507A (en) * | 1996-09-04 | 1999-11-23 | Engelhard Corporation | Catalyst composition |
| US5948723A (en) * | 1996-09-04 | 1999-09-07 | Engelhard Corporation | Layered catalyst composite |
| US5898014A (en) * | 1996-09-27 | 1999-04-27 | Engelhard Corporation | Catalyst composition containing oxygen storage components |
| US6248688B1 (en) | 1996-09-27 | 2001-06-19 | Engelhard Corporation | Catalyst composition containing oxygen storage components |
| US6921738B2 (en) * | 1996-12-06 | 2005-07-26 | Engelhard Corporation | Catalytic metal plate |
| EP1977819A2 (en) | 1996-12-06 | 2008-10-08 | Basf Catalysts Llc | Catalytic metal plate |
| US6110862A (en) * | 1998-05-07 | 2000-08-29 | Engelhard Corporation | Catalytic material having improved conversion performance |
| US6576200B1 (en) | 1998-08-28 | 2003-06-10 | Daihatsu Motor Co., Ltd. | Catalytic converter for automotive pollution control, and oxygen-storing complex oxide used therefor |
| US6682706B1 (en) | 1998-12-09 | 2004-01-27 | Daihatsu Motor Co., Ltd. | Catalytic converter for automotive pollution control, and process for making catalytic converter |
| US6464946B1 (en) | 1999-05-07 | 2002-10-15 | Daihatsu Motor Co., Ltd. | Catalytic converter for cleaning exhaust gas |
| US6261989B1 (en) | 1999-05-19 | 2001-07-17 | Daihatsu Motor Co., Ltd. | Catalytic converter for cleaning exhaust gas |
| US7678347B2 (en) | 2005-07-15 | 2010-03-16 | Basf Catalysts Llc | High phosphorous poisoning resistant catalysts for treating automobile exhaust |
| EP2781261A1 (en) | 2005-07-15 | 2014-09-24 | BASF Catalysts LLC | High phosphorous poisoning resistant catalysts for treating automobile exhaust |
| US7749472B2 (en) | 2006-08-14 | 2010-07-06 | Basf Corporation | Phosgard, a new way to improve poison resistance in three-way catalyst applications |
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