JP2002273239A - Method of manufacturing for alloy catalyst and catalyst for purifying exhaust gas - Google Patents
Method of manufacturing for alloy catalyst and catalyst for purifying exhaust gasInfo
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- JP2002273239A JP2002273239A JP2001072784A JP2001072784A JP2002273239A JP 2002273239 A JP2002273239 A JP 2002273239A JP 2001072784 A JP2001072784 A JP 2001072784A JP 2001072784 A JP2001072784 A JP 2001072784A JP 2002273239 A JP2002273239 A JP 2002273239A
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- metal
- catalyst
- exhaust gas
- slurry
- alloy catalyst
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高い排気ガス浄化
性能を有する合金触媒と排気ガス浄化用触媒の製造方法
に関する。The present invention relates to an alloy catalyst having high exhaust gas purification performance and a method for producing an exhaust gas purification catalyst.
【０００２】[0002]
【従来の技術】自動車用エンジン等の内燃機関から排出
される排気ガスには、窒素酸化物（ＮＯx）、一酸化炭
素（ＣＯ）、炭化水素（ＨＣ）のような有害物質が含ま
れ、これらは、一般に、アルミナ等の金属酸化物担体に
白金等の触媒成分が担持された三元触媒等の排気ガス浄
化用触媒によって浄化される。しかるに、環境保護のた
め、こうした排気ガス浄化用触媒は、より一層の高い排
気ガス浄化性能が要請されている。2. Description of the Related Art Exhaust gas emitted from an internal combustion engine such as an automobile engine contains harmful substances such as nitrogen oxides (NO x ), carbon monoxide (CO) and hydrocarbons (HC). These are generally purified by an exhaust gas purifying catalyst such as a three-way catalyst in which a catalyst component such as platinum is supported on a metal oxide carrier such as alumina. However, for environmental protection, such exhaust gas purifying catalysts are required to have even higher exhaust gas purifying performance.
【０００３】このため、本出願人は、先に、触媒成分の
金属を合金化することにより触媒活性を高めるといった
着想に基づき、特開平１１−１５６１９３号公報、特開
平１１−３４７４２４号公報において、金属粒子の上に
別な金属粒子を積相させた触媒を提案している。ここで
「積相」とは、１つの金属粒子の一部の表面が、１つ以
上の別な種類の金属粒子によって被覆され、それらの異
なる金属粒子の接合領域を介してそれぞれの金属の相が
存在する状態をいう。[0003] For this reason, based on the idea of increasing the catalytic activity by alloying the metal of the catalyst component, the present applicant has disclosed in Japanese Patent Application Laid-Open Nos. 11-156193 and 11-347424. A catalyst in which another metal particle is stacked on a metal particle is proposed. As used herein, the term “product phase” refers to a state in which a part of the surface of one metal particle is covered with one or more different types of metal particles, and the phase of each metal is bonded through the bonding region of the different metal particles. Refers to the state where exists.
【０００４】かかる積相構造を有する触媒は、排気ガス
浄化性能が顕著に改良され、ＮＯx、ＣＯ、ＨＣのいず
れについても、単一金属を触媒成分とした排気ガス浄化
用触媒に比較して浄化性能が改良され、とりわけ、ＣＯ
とＨＣの燃焼浄化について高い触媒作用を発揮すること
ができる。この理由は、金属粒子とその上に積相された
金属粒子の電子状態の違いから、それら金属粒子の表面
の電子状態が最適化されるためと考えられる。[0004] The catalyst having such a product phase structure has remarkably improved exhaust gas purifying performance, and it is possible to reduce NO x , CO, and HC in comparison with an exhaust gas purifying catalyst using a single metal as a catalyst component. Purification performance has been improved, and
And a high catalytic action for HC purification. It is considered that the reason for this is that the electronic state of the surface of the metal particles is optimized due to the difference in the electronic state between the metal particles and the metal particles stacked thereon.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、かかる
積相構造を有する触媒を再現性よく安定して製造するに
は、特有の困難性があり、特定の限定された方法によら
なければ、高い浄化性能を発現する排気ガス浄化用触媒
が製造され難いことが判明した。したがって、本発明
は、高い排気ガス浄化性能を呈する上記の積相構造を有
する触媒を、再現性よく安定して製造する方法を提供す
ることを目的とする。However, there is a particular difficulty in stably producing a catalyst having such a product phase structure with good reproducibility, and high purification is required unless a specific limited method is used. It has been found that it is difficult to manufacture an exhaust gas purifying catalyst exhibiting performance. Therefore, an object of the present invention is to provide a method for stably producing a catalyst having the above-described accumulated phase structure exhibiting high exhaust gas purification performance with good reproducibility.
【０００６】[0006]
【課題を解決するための手段】上記の目的は、金属酸化
物担体上に第１金属を担持させる第１工程、第１工程で
担持された第１金属の上に、第２金属を還元析出させて
積相構造の合金触媒を調製する第２工程、及び第２工程
で得られた合金触媒を排気ガス通路付担体に担持させる
第３工程の各工程を、それぞれ適正化することによって
達成される。The object of the present invention is to provide a first step in which a first metal is supported on a metal oxide support, and a second step in which a second metal is reduced and deposited on the first metal supported in the first step. This is achieved by optimizing the second step of preparing the alloy catalyst having the accumulated phase structure and the third step of supporting the alloy catalyst obtained in the second step on a carrier with an exhaust gas passage. You.
【０００７】本発明の方法において、第１工程は、第１
金属粒子の表面状態を適正化する処理を含むことがで
き、これにより、第２金属粒子が第１金属粒子の上に安
定して積相されるものと考えられる。第２工程は、第２
金属を還元析出させる際に、主として、第１金属の溶出
を防ぐことにより、適切な積相構造を有する合金触媒が
安定して形成されるものと考えられる。[0007] In the method of the present invention, the first step includes the first step.
It may include a treatment for optimizing the surface state of the metal particles, whereby the second metal particles are considered to be stably accumulated on the first metal particles. The second step is a second step.
It is considered that an alloy catalyst having an appropriate accumulated phase structure is formed stably mainly by preventing the elution of the first metal when the metal is reduced and precipitated.
【０００８】第３工程は、合金触媒を排気ガス通路付担
体に担持する際に、主として、第１金属の溶出を防ぐこ
とにより、積相構造が維持されながら、合金触媒が排気
ガス通路付担体に担持されるものと考えられる。これら
の適正化された工程は、好ましくは、第１〜３工程が全
て適正化されるが、いずれか１工程又は２工程を適正化
することによっても、浄化性能が向上された排気ガス浄
化用触媒を得ることができる。図１は、これら工程の概
略のフローチャートである。In the third step, when the alloy catalyst is supported on the carrier with an exhaust gas passage, the alloy catalyst is mainly maintained by preventing elution of the first metal while maintaining the accumulated phase structure. It is considered to be carried on. In these optimized steps, preferably, all of the first to third steps are optimized. However, by optimizing any one or two steps, it is also possible to improve the purification performance for exhaust gas purification. A catalyst can be obtained. FIG. 1 is a schematic flowchart of these steps.
【０００９】[0009]
【発明の実施の形態】本発明の方法は、第１工程におい
て、第１金属が担持された金属酸化物担体を調製する。
ここで、金属酸化物担体には、アルミナ、シリカ、シリ
カ−アルミナ、ゼオライト、ジルコニア、セリア、ジル
コニア−セリア、又はこれらの混合物もしくは複合酸化
物からなるものが好適に使用可能である。DETAILED DESCRIPTION OF THE INVENTION In the method of the present invention, in a first step, a metal oxide support carrying a first metal is prepared.
Here, as the metal oxide carrier, alumina, silica, silica-alumina, zeolite, zirconia, ceria, zirconia-ceria, or a mixture of these or a composite oxide can be suitably used.
【００１０】第１金属は、ｓ−ブロック金属元素、ｄ−
ブロック金属元素、ｐ−ブロック金属元素、及びｆ−ブ
ロック金属元素から広範囲に選択されることができ、好
ましくは、白金、金、パラジウム、ルテニウム、ロジウ
ムのような貴金属である。The first metal is an s-block metal element, d-
It can be selected from a wide range of block metal elements, p-block metal elements, and f-block metal elements, and is preferably a noble metal such as platinum, gold, palladium, ruthenium, and rhodium.
【００１１】金属酸化物担体上に第１金属を担持するの
は、担体上に金属粒子を堆積させることができる任意の
方法から選択された、例えば、蒸発乾固法、沈殿法、イ
オン交換法、吸着法、還元析出法等によって行うことが
できる。次いで、好ましくは、大気中で３００〜９００
℃の温度に数時間加熱することにより、担持された金属
を担体に強固に固定することができる。The loading of the first metal on the metal oxide support may be selected from any method capable of depositing metal particles on the support, for example, evaporating to dryness, precipitation, ion exchange. , Adsorption method, reduction precipitation method and the like. Then, preferably, 300 to 900 in the atmosphere.
By heating to a temperature of ° C for several hours, the supported metal can be firmly fixed to the carrier.
【００１２】第１工程において、好ましい態様として、
このようにして金属酸化物担体上に第１金属を担持した
後、第１金属に還元処理を施す。これは、上記のように
して金属酸化物担体上に担持された第１金属の粒子は、
多くは表面に酸素が結合しており、この酸素を還元処理
によって除去することで、第２工程において、第２金属
の粒子が安定して積相されるためと考えられる。[0012] In the first step, as a preferred embodiment,
After carrying the first metal on the metal oxide carrier in this way, the first metal is subjected to a reduction treatment. This is because the particles of the first metal supported on the metal oxide support as described above are:
It is considered that in most cases, oxygen is bonded to the surface, and by removing this oxygen by reduction treatment, particles of the second metal are stably accumulated in the second step.
【００１３】この還元処理は、具体的には、テトラヒド
ロホウ酸ナトリウムＮａＢＨ4のような比較的還元力の
強い化合物を、第１金属を担持した金属酸化物担体のス
ラリーに添加し、好ましくは攪拌しながら、必要により
スラリーを加熱することで行うことができる。あるい
は、Ｈ2、ＣＯ、ＮＨ3のような還元性ガスを、好ましく
は、０.５〜１０体積％、より好ましくは、１〜５体積
％で含む窒素やアルゴン等のガス雰囲気中で、第１金属
を担持した金属酸化物担体を、好ましくは、３００〜１
０００℃の温度で５分間〜１０時間、より好ましくは、
４００〜５００℃温度で１０分間〜５時間の加熱に供す
ることにより還元処理を行うことができる。In the reduction treatment, specifically, a compound having a relatively strong reducing power, such as sodium tetrahydroborate NaBH 4 , is added to the slurry of the metal oxide carrier supporting the first metal, preferably with stirring. It can be performed by heating the slurry, if necessary. Alternatively, a reducing gas such as H 2 , CO, and NH 3 is preferably contained in a gas atmosphere such as nitrogen or argon containing 0.5 to 10% by volume, more preferably 1 to 5% by volume. The metal oxide carrier supporting one metal is preferably 300 to 1
5 minutes to 10 hours at a temperature of 000 ° C., more preferably
The reduction treatment can be performed by subjecting to heating at a temperature of 400 to 500 ° C. for 10 minutes to 5 hours.
【００１４】次に、第２工程として、第１工程で金属酸
化物担体上に担持された第１金属の上に、第２金属を還
元析出させて積相構造の合金触媒を調製する。ここで
「還元析出」とは、溶液中で金属イオンを生成する金属
化合物の溶液に還元剤を添加し、金属イオンを還元して
不溶性にすることで、その金属化合物の金属を析出させ
ることのほか、金属化合物中で正電荷を帯びたイオン結
合性を有する金属原子を、金属として析出させることを
含む。Next, as a second step, the second metal is reduced and precipitated on the first metal supported on the metal oxide support in the first step to prepare an alloy catalyst having a stacked phase structure. Here, "reduction precipitation" refers to the process of adding a reducing agent to a solution of a metal compound that generates metal ions in a solution, and reducing the metal ions to make them insoluble, thereby precipitating the metal of the metal compound. In addition, the method includes depositing a positively charged metal atom having ionic bonding property in a metal compound as a metal.
【００１５】第２金属は、第１金属と同様に、ｓ−ブロ
ック金属元素、ｄ−ブロック金属元素、ｐ−ブロック金
属元素、及びｆ−ブロック金属元素の、第１金属以外の
金属から広範囲に選択されることができる。好ましく
は、第２金属は、第１金属以外の貴金属又は遷移金属で
あり、ここで「遷移金属」とは、周期律表の３Ａ〜７Ａ
族、８族、及び１Ｂ族の元素であり、例えば、チタン、
バナジウム、クロム、マンガン、鉄、コバルト、ニッケ
ル、銅、ジルコニウム、ニオブ、ランタン、セリウムが
挙げられ、好ましくは、鉄、ニッケル、マンガン、コバ
ルト、銅である。The second metal is, similarly to the first metal, a wide range from metals other than the first metal, such as s-block metal element, d-block metal element, p-block metal element, and f-block metal element. Can be selected. Preferably, the second metal is a noble metal or a transition metal other than the first metal, wherein “transition metal” refers to 3A to 7A of the periodic table.
Group, group 8 and group 1B elements, such as titanium,
Examples include vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, lanthanum, and cerium, and preferably iron, nickel, manganese, cobalt, and copper.
【００１６】このような第２金属を還元析出させるの
は、例えば、第１金属を担持した金属酸化物担体を分散
させてスラリーにし、第２金属の硝酸塩、塩化物、炭酸
塩、硫酸塩、金属酸のような無機化合物、あるいは、ア
セチルアセトナートのような有機化合物を溶解した水溶
液をこのスラリーに添加し、さらに、還元剤を添加し、
好ましくは、穏やかな攪拌下に置くことによって行うこ
とができる。The reduction precipitation of the second metal is carried out, for example, by dispersing a metal oxide carrier supporting the first metal to form a slurry, and nitrate, chloride, carbonate, sulfate, and the like of the second metal. An aqueous solution in which an inorganic compound such as a metal acid or an organic compound such as acetylacetonate is dissolved is added to the slurry, and a reducing agent is further added.
Preferably, it can be performed by placing under gentle stirring.
【００１７】この還元剤としては、チオ硫酸ナトリウム
Ｎａ2Ｓ2Ｏ3、チオ硫酸カリウムＫ2Ｓ2Ｏ3、チオ硫酸ア
ンモニウム(ＮＨ4)2Ｓ2Ｏ3、亜硫酸ナトリウムＮａ2Ｓ
Ｏ3、メタ重亜硫酸ナトリウムＮａ2Ｓ2Ｏ5、メタ重亜硫
酸カリウムＫ2Ｓ2Ｏ5、メタ重亜硫酸アンモニウム(ＮＨ
4)2Ｓ2Ｏ5、L-アスコルビン酸ナトリウムＣ6Ｈ7Ｏ6Ｎ
ａ、ポリエチレングリコール、エタノール、及び上記の
テトラヒドロホウ酸ナトリウム等が好適に使用可能であ
る。The reducing agent includes sodium thiosulfate Na 2 S 2 O 3 , potassium thiosulfate K 2 S 2 O 3 , ammonium thiosulfate (NH 4 ) 2 S 2 O 3 , sodium sulfite Na 2 S
O 3 , sodium metabisulfite Na 2 S 2 O 5 , potassium metabisulfite K 2 S 2 O 5 , ammonium metabisulfite (NH
4 ) 2 S 2 O 5 , sodium L-ascorbate C 6 H 7 O 6 N
a, polyethylene glycol, ethanol, the above-mentioned sodium tetrahydroborate and the like can be suitably used.
【００１８】ここで、第１金属がパラジウムの場合、還
元析出させる第２金属の化合物と還元剤を溶解し、第１
金属を担持した金属酸化物担体のスラリーは、ｐＨが４
以上、より好ましくは、ｐＨ４〜６の範囲であることが
好ましい。また、第１金属が白金の場合、このスラリー
は１０以下のｐＨであることが好ましい。ｐＨがこれら
の範囲にあれば、還元析出させる工程で第１金属の溶出
を抑えることができ、第１金属の上に第２金属が積相さ
れた状態を安定して形成することができるためである。Here, when the first metal is palladium, the compound of the second metal to be reduced and precipitated and the reducing agent are dissolved, and the first metal is dissolved in the first metal.
The slurry of the metal oxide carrier supporting the metal has a pH of 4
As described above, the pH is more preferably in the range of 4 to 6. When the first metal is platinum, the slurry preferably has a pH of 10 or less. When the pH is within these ranges, the elution of the first metal can be suppressed in the step of reducing and precipitating, and the state in which the second metal is accumulated on the first metal can be stably formed. It is.
【００１９】このｐＨの調節は、適量の酸又はアルカリ
の添加によって行うことができ、その酸又はアルカリの
種類は、特に限定する必要はなく、添加の時期は、スラ
リーに還元剤を添加する前又は後のいずれでもよい。こ
こで、スラリーに必要量の還元剤を添加した後、硝酸水
溶液やアンモニア水溶液のような酸又はアルカリを使用
することが、スラリーｐＨを所定値に設定し易く、ま
た、ｐＨ調節による異種成分の混入が抑制されることか
ら、好ましい態様として挙げられる。The pH can be adjusted by adding an appropriate amount of acid or alkali, and the type of acid or alkali need not be particularly limited. Or any of the latter. Here, after adding a required amount of reducing agent to the slurry, it is easy to set the slurry pH to a predetermined value by using an acid or an alkali such as an aqueous nitric acid solution or an aqueous ammonia solution, This is a preferred embodiment because mixing is suppressed.
【００２０】好ましい態様として、第２工程は、還元析
出させる第２金属の化合物と還元剤を溶解し、第１金属
が担持された金属酸化物担体を分散したスラリーに、超
音波、プラズマ、及び電磁波の少なくとも１種を照射し
ながら、第１金属の上に第２金属を還元析出させる。こ
の電磁波は、マイクロ波、赤外線、可視光、紫外線のよ
うな光エネルギーを供給することができる波長の電磁波
である。スラリー中の第２金属の化合物に超音波等の物
理的エネルギーを供給することで、第２金属の還元析出
を促進することができるためである。この場合、ポリエ
チレングリコールやエタノールのような比較的還元力の
低い有機化合物を還元剤として用いても、第２金属の化
合物を還元することができ、さらには、アセチルアセト
ナートのような有機金属化合物を使用すれば、かかる還
元剤を使用しなくても第２金属を還元析出させること可
能となる。In a preferred embodiment, the second step comprises dissolving a compound of a second metal to be precipitated by reduction and a reducing agent, and dispersing a metal oxide carrier carrying the first metal in a slurry, by using ultrasonic waves, plasma, While irradiating at least one kind of electromagnetic wave, the second metal is reduced and deposited on the first metal. This electromagnetic wave has a wavelength capable of supplying light energy such as microwave, infrared light, visible light, and ultraviolet light. By supplying physical energy such as ultrasonic waves to the second metal compound in the slurry, reduction precipitation of the second metal can be promoted. In this case, the compound of the second metal can be reduced even if an organic compound having relatively low reducing power such as polyethylene glycol or ethanol is used as a reducing agent, and further, an organic metal compound such as acetylacetonate can be reduced. Is used, the second metal can be reduced and precipitated without using such a reducing agent.
【００２１】したがって、この超音波等の物理的エネル
ギーを供給する態様においては、上記の硫黄やナトリウ
ム等を含むチオ硫酸ナトリウム等の還元剤を使用せず
に、又は使用しても僅かな量でよいため、硫黄やナトリ
ウム等の混入が抑えられた合金触媒を製造することがで
きる。Therefore, in this mode of supplying physical energy such as ultrasonic waves, a small amount of a reducing agent such as sodium thiosulfate containing sulfur or sodium is not used or even if used. Therefore, it is possible to manufacture an alloy catalyst in which the incorporation of sulfur, sodium and the like is suppressed.
【００２２】還元析出させる第２金属の化合物を添加さ
れたスラリーに照射する超音波、プラズマ、又は電磁波
の照射エネルギー量、周波数等の最適範囲は、使用され
る金属酸化物担体、第１金属、第２金属、還元剤等の条
件によって変化するため一概ではなく、当業者は本発明
の開示に基づき、これらの条件に応じて、容易に確認
し、実現することができる。The optimum range of the irradiation energy amount, frequency, etc. of the ultrasonic wave, plasma, or electromagnetic wave for irradiating the slurry to which the compound of the second metal to be reduced and precipitated is added depends on the metal oxide carrier, the first metal, Since it changes depending on the conditions of the second metal, the reducing agent and the like, it is not unconditional, and those skilled in the art can easily confirm and realize the conditions according to these conditions based on the disclosure of the present invention.
【００２３】ここで、限定されるものではないが、超音
波では、２ＭＨｚ以下、好ましくは１００ｋＨｚ〜１Ｍ
Ｈｚの周波数が適切であり、電磁波では、紫外線領域の
４〜４００ｎｍの波長が適切であり、スラリー１リット
ルあたりに供給されるこれらの物理的エネルギーは、１
〜１００００ｋＪ、好ましくは、５〜１０００ｋＪが一
応の目安である。Here, although not limited, in the case of ultrasonic waves, 2 MHz or less, preferably 100 kHz to 1 M
A frequency of 4 to 400 nm is suitable for electromagnetic waves, and a wavelength of 4 to 400 nm in the ultraviolet region is appropriate, and the physical energy supplied per liter of slurry is 1
A value of 1 to 10,000 kJ, preferably 5 to 1000 kJ is a tentative standard.
【００２４】好ましい態様において、第２金属を還元析
出させた後のスラリーは、マイクロ波を用いて乾燥させ
る。これは、通常の外部加熱によって乾燥させる仕方で
は、乾燥中に、第１金属又は第２金属が粗大化する傾向
があるためであり、この理由は、水分が徐々に減少した
ときに溶液のｐＨが局部的に強酸又は強塩基になり易
く、それにより、第１金属又は第２金属が溶出されるた
めと考えられる。これに対し、マイクロ波を用いて加熱
すれば、水分は溶液の全体から比較的低い温度からでも
蒸発するため、局部的なｐＨの高低の発生が抑えられ、
積相構造が安定して維持されるものと考えられる。In a preferred embodiment, the slurry after the second metal has been reduced and precipitated is dried using microwaves. This is because the first metal or the second metal tends to coarsen during drying in a method of drying by ordinary external heating, because the pH of the solution is gradually reduced when the water gradually decreases. Is likely to locally become a strong acid or a strong base, whereby the first metal or the second metal is eluted. On the other hand, if heating is performed using microwaves, water evaporates from a relatively low temperature from the whole solution, so that the occurrence of local pH fluctuation is suppressed,
It is considered that the accumulated phase structure is stably maintained.
【００２５】別な好ましい態様として、第２金属を還元
析出させた後のスラリーは、分散媒の水を有機溶媒に置
換した後、好ましくは、窒素のような不活性雰囲気中で
乾燥させる。これは、水を有機溶媒に置換することで、
水溶性成分を系外に排除する又はイオン解離度を抑える
ことができ、局部的なｐＨの高低の発生による第１金属
又は第２金属の溶出が抑えられることによるものと考え
られる。この有機溶媒としては、メタノール、エタノー
ル等の水溶性有機化合物が適切である。In another preferred embodiment, the slurry after the second metal is reduced and precipitated is dried in an inert atmosphere such as nitrogen after replacing water of the dispersion medium with an organic solvent. This is by replacing water with an organic solvent,
This is considered to be because water-soluble components can be excluded from the system or the degree of ionic dissociation can be suppressed, and the elution of the first metal or the second metal due to the occurrence of local high or low pH can be suppressed. As this organic solvent, a water-soluble organic compound such as methanol and ethanol is suitable.
【００２６】次に、第３工程として、このようにして得
られた積相構造を有する合金触媒を、排気ガス通路付担
体に担持することで、排気ガス浄化用触媒を得ることが
できる。ここで「排気ガス通路付担体」とは、排気ガス
が流通し得る通路を有し、かつ合金触媒を担持すること
ができる担体であり、例えば、ハニカム形状のモノリス
担体のほか、排気管や燃焼室そのものであることもでき
る。Next, as a third step, the catalyst for exhaust gas purification can be obtained by supporting the alloy catalyst having the accumulated phase structure thus obtained on a carrier with an exhaust gas passage. Here, the “carrier with exhaust gas passage” is a carrier that has a passage through which exhaust gas can flow and that can support an alloy catalyst. For example, in addition to a honeycomb-shaped monolithic carrier, an exhaust pipe or a combustion pipe It can be the room itself.
【００２７】ここで、モノリス担体を排気ガス通路付担
体として用いる場合、ウォッシュコートのような通常の
仕方で合金触媒をモノリス担体の壁にコートすること
で、排気ガス浄化用触媒を得ることができ、排気管や燃
焼室を排気ガス通路付担体として用いる場合、同様にし
て、これら排気管や燃焼室の内壁に合金触媒をコートす
ることで、排気ガス浄化用触媒を形成することができ
る。Here, when the monolithic carrier is used as a carrier with an exhaust gas passage, an exhaust gas purifying catalyst can be obtained by coating the alloy catalyst on the wall of the monolithic carrier in a usual manner such as wash coating. When an exhaust pipe or a combustion chamber is used as a carrier with an exhaust gas passage, an exhaust gas purifying catalyst can be similarly formed by coating the inner wall of the exhaust pipe or the combustion chamber with an alloy catalyst.
【００２８】好ましい態様において、合金触媒を排気ガ
ス通路付担体に担持する際に、合金触媒が分散されたス
ラリーを、所定のｐＨ範囲で、ウォッシュコート等によ
って排気ガス通路付担体にコートする。この所定のｐＨ
範囲とすることで、第３工程におけるコートの際に、積
相構造を有する合金触媒の第１金属又は第２金属の溶出
を抑制し、積相構造を維持したままで合金触媒が排気ガ
ス通路付担体に安定して担持されるものと考えられる。In a preferred embodiment, when the alloy catalyst is supported on the carrier with an exhaust gas passage, the slurry in which the alloy catalyst is dispersed is coated on the carrier with an exhaust gas passage by a wash coat or the like in a predetermined pH range. This predetermined pH
By setting the range, the elution of the first metal or the second metal of the alloy catalyst having the accumulated phase structure during the coating in the third step is suppressed, and the alloy catalyst is kept in the exhaust gas passage while maintaining the accumulated phase structure. It is considered that the carrier is stably supported on the carrier.
【００２９】このスラリーの「所定のｐＨ範囲」は、第
１金属と第２金属の種類等の条件によって変化するため
一概ではなく、当業者は本発明の開示に基づき、これら
の条件に応じて、容易に確認し、実現することができ
る。ここで、上述の第２工程と同様に、第１金属がパラ
ジウムの場合、このスラリーのｐＨは、４以上が好まし
く、より好ましくは、４〜６の範囲であり、第１金属が
白金の場合、このスラリーのｐＨは１０以下であること
が好ましい。また、第２金属が、鉄やニッケルのような
遷移金属の場合、このスラリーのｐＨは６以上であるこ
とが好ましい。The "predetermined pH range" of the slurry varies depending on the conditions such as the types of the first metal and the second metal, and is not unconditional. , Can be easily confirmed and realized. Here, similarly to the above-mentioned second step, when the first metal is palladium, the pH of this slurry is preferably 4 or more, more preferably in the range of 4 to 6, and when the first metal is platinum. The pH of the slurry is preferably 10 or less. When the second metal is a transition metal such as iron or nickel, the pH of the slurry is preferably 6 or more.
【００３０】このｐＨの調節は、第２工程と同様に、任
意の酸又はアルカリの添加によって行うことができる
が、さらに、ウォッシュコート等でコートする際に使用
されるバインダー、例えば、硝酸アルミニウム、アルミ
ナゾル、ジルコニアゾルの添加量又はこれらゾルのｐＨ
によっても調節することができる。The adjustment of the pH can be carried out by the addition of an optional acid or alkali, as in the second step. Further, a binder used for coating with a wash coat or the like, for example, aluminum nitrate, Addition amount of alumina sol and zirconia sol or pH of these sols
Can also be adjusted.
【００３１】好ましい態様において、排気ガス通路付担
体にコートされたスラリーは、マイクロ波を用いて乾燥
させる。これは、第１工程と同様に、乾燥中の第１金属
又は第２金属の粗大化を抑制するためである。In a preferred embodiment, the slurry coated on the carrier with exhaust gas passages is dried using microwaves. This is for suppressing the coarsening of the first metal or the second metal during drying, as in the first step.
【００３２】以上、高い排気ガス浄化性能を提供する積
相構造を有する触媒が、再現性よく安定して製造される
ことができる各種の適正化された態様を、第１〜３工程
に区分して説明した。As described above, various optimized aspects in which a catalyst having a product phase structure providing high exhaust gas purification performance can be stably produced with good reproducibility are classified into first to third steps. Explained.
【００３３】ここで、好ましくは、第１〜３工程の全て
が、上記の適正化されたいずれかの態様にしたがって実
施されるが、いずれか１工程又は２工程が、適正化され
た態様で実施されても、浄化性能が向上された排気ガス
浄化用触媒を得ることができる。なお、第３工程が、上
記の適正化された態様にしたがって実施される場合、第
１工程又は第２工程の少なくとも一方は、上記の適正化
された態様にしたがって実施されることが好ましい。Here, preferably, all of the first to third steps are carried out in accordance with any of the above-mentioned optimized modes, but any one or two steps are performed in an optimized mode. Even if it is implemented, it is possible to obtain an exhaust gas purifying catalyst with improved purification performance. When the third step is performed according to the above-described optimized aspect, at least one of the first step and the second step is preferably performed according to the above-described optimized aspect.
【００３４】[0034]
【実施例】以下の実施例は、合金触媒と排気ガス浄化用
触媒の適正化された態様を例証する。ここで、実施例１
〜１６は第１工程の適正化、実施例１７〜３３は第２工
程の適正化、実施例３４〜４４は第３工程の適正化に関
するものである。The following examples illustrate the optimized aspects of alloy catalysts and exhaust gas purification catalysts. Here, Example 1
16 to 16 relate to the optimization of the first step, Examples 17 to 33 relate to the optimization of the second step, and Examples 34 to 44 relate to the optimization of the third step.
【００３５】実施例１ 第１工程として、金属酸化物担体のアルミナ（比表面積
約１８０ｍ2／ｇ）の５０ｇに、ジニトロジアンミン白
金Ｐｔ(ＮＨ3)2(ＮＯ2)2の水溶液を、アルミナとＰｔの
合計質量を基準にＰｔが１.９８質量％となる量で含浸
し、１２０℃の大気中で５時間乾燥させた後、５００℃
の大気中で２時間焼成し、Ｐｔが担持されたアルミナを
得た。このＰｔ担持アルミナを５００ｃｃのイオン交換
水に分散させ、攪拌しながら７.７６ｇのテトラヒドロ
ホウ酸ナトリウムを添加し、穏やかな攪拌下で３０℃に
２４時間置くことで、第１金属のＰｔに還元処理を施
し、その後、乾燥させた。Example 1 As a first step, an aqueous solution of dinitrodiammineplatinum Pt (NH 3 ) 2 (NO 2 ) 2 was added to 50 g of alumina (specific surface area: about 180 m 2 / g) as a metal oxide carrier. Impregnated in an amount such that Pt becomes 1.98% by mass based on the total mass of Pt, dried in air at 120 ° C. for 5 hours, and then dried at 500 ° C.
For 2 hours to obtain Pt-supported alumina. This Pt-supported alumina was dispersed in 500 cc of ion-exchanged water, 7.76 g of sodium tetrahydroborate was added with stirring, and the mixture was placed at 30 ° C. for 24 hours under gentle stirring to reduce the Pt as the first metal. The treatment was applied and then dried.
【００３６】次に、第２工程として、上記の還元処理を
施したＰｔ担持アルミナを、６０℃のイオン交換水４０
０ｃｃに分散させ、攪拌しながら６質量％塩化金酸ＨＡ
ｕＣｌ4水溶液を０.１７ｇ添加し、さらに、チオ硫酸ナ
トリウム０.１２ｇ、亜硫酸ナトリウム０.２６ｇ、L-ア
スコルビン酸ナトリウム１.０２ｇを順次に添加し、０.
０２質量％のＡｕをＰｔ担持アルミナの上に還元析出さ
せた。Next, as a second step, the Pt-supported alumina having been subjected to the above-mentioned reduction treatment is mixed with ion-exchanged water
0 cc and 6 mass% chloroauric acid HA while stirring.
0.17 g of an aqueous uCl 4 solution was added, and 0.12 g of sodium thiosulfate, 0.26 g of sodium sulfite, and 1.02 g of sodium L-ascorbate were sequentially added.
02% by mass of Au was reduced and precipitated on Pt-supported alumina.
【００３７】次に、このスラリーを濾過・洗浄・乾燥し
た後、５００℃の大気中で２時間焼成し、アルミナ粉末
の上にＰｔとＡｕが担持されたＰｔ−Ａｕ／アルミナ粉
末（Ｐｔ／Ａｕ質量比＝９９／１）の合金触媒を得た。
次いで、これを圧縮成形した後、粉砕し、粒子径１〜３
ｍｍのペレット形状の合金触媒を得た。Next, this slurry was filtered, washed and dried, and then calcined in the air at 500 ° C. for 2 hours, so that Pt—Au / alumina powder (Pt / Au) in which Pt and Au were supported on alumina powder. An alloy catalyst having a mass ratio of 99/1) was obtained.
Next, after compression-molding this, it is pulverized to obtain a particle size of 1 to 3.
Thus, an alloy catalyst having a pellet shape of mm was obtained.
【００３８】実施例２〜５ 第１工程として、実施例１におけるアルミナの他に、セ
リア（比表面積約９５ｍ2／ｇ）、セリア−ジルコニア
（比表面積約９０ｍ2／ｇ）を金属酸化物担体として用
いた以外は実施例１と同様にして、Ｐｔに還元処理が施
され、Ｐｔが１.９８質量％担持された金属酸化物担体
を調製した。次に、第２工程として、Ｐｔ／Ａｕの質量
比を変えた以外は実施例１と同様にして０.０２質量％
のＡｕを還元析出させ、表１に摘要を示す実施例２〜５
のペレット形状の合金触媒を得た。[0038] As Examples 2 to 5 the first step, in addition to the alumina in Example 1, ceria (specific surface area about 95 m 2 / g), ceria - zirconia (specific surface area of about 90m 2 / g) metal oxide support Pt was subjected to a reduction treatment in the same manner as in Example 1 except that Pt was used to prepare 1.98% by mass of a Pt-supported metal oxide carrier. Next, as a second step, 0.02% by mass in the same manner as in Example 1 except that the mass ratio of Pt / Au was changed.
Examples 2 to 5 in which Au was precipitated by reduction and summarized in Table 1
Was obtained in the form of a pellet.
【００３９】実施例６〜７ 第１工程として、実施例１と同様にして、Ｐｔに還元処
理が施され、Ｐｔが２質量％担持されたアルミナを調製
し、次に、第２工程として、塩化金酸水溶液に代えて純
度９９.５％の塩化ニッケルＮｉＣｌ2・６Ｈ2Ｏ試薬を
０.４１ｇ添加した以外は実施例１と同様にしてＮｉを
還元析出させ、表１に摘要を示す実施例６〜７のペレッ
ト形状の合金触媒を得た。Examples 6 to 7 In the first step, Pt was reduced in the same manner as in Example 1 to prepare alumina carrying 2% by mass of Pt. Next, in the second step, Ni was reduced and precipitated in the same manner as in Example 1 except that 0.41 g of nickel chloride NiCl 2 .6H 2 O reagent having a purity of 99.5% was added in place of the aqueous solution of chloroauric acid. The pellet-shaped alloy catalysts of Examples 6 to 7 were obtained.
【００４０】実施例８〜９ 第１工程として、実施例１と同様にして、Ｐｔに還元処
理が施され、Ｐｔが２質量％担持されたアルミナを調製
し、次に、第２工程として、塩化金酸水溶液に代えて純
度９９.５％の塩化鉄ＦｅＣｌ3を１.４５ｇ添加した以
外は実施例１と同様にしてＦｅを還元析出させ、表１に
摘要を示す実施例８〜９のペレット形状の合金触媒を得
た。Examples 8 to 9 As a first step, Pt was reduced in the same manner as in Example 1 to prepare an alumina carrying 2% by mass of Pt. Next, as a second step, Fe was reduced and precipitated in the same manner as in Example 1 except that 1.45 g of iron chloride FeCl 3 having a purity of 99.5% was added instead of the aqueous solution of chloroauric acid, and Fe and Fe of Examples 8 to 9 shown in Table 1 were summarized. A pellet-shaped alloy catalyst was obtained.
【００４１】比較例１〜９ 実施例１〜９における第１工程のテトラヒドロホウ酸ナ
トリウム添加による還元処理を行わなかった以外は、そ
れぞれ実施例１〜９と同様にして、表１に摘要を示す比
較例１〜９のペレット形状の合金触媒を得た。Comparative Examples 1 to 9 The summary is shown in Table 1 in the same manner as in Examples 1 to 9 except that the reduction treatment by adding sodium tetrahydroborate in the first step in Examples 1 to 9 was not performed. Pellet-shaped alloy catalysts of Comparative Examples 1 to 9 were obtained.
【００４２】比較例１０〜１２ 実施例２〜４における、第１工程のテトラヒドロホウ酸
ナトリウム添加による還元処理と、第２工程におけるＡ
ｕの還元析出を行わなかった以外は、それぞれ実施例２
〜４と同様にして、表１に摘要を示す比較例１０〜１２
のペレット形状のＰｔ／アルミナの触媒を得た。Comparative Examples 10 to 12 In Examples 2 to 4, the reduction treatment by the addition of sodium tetrahydroborate in the first step and the A treatment in the second step
Example 2 except that reduction precipitation of u was not performed.
Comparative Examples 10 to 12 showing the summary in Table 1 in the same manner as in Comparative Examples 10 to 12.
A Pt / alumina catalyst in the form of pellets was obtained.
【００４３】実施例１０〜１６ 実施例１〜７における第１工程のテトラヒドロホウ酸ナ
トリウム添加による還元処理に代えて、Ｎ2中に２体積
％のＨ2を含む還元性ガス雰囲気中で４００℃×３０分
間の還元処理を行った以外は、それぞれ実施例１〜７と
同様にして、表２に摘要を示す実施例１０〜１６のペレ
ット形状の合金触媒を得た。[0043] Example 10 to 16 instead of the reduction process by the first step sodium tetrahydroborate adding in Examples 1 to 7, 400 ° C. in a reducing gas atmosphere containing H 2 of 2 vol% in N 2 Except that the reduction treatment was performed for × 30 minutes, the pellet-shaped alloy catalysts of Examples 10 to 16 shown in Table 2 were obtained in the same manner as Examples 1 to 7, respectively.
【００４４】実施例１７ 第１工程として、アルミナの５０ｇに、硝酸パラジウム
Ｐｄ(ＮＯ3)2の水溶液を、アルミナとＰｄの合計質量を
基準にＰｄが４質量％となる量で含浸し、１２０℃の大
気中で５時間乾燥させた後、５００℃の大気中で２時間
焼成し、Ｐｄが４質量％担持されたアルミナを得た。Example 17 As a first step, 50 g of alumina was impregnated with an aqueous solution of palladium nitrate Pd (NO 3 ) 2 in such an amount that Pd was 4% by mass based on the total mass of alumina and Pd. After drying for 5 hours in the air at 500 ° C., it was calcined for 2 hours in the air at 500 ° C. to obtain alumina carrying 4% by mass of Pd.
【００４５】次に、第２工程として、上記のＰｄ担持ア
ルミナを６０℃のイオン交換水４００ｃｃに分散させ、
攪拌しながら６質量％塩化金酸水溶液を１.８５ｇ添加
した後、０.１ｇの炭酸ナトリウムＮａ2ＣＯ3を添加
し、さらに、チオ硫酸ナトリウム１.１２ｇ、亜硫酸ナ
トリウム２.８４ｇ、L-アスコルビン酸ナトリウム１１.
２ｇを順次に添加し、スラリーｐＨ４.８７の条件で、
ＡｕをＰｄ担持アルミナの上に還元析出させた。Next, as a second step, the above Pd-supported alumina was dispersed in 400 cc of ion-exchanged water at 60 ° C.
After stirring, 1.85 g of a 6% by mass aqueous solution of chloroauric acid was added, 0.1 g of sodium carbonate Na 2 CO 3 was added, further, 1.12 g of sodium thiosulfate, 2.84 g of sodium sulfite, and L-ascorbin Sodium acid acid 11.
2 g were added sequentially, and under the condition of slurry pH 4.87,
Au was reduced and precipitated on Pd-supported alumina.
【００４６】次に、このスラリーを濾過・洗浄・乾燥し
た後、５００℃の大気中で２時間焼成し、アルミナ粉末
の上にＰｄとＡｕが担持されたＰｄ−Ａｕ／アルミナ粉
末（Ｐｄ／Ａｕ質量比＝９／１）の合金触媒を得た。次
いで、これを圧縮成形した後、粉砕し、粒子径１〜３ｍ
ｍのペレット形状の合金触媒を得た。Next, this slurry was filtered, washed and dried, and then calcined in the air at 500 ° C. for 2 hours to obtain Pd-Au / alumina powder (Pd / Au) in which Pd and Au were supported on alumina powder. An alloy catalyst having a mass ratio of 9/1) was obtained. Then, after compression-molding this, it is pulverized to a particle size of 1 to 3 m.
Thus, an alloy catalyst having a pellet shape of m was obtained.
【００４７】実施例１８〜２０ 実施例１７における第２工程での炭酸ナトリウムの添加
量を変えて、スラリーｐＨを表３に示す条件とした以外
は実施例１７と同様にして、表３に摘要を示す実施例１
８〜２０のペレット形状のＰｄ−Ａｕ／アルミナの合金
触媒を得た。Examples 18 to 20 In the same manner as in Example 17, except that the amount of sodium carbonate added in the second step in Example 17 was changed and the slurry pH was changed to the condition shown in Table 3, Example 1 showing
Pd-Au / alumina alloy catalysts in the form of 8 to 20 pellets were obtained.
【００４８】比較例１３〜１４ 実施例１７における第２工程での炭酸ナトリウムの添加
量を変えて、スラリーｐＨを表３に示す条件とした以外
は実施例１７と同様にして、表３に摘要を示す比較例１
３〜１４のペレット形状のＰｄ−Ａｕ／アルミナの合金
触媒を得た。Comparative Examples 13 and 14 The procedure of Example 17 was repeated except that the amount of sodium carbonate added in the second step was changed and the slurry pH was changed to the condition shown in Table 3. Comparative Example 1 showing
Pd-Au / alumina alloy catalysts in the form of 3 to 14 pellets were obtained.
【００４９】比較例１５ 実施例１７における第１工程で得られたＰｄが４質量％
担持されたアルミナをペレット形状にし、これを比較用
の触媒とした。Comparative Example 15 Pd obtained in the first step in Example 17 was 4% by mass.
The supported alumina was formed into a pellet, and this was used as a catalyst for comparison.
【００５０】実施例２１ 第１工程として、５０ｇのアルミナに、ジニトロジアン
ミン白金の水溶液をアルミナとＰｔの全体でＰｔが４質
量％となる量で含浸し、１２０℃の大気中で５時間乾燥
させた後、５００℃の大気中で２時間焼成し、Ｐｔが４
質量％担持されたアルミナを得た。Example 21 As a first step, 50 g of alumina was impregnated with an aqueous solution of dinitrodiammine platinum in such an amount that the total amount of alumina and Pt was 4% by mass, and dried in air at 120 ° C. for 5 hours. After firing for 2 hours in the air at 500 ° C.,
A mass% supported alumina was obtained.
【００５１】次に、第２工程として、Ｐｔ担持アルミナ
を６０℃のイオン交換水４００ｃｃに分散させ、攪拌し
ながら６質量％塩化金酸水溶液を１.６７ｇ添加し、さ
らに、チオ硫酸ナトリウム１.１２ｇを添加し、０.１Ｎ
硝酸水溶液を添加してｐＨ１０に調節した。次に、亜硫
酸ナトリウム２.８４ｇ、L-アスコルビン酸ナトリウム
１１.２ｇを順次に添加し、０.１Ｎ硝酸水溶液を適宜添
加してｐＨ１０を維持しながらＡｕをＰｔ担持アルミナ
の上に還元析出させた。Next, as a second step, Pt-supported alumina was dispersed in 400 cc of ion-exchanged water at 60 ° C., and while stirring, 1.67 g of a 6% by mass aqueous solution of chloroauric acid was added. 12 g and 0.1N
The pH was adjusted to 10 by adding an aqueous nitric acid solution. Next, 2.84 g of sodium sulfite and 11.2 g of sodium L-ascorbate were sequentially added, and a 0.1N aqueous nitric acid solution was appropriately added to reduce and precipitate Au on Pt-supported alumina while maintaining the pH at 10. .
【００５２】次に、このスラリーを濾過・洗浄・乾燥の
後、５００℃の大気中で２時間焼成し、アルミナ粉末の
上にＰｔとＡｕが担持されたＰｔ−Ａｕ／アルミナ粉末
（Ｐｔ／Ａｕ質量比＝９５／５）の合金触媒を得た。次
いで、これを圧縮成形した後、粉砕し、粒子径１〜３ｍ
ｍのペレット形状の合金触媒を得た。Next, this slurry was filtered, washed, and dried, and then calcined in the air at 500 ° C. for 2 hours to obtain Pt—Au / alumina powder (Pt / Au) in which Pt and Au were supported on alumina powder. An alloy catalyst having a mass ratio of 95/5) was obtained. Then, after compression-molding this, it is pulverized to a particle size of 1 to 3 m.
Thus, an alloy catalyst having a pellet shape of m was obtained.
【００５３】実施例２２〜２４ 実施例２１における第２工程で、Ｐｔ担持アルミナのス
ラリーのｐＨを１０に調節したことに代え、０.１Ｎ硝
酸水溶液の添加によりｐＨを９、７、６に調節した以外
は、それぞれ実施例２１と同様にして、表４に摘要を示
す実施例２２〜２４のペレット形状のＰｔ−Ａｕ／アル
ミナの合金触媒を得た。Examples 22 to 24 Instead of adjusting the pH of the slurry of Pt-supported alumina to 10 in the second step in Example 21, the pH was adjusted to 9, 7, and 6 by adding a 0.1N aqueous nitric acid solution. Except that, in the same manner as in Example 21, pellet-shaped Pt-Au / alumina alloy catalysts of Examples 22 to 24 whose summary is shown in Table 4 were obtained.
【００５４】比較例１６〜１７ 実施例２１における第２工程で、Ｐｔ担持アルミナのス
ラリーのｐＨを１０に調節したことに代え、０.１Ｎ硝
酸水溶液の添加によりｐＨを１２、１３に調節した以外
は、それぞれ実施例２１と同様にして、表４に摘要を示
す比較例１６〜１７のペレット形状のＰｔ−Ａｕ／アル
ミナの合金触媒を得た。Comparative Examples 16-17 In the second step in Example 21, except that the pH of the slurry of Pt-supported alumina was adjusted to 10 and the pH was adjusted to 12 and 13 by adding a 0.1N aqueous nitric acid solution. In the same manner as in Example 21, Pt-Au / alumina alloy catalysts in the form of pellets of Comparative Examples 16 to 17 whose summary is shown in Table 4 were obtained.
【００５５】比較例１８ 実施例２１における第１工程で得られたＰｔが４質量％
担持されたアルミナをペレット形状にし、これを比較用
の触媒とした。Comparative Example 18 Pt obtained in the first step in Example 21 was 4% by mass.
The supported alumina was formed into a pellet, and this was used as a catalyst for comparison.
【００５６】実施例２５ 第１工程として、金属酸化物担体のアルミナの５０ｇ
に、ジニトロジアンミン白金の水溶液を、アルミナとＰ
ｔの合計質量を基準にＰｔが１質量％となる量で含浸
し、１２０℃の大気中で５時間乾燥させた後、３００℃
の大気中で２時間焼成し、Ｐｔが１質量％担持されたア
ルミナを得た。Example 25 As a first step, 50 g of alumina as a metal oxide carrier was used.
Then, an aqueous solution of dinitrodiammineplatinum was mixed with alumina and P
impregnated in an amount such that Pt becomes 1% by mass based on the total mass of t, and dried in air at 120 ° C for 5 hours.
For 2 hours to obtain alumina carrying 1% by mass of Pt.
【００５７】次に、第２工程として、このＰｔ担持アル
ミナの３０ｇを５００ｃｃのイオン交換水に分散させ、
これに０.０３１４ｇの塩化金酸、及び還元剤の０.０３
８ｇのチオ硫酸ナトリウムＮａ2Ｓ2Ｏ3・５Ｈ2Ｏと０.
３０５ｇのポリエチレングリコール（分子量約１００
０）を加え、穏やかな攪拌下で２００ｋＨｚの超音波
（出力０.６６Ｗ／ｃｍ2）に２時間曝し、ＡｕをＰｔ担
持アルミナの上に還元析出させた。Next, as a second step, 30 g of the Pt-supported alumina was dispersed in 500 cc of ion-exchanged water.
To this, 0.0314 g of chloroauric acid and 0.03 g of a reducing agent were added.
8 g of sodium thiosulfate Na 2 S 2 O 3 .5H 2 O and 0.1 g
305 g of polyethylene glycol (molecular weight of about 100
0) was added thereto, and the mixture was exposed to 200 kHz ultrasonic waves (output: 0.66 W / cm 2 ) for 2 hours under gentle stirring to deposit Au on Pt-supported alumina by reduction.
【００５８】次に、このスラリーを濾過・洗浄・乾燥の
後、５００℃の大気中で２時間焼成し、アルミナ粉末の
上にＰｔとＡｕが担持されたＰｔ−Ａｕ／アルミナ粉末
（Ｐｔ／Ａｕ質量比＝９／１）の合金触媒を得た。次
に、これを圧縮成形した後、粉砕し、粒子径１〜３ｍｍ
のペレット形状の合金触媒を得た。Next, this slurry was filtered, washed, and dried, and then calcined in the air at 500 ° C. for 2 hours. Pt—Au / alumina powder (Pt / Au) in which Pt and Au were supported on alumina powder An alloy catalyst having a mass ratio of 9/1) was obtained. Next, after compression-molding this, it is pulverized to a particle size of 1 to 3 mm.
Was obtained in the form of a pellet.
【００５９】比較例１９ 実施例２５と同様にして、第１工程として、Ｐｔが１質
量％担持されたアルミナを調製し、次に、第２工程とし
て、ポリエチレングリコールを加えない以外は実施例２
５と同様にして、表５に摘要を示す比較例１９のペレッ
ト形状のＰｔ−Ａｕ／アルミナの合金触媒を得た。Comparative Example 19 In the same manner as in Example 25, as the first step, alumina containing 1% by mass of Pt was prepared, and then, as the second step, polyethylene glycol was not added.
In the same manner as in No. 5, a pellet-shaped Pt-Au / alumina alloy catalyst of Comparative Example 19 whose summary is shown in Table 5 was obtained.
【００６０】比較例２０ 実施例２５における第１工程で得られたＰｔが１質量％
担持されたアルミナをペレット形状にし、これを比較用
の触媒とした。Comparative Example 20 1% by mass of Pt obtained in the first step in Example 25
The supported alumina was formed into a pellet, and this was used as a catalyst for comparison.
【００６１】実施例２６ 第１工程として、金属酸化物担体のアルミナの５０ｇ
に、ジニトロジアンミン白金の水溶液を、アルミナとＰ
ｔの合計質量を基準にＰｔが２質量％となる量で含浸
し、１２０℃の大気中で５時間乾燥させた後、３００℃
の大気中で２時間焼成し、Ｐｔが２質量％担持されたア
ルミナを得た。Example 26 As a first step, 50 g of alumina as a metal oxide carrier was used.
Then, an aqueous solution of dinitrodiammineplatinum was mixed with alumina and P
impregnated in an amount such that Pt becomes 2% by mass based on the total mass of t, dried in air at 120 ° C for 5 hours, and then dried at 300 ° C.
For 2 hours to obtain alumina carrying 2% by mass of Pt.
【００６２】次に、第２工程として、ジメチル金(III)
アセチルアセトナート(ＣＨ3)2Ａｕ(ＣＨ3ＣＯＣＨＣＯ
ＣＨ3)の０.０１６ｇを５００ｃｃのイオン交換水に分
散させ、これに、穏やかな攪拌下で波長３６７ｎｍ×出
力１ｍＷの紫外線を２時間照射し、ＡｕをＰｔ担持アル
ミナの上に還元析出させた。次に、このスラリーを濾過
・洗浄・乾燥の後、実施例１と同様にして焼成し、圧縮
成形して、表５に摘要を示すペレット形状のＰｔ−Ａｕ
／アルミナの合金触媒を得た。Next, as a second step, dimethyl gold (III)
Acetylacetonate (CH 3 ) 2 Au (CH 3 COCHCO
CH 3 ) was dispersed in 500 cc of ion-exchanged water, and irradiated with ultraviolet light having a wavelength of 367 nm and an output of 1 mW for 2 hours under gentle stirring, thereby reducing and depositing Au on Pt-supported alumina. . Next, after filtering, washing and drying the slurry, it was baked and compression-molded in the same manner as in Example 1, and the pellet-shaped Pt-Au as summarized in Table 5 was obtained.
/ Alumina alloy catalyst was obtained.
【００６３】実施例２７ 第２工程として、ジメチル金(III)アセチルアセトナー
トを０.０８０ｇに増やした以外は実施例２６と同様に
して、表５に摘要を示す実施例２７のペレット形状のＰ
ｔ−Ａｕ／アルミナの合金触媒を得た。Example 27 As a second step, the same procedure as in Example 26 was carried out except that the amount of dimethyl gold (III) acetylacetonate was increased to 0.080 g, and the pellet-shaped P of Example 27 shown in Table 5 is summarized.
An alloy catalyst of t-Au / alumina was obtained.
【００６４】実施例２８ 第１工程として、実施例２６と同様にして、５０ｇのア
ルミナに２質量％のＰｔを担持させた。次に、第２工程
として、このＰｔ担持アルミナを、６０℃のイオン交換
水４００ｃｃに分散させ、攪拌しながら６質量％塩化金
酸水溶液を０.１７ｇ添加し、さらに、チオ硫酸ナトリ
ウム０.１２ｇ、亜硫酸ナトリウム０.２６ｇ、L-アスコ
ルビン酸ナトリウム１.０２ｇを順次に添加し、Ａｕを
Ｐｔ担持アルミナの上に還元析出させた。Example 28 As a first step, 2 g% of Pt was supported on 50 g of alumina in the same manner as in Example 26. Next, as a second step, this Pt-supported alumina was dispersed in 400 cc of ion-exchanged water at 60 ° C., 0.17 g of a 6% by mass aqueous solution of chloroauric acid was added with stirring, and 0.12 g of sodium thiosulfate was further added. Then, 0.26 g of sodium sulfite and 1.02 g of sodium L-ascorbate were sequentially added, and Au was reduced and precipitated on Pt-supported alumina.
【００６５】次に、このスラリーを濾過・洗浄した後、
波長０.４１ｎｍ×出力８００Ｗのマイクロ波を照射し
て乾燥させ、５００℃の大気中で２時間焼成し、次い
で、この合金触媒を圧縮成形し、粒子径１〜３ｍｍのペ
レット形状にした。Next, after filtering and washing this slurry,
Microwaves having a wavelength of 0.41 nm and an output of 800 W were irradiated to dry, and calcined in the air at 500 ° C. for 2 hours. Then, the alloy catalyst was compression-molded into pellets having a particle diameter of 1 to 3 mm.
【００６６】実施例２９〜３０ 実施例２８で使用した金属酸化物担体のアルミナに代え
て、それぞれ実施例３〜４で用いたのと同じセリア、セ
リア−ジルコニアを用いた以外は実施例２８と同様にし
て、表６に摘要を示す実施例２９〜３０のペレット形状
のＰｔ−Ａｕ／アルミナの合金触媒を得た。Examples 29 to 30 The same procedures as in Example 28 were carried out except that the same ceria and ceria-zirconia as those used in Examples 3 and 4 were used instead of alumina as the metal oxide carrier used in Example 28. Similarly, pellet-shaped Pt-Au / alumina alloy catalysts of Examples 29 to 30 whose summary is shown in Table 6 were obtained.
【００６７】実施例３１ 実施例２８で使用した塩化金酸水溶液に代えて、塩化ニ
ッケル水溶液を使用した以外は実施例２８と同様にし
て、表６に摘要を示すペレット形状のＰｔ−Ｎｉ／アル
ミナの合金触媒を得た。Example 31 Pt-Ni / alumina in the form of pellets as summarized in Table 6 was prepared in the same manner as in Example 28 except that an aqueous solution of nickel chloride was used instead of the aqueous solution of chloroauric acid used in Example 28. Was obtained.
【００６８】実施例３２〜３３ 実施例２８と実施例３１の第２工程において、第２金属
を還元析出させ、スラリーを濾過・洗浄した後、得られ
た合金触媒を再度３００ｃｃのエタノールに分散させ、
濾過し、さらにエタノールで洗浄することによって、水
分をエタノールで十分に置換し、次いで８０℃の窒素雰
囲気中で２時間加熱して乾燥させた以外は、それぞれ実
施例２８、実施例３１と同様にして、表６に摘要を示す
実施例３２〜３３のペレット形状の合金触媒を得た。Examples 32 to 33 In the second step of Examples 28 and 31, the second metal was reduced and precipitated, the slurry was filtered and washed, and the obtained alloy catalyst was dispersed again in 300 cc of ethanol. ,
Filtration and further washing with ethanol were carried out in the same manner as in Example 28 and Example 31, except that the water was sufficiently replaced with ethanol, and then heated and dried in a nitrogen atmosphere at 80 ° C for 2 hours. Thus, pellet-shaped alloy catalysts of Examples 32 to 33 whose summary is shown in Table 6 were obtained.
【００６９】実施例３４ 実施例１７と同様にして第１工程と第２工程を行い、Ｐ
ｄ−Ａｕ／アルミナ粉末（Ｐｄ／Ａｕ質量比＝９／１）
の合金触媒を得た。次に、第３工程として、この合金触
媒の１００ｇに、４０質量％硝酸アルミニウム水溶液を
３０ｇ、ベーマイトを１.５ｇ、イオン交換水を６０ｃ
ｃ加えてスラリーを作成し、このスラリーをミリング
し、ｐＨ５.８の均一なスラリーを得た。Example 34 The first and second steps were performed in the same manner as in Example 17,
d-Au / alumina powder (Pd / Au mass ratio = 9/1)
Was obtained. Next, as a third step, 30 g of a 40 mass% aluminum nitrate aqueous solution, 1.5 g of boehmite, and 60 c of ion-exchanged water were added to 100 g of the alloy catalyst.
c was added to prepare a slurry, and the slurry was milled to obtain a uniform slurry having a pH of 5.8.
【００７０】このスラリーを直径３０ｍｍ×長さ５０ｍ
ｍのモノリス担体（壁厚７５μｍ、セル密度９３セル／
ｃｍ2、六角セル）にウォッシュコートし、大気中で、
１００℃×２時間の仮乾燥と２５０℃×３時間の乾燥の
後、５５０℃で２時間焼成し、排気ガス通路付担体とし
てのモノリス担体に合金触媒がコートされた排気ガス浄
化用触媒を得た。This slurry was prepared with a diameter of 30 mm and a length of 50 m.
m monolithic carrier (wall thickness 75 μm, cell density 93 cells /
cm 2 , hexagonal cell)
After tentative drying at 100 ° C. × 2 hours and drying at 250 ° C. × 3 hours, calcination is performed at 550 ° C. for 2 hours to obtain a catalyst for exhaust gas purification in which a monolithic carrier as a carrier with an exhaust gas passage is coated with an alloy catalyst. Was.
【００７１】実施例３５〜３７ 実施例３４におけるスラリー中の硝酸アルミニウムの量
を変え、スラリーｐＨを表７に示す条件とした以外は実
施例３４と同様にして、表７に摘要を示す実施例３５〜
３７の排気ガス浄化用触媒を得た。Examples 35 to 37 The same procedures as in Example 34 were conducted except that the amount of aluminum nitrate in the slurry was changed and the pH of the slurry was changed to the conditions shown in Table 7. 35 ~
37 exhaust gas purifying catalysts were obtained.
【００７２】比較例２１〜２２ 実施例３４におけるスラリー中の硝酸アルミニウムの量
を変え、スラリーｐＨを表７に示す条件とした以外は実
施例３４と同様にして、表７に摘要を示す比較例２１〜
２２の排気ガス浄化用触媒を得た。Comparative Examples 21 to 22 Comparative examples having the summary in Table 7 in the same manner as in Example 34 except that the amount of aluminum nitrate in the slurry was changed and the slurry pH was changed to the conditions shown in Table 7. 21-
Thus, 22 exhaust gas purifying catalysts were obtained.
【００７３】比較例２３ 実施例１７における第１工程で得られたＰｄ／アルミナ
粉末を、実施例３４と同様にしてスラリーにし、モノリ
ス担体にコートしたものを比較用の排気ガス浄化用触媒
とした。Comparative Example 23 The Pd / alumina powder obtained in the first step in Example 17 was slurried in the same manner as in Example 34, and the slurry coated on a monolithic carrier was used as a comparative exhaust gas purifying catalyst. .
【００７４】実施例３８〜４１ ジニトロジアンミン白金と塩化ニッケルの量をそれぞれ
２倍にした以外は実施例３１と同様にして第１工程と第
２工程を行い、Ｐｔ−Ｎｉ／アルミナ粉末（Ｐｔ／Ａｕ
質量比＝９／１）の合金触媒を得た。次に、第３工程と
して、実施例３４における硝酸アルミニウム水溶液とベ
ーマイトに代え、ｐＨの異なるジルコニアゾルを使用
し、表８に示すｐＨのスラリーを調製してウォッシュコ
ートした以外は、実施例３４と同様にして、表８に摘要
を示す実施例３８〜４１の排気ガス浄化用触媒を得た。Examples 38 to 41 The first and second steps were carried out in the same manner as in Example 31 except that the amounts of dinitrodiammineplatinum and nickel chloride were each doubled to obtain Pt-Ni / alumina powder (Pt / Au
An alloy catalyst having a mass ratio of 9/1) was obtained. Next, as a third step, zirconia sols having different pHs were used instead of the aluminum nitrate aqueous solution and boehmite in Example 34, and a slurry having a pH shown in Table 8 was prepared and wash-coated. Similarly, the exhaust gas purifying catalysts of Examples 38 to 41 whose summary is shown in Table 8 were obtained.
【００７５】比較例２４〜２６ 第３工程として、実施例３８におけるスラリー中のジル
コニアゾルの量を変え、表８に示すｐＨのスラリーを用
いた以外は実施例３８と同様にして、表８に摘要を示す
比較例２４〜２６の排気ガス浄化用触媒を得た。Comparative Examples 24-26 As a third step, the amount of zirconia sol in the slurry in Example 38 was changed, and a slurry having the pH shown in Table 8 was used. The exhaust gas purifying catalysts of Comparative Examples 24 to 26 showing the summary were obtained.
【００７６】実施例４２〜４４ 実施例２８〜３０と同様にして得られたＰｔ−Ａｕ／ア
ルミナの合金触媒を用い、第３工程として、それぞれ実
施例３４と同様にしてスラリーを作成し、モノリス担体
にこれらのスラリーをウォッシュコートした。次に、こ
れらのスラリーを乾燥させるにおいて、それぞれ波長
０.４１ｎｍ×出力６００Ｗのマイクロ波を照射して乾
燥させ、次いで５００℃の大気中で２時間焼成し、表９
に摘要を示す実施例４２〜４４の排気ガス浄化用触媒を
得た。Examples 42 to 44 Using a Pt-Au / alumina alloy catalyst obtained in the same manner as in Examples 28 to 30, a slurry was prepared in the same manner as in Example 34 as a third step. The carrier was wash coated with these slurries. Next, in drying these slurries, each was irradiated with a microwave having a wavelength of 0.41 nm and an output of 600 W to be dried, and then baked in the air at 500 ° C. for 2 hours.
The exhaust gas purifying catalysts of Examples 42 to 44, which are summarized in the following, were obtained.
【００７７】比較例２７〜２９ 実施例２８〜３０と同様にして得られたＰｔ−Ａｕ／ア
ルミナの合金触媒を用い、第３工程として、実施例３４
と同様にしてスラリーを作成し、モノリス担体にスラリ
ーをウォッシュコートした。次に、このスラリーを乾燥
させるにおいて、それぞれ大気中で、１００℃×２時間
の仮乾燥と２５０℃×３時間の乾燥の後、５５０℃で２
時間焼成し、表９に摘要を示す比較例２７〜２９の排気
ガス浄化用触媒を得た。Comparative Examples 27 to 29 Using a Pt-Au / alumina alloy catalyst obtained in the same manner as in Examples 28 to 30, and as a third step, Example 34
A slurry was prepared in the same manner as described above, and the slurry was wash-coated on a monolithic carrier. Next, the slurry is dried at 550 ° C. after temporary drying at 100 ° C. × 2 hours and drying at 250 ° C. × 3 hours in the air.
After calcining for hours, the exhaust gas purifying catalysts of Comparative Examples 27 to 29 whose summary is shown in Table 9 were obtained.
【００７８】比較例３０ 比較例１０のＰｔ／アルミナの触媒を用い、第３工程と
して、実施例４２と同様にしてスラリーを作成し、モノ
リス担体にスラリーをウォッシュコートし、マイクロ波
を照射して乾燥させ、次いで５００℃の大気中で２時間
焼成したものを比較用の排気ガス浄化用触媒とした。Comparative Example 30 Using the Pt / alumina catalyst of Comparative Example 10, as a third step, a slurry was prepared in the same manner as in Example 42, the slurry was wash-coated on a monolithic carrier, and irradiated with microwaves. The catalyst was dried and then calcined in the air at 500 ° C. for 2 hours to obtain a comparative exhaust gas purifying catalyst.
【００７９】−排気ガス浄化性能試験− 上記の実施例１〜４４と比較例１〜３０の各触媒を、常
圧流通式の耐久処理装置に配置し、空気／燃料（Ａ／
Ｆ）の比が１４.６／１のモデル排気ガス雰囲気下で９
００℃×５時間の加熱を行う耐久処理に供した。-Exhaust Gas Purification Performance Test- Each of the catalysts of Examples 1 to 44 and Comparative Examples 1 to 30 was placed in a normal pressure flow type durable treatment apparatus, and air / fuel (A /
F) in a model exhaust gas atmosphere with a ratio of 14.6 / 1
It was subjected to a durability treatment of heating at 00 ° C. × 5 hours.
【００８０】これらの耐久処理後の各触媒を、固定床流
通反応装置に配置し、下記のリーン雰囲気とリッチ雰囲
気が１秒間ごとに切り替わるモデル排気ガスを流通さ
せ、触媒温度を高めながらＣ3Ｈ6の浄化率を測定した。 リッチ雰囲気のガス組成： ０.１５％Ｃ3Ｈ6＋１.０５％ＣＯ＋０.３３％Ｏ2＋０.３％ＮＯ ＋０.３５％Ｈ2＋１４.１９％ＣＯ2＋１０％Ｈ2Ｏ （残余Ｎ2） リーン雰囲気のガス組成： ０.０５％Ｃ3Ｈ6＋０.１４％ＣＯ＋０.９４％Ｏ2＋０.３４％ＮＯ ＋１４.２７％ＣＯ2＋１０％Ｈ2Ｏ （残余Ｎ2） なお、実施例１７〜２０と比較例１３〜１５の触媒につ
いては、下記のモデル排気ガスを流通させ、触媒温度を
高めながらＣＯの浄化率を測定した。 ０.０６６７％Ｃ3Ｈ6＋１.００％ＣＯ＋１.６％Ｏ2 （残余Ｎ2）Each of these catalysts after the durability treatment was placed in a fixed bed flow reactor, and the following model exhaust gas in which a lean atmosphere and a rich atmosphere were switched every 1 second was passed, and C 3 H was increased while increasing the catalyst temperature. The purification rate of 6 was measured. Of rich atmosphere gas composition: 0.15% C 3 H 6 + 1.05% CO + 0.33% O 2 + 0.3% NO + 0.35% H 2 + 14.19% CO 2 + 10% H 2 O ( residual N 2 ) lean atmosphere gas composition: 0.05% C 3 H 6 + 0.14% CO + 0.94% O 2 + 0.34% NO + 14.27% CO 2 + 10% H 2 O ( the remainder N 2) in examples For the catalysts of Nos. 17 to 20 and Comparative Examples 13 to 15, the following model exhaust gas was passed, and the purification rate of CO was measured while increasing the catalyst temperature. 0.0667% C 3 H 6 + 1.00% CO + 1.6% O 2 (residual N 2 )
【００８１】この排気ガス浄化性能試験において、実施
例１〜３３と比較例１〜２０のペレット形状の触媒で
は、サンプル量は１ｇ、モデル排気ガスの流量は７リッ
トル／分、昇温速度は１０℃／分とし、実施例３４〜４
４と比較例２１〜３０のハニカム形状の触媒では、モデ
ル排気ガスの流量は３０リットル／分、昇温速度は２５
とした。各触媒の５０％浄化率を表１〜９にまとめて示
す。In this exhaust gas purification performance test, the pellet-shaped catalysts of Examples 1 to 33 and Comparative Examples 1 to 20 had a sample amount of 1 g, a model exhaust gas flow rate of 7 liter / min, and a heating rate of 10 g / min. C./min.
4 and the honeycomb-shaped catalysts of Comparative Examples 21 to 30, the flow rate of the model exhaust gas was 30 liter / min, and the heating rate was 25.
And Tables 1 to 9 show the 50% purification rates of each catalyst.
【００８２】−排気ガス浄化性能試験の結果より− （１）実施例１〜９と比較例１〜９を吟味して、第１工
程においてテトラヒドロホウ酸ナトリウムで還元処理を
行うことにより、排気ガス浄化性能がかなり向上するこ
とが分かる。また、この向上は、第２金属がＡｕ、Ｎ
ｉ、Ｆｅのいずれであっても発現し、金属酸化物担体が
アルミナ、セリア、セリア−ジルコニアのいずれであっ
ても発現することが分かる。また、実施例１〜９と比較
例１０〜１２を吟味して、第２金属を還元析出させるこ
とにより、排気ガス浄化性能がかなり向上することが分
かる。-From the results of the exhaust gas purification performance test-(1) After examining Examples 1 to 9 and Comparative Examples 1 to 9, in the first step, a reduction treatment with sodium tetrahydroborate was carried out to obtain an exhaust gas. It can be seen that the purification performance is significantly improved. Also, this improvement is achieved because the second metal is Au, N
It can be seen that the expression occurs regardless of whether the metal oxide carrier is alumina, ceria, or ceria-zirconia. Further, by examining Examples 1 to 9 and Comparative Examples 10 to 12, it can be seen that the reduction and precipitation of the second metal significantly improves the exhaust gas purification performance.
【００８３】（２）実施例１０〜１６と比較例１〜９を
吟味して、第１工程においてＨ2で還元処理を行うこと
により、排気ガス浄化性能がかなり向上することが分か
る。また、この向上は、第２金属がＡｕ、Ｎｉのいずれ
でも発現し、金属酸化物担体がアルミナ、セリア、セリ
ア−ジルコニアのいずれでも発現することが分かる。(2) Examination of Examples 10 to 16 and Comparative Examples 1 to 9 reveals that the reduction treatment with H 2 in the first step significantly improves the exhaust gas purification performance. In addition, it can be seen that this improvement is exhibited by any of Au and Ni as the second metal, and is exhibited by any of alumina, ceria, and ceria-zirconia as the metal oxide carrier.
【００８４】（３）実施例１７〜２０と比較例１３〜１
５を吟味して、第２工程において第２金属の金を還元析
出させる溶液にｐＨの下限があることが分かる。これ
は、塩化金酸の第２金属含有化合物が強酸であるため、
ｐＨ値の調節を行わないと溶液のｐＨが低下し、パラジ
ウムが再溶出して粗大化するためと考えられ、第１金属
がパラジウムの場合、還元析出させる溶液のｐＨは、４
以上が適切であると考えられる。(3) Examples 17 to 20 and Comparative Examples 13 to 1
Examination of No. 5 reveals that the solution for reducing and depositing the second metal, gold, in the second step has a lower limit of pH. This is because the second metal-containing compound of chloroauric acid is a strong acid,
If the pH value is not adjusted, it is considered that the pH of the solution decreases, and the palladium is re-eluted and coarsened. When the first metal is palladium, the pH of the solution to be reduced and precipitated is 4
The above is considered appropriate.
【００８５】また、同様に、実施例２１〜２４と比較例
１６〜１７を吟味して、第１金属が白金の場合は、第２
工程において第２金属の金を還元析出させる溶液にｐＨ
の上限があることが分かる。これは、還元剤の亜硫酸ナ
トリウム等は強アルカリであり、ｐＨ値の調節を行わな
いと溶液のｐＨが上昇し、白金が再溶出して粗大化する
ためと考えられ、第１金属が白金の場合、還元析出させ
る溶液のｐＨは、１０以下が適切であると考えられる。Similarly, by examining Examples 21 to 24 and Comparative Examples 16 to 17, when the first metal was platinum,
PH in the solution for reducing and depositing the second metal in the process
It can be seen that there is an upper limit. This is considered to be because sodium sulfite or the like as a reducing agent is a strong alkali, and if the pH value is not adjusted, the pH of the solution rises, and platinum is re-eluted and coarsened. In this case, the pH of the solution to be reduced and precipitated is considered to be suitably 10 or less.
【００８６】（４）実施例２５と比較例１９を吟味し
て、実施例２５は、超音波に曝しながらＡｕを還元析出
させることで、比較的少量のチオ硫酸ナトリウムとポリ
エチレングリコールの使用によって高い性能の触媒が得
られることを示しており、比較例１９は、ポリエチレン
グリコールを使用しなければ、超音波に曝しても高い性
能の触媒は得られないことを示している。(4) Examining Example 25 and Comparative Example 19, Example 25 shows that by reducing and depositing Au while exposing to ultrasonic waves, the use of a relatively small amount of sodium thiosulfate and polyethylene glycol is high. This shows that a high-performance catalyst can be obtained, and Comparative Example 19 shows that a high-performance catalyst cannot be obtained even when exposed to ultrasonic waves unless polyethylene glycol is used.
【００８７】実施例２６〜２７は、紫外線を照射するこ
とで、ジメチル金(III)アセチルアセトナートからＡｕ
を還元析出させることができ、高い性能の触媒が得られ
ることを示している。したがって、還元析出時に超音波
や紫外線を利用することで、還元剤に含まれるＮａやＳ
等の触媒への混入量を低下させる効果が得られることが
分かる。In Examples 26 and 27, Au was irradiated with ultraviolet light to convert Au from dimethyl gold (III) acetylacetonate.
Shows that a high-performance catalyst can be obtained. Therefore, by using ultrasonic waves or ultraviolet rays at the time of reductive precipitation, Na or S contained in the reducing agent is reduced.
It can be seen that the effect of reducing the amount of the catalyst mixed into the catalyst can be obtained.
【００８８】（５）実施例２８〜３３と、比較例１、
３、４、及び６を吟味して、これらの例は、乾燥の仕方
がマイクロ波加熱と伝熱加熱の点で相違するが、排気ガ
ス浄化性能にかなりの相違が見られる。このことは、水
を沸点付近で蒸発させる通常の伝熱加熱では、ｐＨが局
所的に強酸又は強アルカリとなり、第１金属又は第２金
属が再溶出するが、マイクロ波加熱では、こうした局所
的なｐＨの変化は生じにくいためと考えられる。また、
実施例３２〜３３では、乾燥前に水をエタノールで置換
することで、解離イオンの量を抑えることができ、通常
の伝熱加熱でも、同様に、第１金属又は第２金属の再溶
出が抑制されるものと考えられる。(5) Examples 28 to 33 and Comparative Example 1,
Examining 3, 4, and 6, these examples differ in the way of drying between microwave heating and heat transfer heating, but show significant differences in exhaust gas purification performance. This means that in normal heat transfer heating in which water is evaporated near the boiling point, the pH locally becomes a strong acid or strong alkali, and the first metal or the second metal is re-eluted. It is considered that a significant change in pH is unlikely to occur. Also,
In Examples 32 to 33, the amount of dissociated ions can be suppressed by substituting water with ethanol before drying, and the re-elution of the first metal or the second metal can be similarly performed by ordinary heat transfer heating. It is considered to be suppressed.
【００８９】（６）実施例３４〜３７と比較例２１〜２
３、及び実施例３８〜４１と比較例２４〜２６を吟味し
て、第３工程においてウォッシュコートさせるスラリー
に適切なｐＨの範囲があることが分かる。この理由は、
第２工程と同様に、第１金属又は第２金属の溶出を抑え
るのに適切なｐＨの範囲があるためと考えられる。(6) Examples 34 to 37 and Comparative Examples 21 to 2
3, and Examples 38-41 and Comparative Examples 24-26 show that the slurry to be wash-coated in the third step has an appropriate pH range. The reason for this is
As in the second step, it is considered that there is an appropriate pH range for suppressing the elution of the first metal or the second metal.
【００９０】（７）実施例４２〜４４と比較例２７〜３
０を吟味して、ウォッシュコートされたスラリーを乾燥
させるにおいても、マイクロ波加熱の方が通常の伝熱加
熱よりも高い浄化性能の触媒が得られることが分かり、
この理由は、第２工程と同様に、マイクロ波加熱により
第１金属又は第２金属の溶出が抑制されるためと考えら
れる。(7) Examples 42 to 44 and Comparative Examples 27 to 3
Examining 0, even in drying the wash-coated slurry, it can be seen that microwave heating can obtain a catalyst with higher purification performance than normal heat transfer heating,
This is probably because the elution of the first metal or the second metal is suppressed by the microwave heating, as in the second step.
【００９１】[0091]
【発明の効果】高い排気ガス浄化性能を提供する積相構
造を有する触媒を、再現性よく安定して製造することが
できる。According to the present invention, it is possible to stably produce a catalyst having a product phase structure that provides high exhaust gas purification performance with good reproducibility.
【００９２】[0092]
【表１】 [Table 1]
【００９３】[0093]
【表２】 [Table 2]
【００９４】[0094]
【表３】 [Table 3]
【００９５】[0095]
【表４】 [Table 4]
【００９６】[0096]
【表５】 [Table 5]
【００９７】[0097]
【表６】 [Table 6]
【００９８】[0098]
【表７】 [Table 7]
【００９９】[0099]
【表８】 [Table 8]
【０１００】[0100]
【表９】 [Table 9]
【図１】本発明の排気ガス浄化用触媒を製造する工程の
概略のフローチャートである。FIG. 1 is a schematic flowchart of a process for producing an exhaust gas purifying catalyst of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 37/02 １０１ Ｂ０１Ｊ 37/02 ３０１Ｃ ３０１ 37/34 37/34 Ｃ２３Ｃ 18/31 Ｚ Ｃ２３Ｃ 18/31 24/08 Ｚ 24/08 Ｂ０１Ｄ 53/36 １０４Ａ (72)発明者 伊藤 祐介 愛知県豊田市トヨタ町１番地 トヨタ自動 車株式会社内 Ｆターム(参考） 4D048 AA06 AA13 AA18 AB05 BA03X BA06Y BA07Y BA08X BA11Y BA18Y BA19X BA23Y BA24Y BA25Y BA28Y BA30X BA31X BA34X BA35Y BA36X BA37Y BA38X BA41X BA42X BB01 BB02 4G069 AA03 AA08 BA01A BA01B BA02A BA03A BA05A BA07A BB02A BB02B BB04A BB04B BB06A BB06B BC29A BC31A BC33A BC33B BC42A BC43A BC43B BC50A BC51A BC51B BC54A BC55A BC58A BC62A BC66A BC66B BC67A BC68A BC68B BC70A BC71A BC72A BC72B BC75A BC75B CA02 CA03 CA09 EA02Y EA19 EB12Y EB14Y EB18Y EC02Y EC03Y FA02 FA03 FB14 FB15 FB19 FB20 FB23 FB43 FB44 FB45 FB57 FB58 FB78 FC09 4K022 AA02 BA03 BA06 BA07 BA08 BA09 BA11 BA14 BA18 BA22 BA26 BA28 BA31 BA32 BA36 DA01 DA06 DB08 DB11 EA01 4K044 AB01 BA02 BA06 BA08 CA24 CA27 CA53 CA55 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01J 37/02 101 B01J 37/02 301C 301 37/34 37/34 C23C 18/31 Z C23C 18/31 24 / 08 Z 24/08 B01D 53/36 104A (72) Inventor Yusuke Ito 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Corporation F-term (reference) 4D048 AA06 AA13 AA18 AB05 BA03X BA06Y BA07Y BA08X BA11Y BA18Y BA19X BA23Y BA24Y BA25Y BA28Y BA30X BA31X BA34X BA35Y BA36X BA37Y BA38X BA41X BA42X BB01 BB02 4G069 AA03 AA08 BA01A BA01B BA02A BA03A BA05A BA07A BB02A BB02B BB04A BB04B BB06A BB06B BC29A BC31A BC33A BC33B BC42A BC43A BC43B BC50A BC51A BC51B BC54A BC55A BC58A BC62A BC66A BC66B BC67A BC68A BC68B BC70A BC71A BC72A BC72B BC75A BC75B CA02 CA03 CA09 EA02Y EA19 EB12Y EB14Y EB18Y EC02Y E C03Y FA02 FA03 FB14 FB15 FB19 FB20 FB23 FB43 FB44 FB45 FB57 FB58 FB78 FC09 4K022 AA02 BA03 BA06 BA07 BA08 BA09 BA11 BA14 BA18 BA22 BA26 BA28 BA31 BA32 BA36 DA01 DA06 DB08 DB11 EA01 4K044 AB01 CA02 BA06 BA06
Claims (8)
後、前記第１金属上に第２金属を還元析出させる合金触
媒の製造方法において、担持された前記第１金属に還元
処理を施した後に前記第２金属を還元析出させることを
特徴とする合金触媒の製造方法。1. A method for producing an alloy catalyst in which a first metal is supported on a metal oxide support and then a second metal is reduced and deposited on the first metal, wherein the supported first metal is subjected to a reduction treatment. A method for producing an alloy catalyst, wherein the second metal is reduced and precipitated after the application.
ムを担持した後、前記パラジウム上に第２金属を還元析
出させる合金触媒の製造方法において、前記第２金属の
化合物を溶解し、前記パラジウムが担持された前記金属
酸化物担体を分散したスラリーのｐＨが４〜６の範囲
で、前記第２金属を前記パラジウム上に還元析出させる
ことを特徴とする合金触媒の製造方法。2. A method for producing an alloy catalyst in which palladium of a first metal is supported on a metal oxide carrier and then a second metal is reduced and deposited on the palladium, the compound of the second metal is dissolved, A method for producing an alloy catalyst, wherein the second metal is reduced and precipitated on the palladium within a pH range of 4 to 6 of a slurry in which the metal oxide carrier supporting palladium is dispersed.
後、前記第１金属上に第２金属を還元析出させる合金触
媒の製造方法において、前記第２金属の化合物を溶解
し、前記第１金属が担持された前記金属酸化物担体を分
散したスラリーに、超音波、プラズマ、及び電磁波の少
なくとも１種を照射しながら前記第１金属上に前記第２
金属を還元析出させることを特徴とする合金触媒の製造
方法。3. A method for producing an alloy catalyst in which a first metal is supported on a metal oxide carrier and then a second metal is reduced and precipitated on the first metal, wherein a compound of the second metal is dissolved. While irradiating the slurry in which the metal oxide carrier carrying the first metal is dispersed with at least one of ultrasonic waves, plasma, and electromagnetic waves, the second metal
A method for producing an alloy catalyst, comprising reducing and depositing a metal.
クロ波を用いて、前記金属酸化物担体を分散したスラリ
ーを乾燥させる請求項１〜３のいずれか１項に記載の合
金触媒の製造方法。4. The alloy catalyst according to claim 1, wherein after the second metal is reduced and precipitated, the slurry in which the metal oxide carrier is dispersed is dried using microwaves. Production method.
金属酸化物担体を分散したスラリーの分散媒を水から有
機溶媒に置換する請求項１〜４のいずれか１項に記載の
合金触媒の製造方法。5. The alloy according to claim 1, wherein after the second metal is reduced and precipitated, the dispersion medium of the slurry in which the metal oxide carrier is dispersed is replaced with water from an organic solvent. Method for producing catalyst.
れ、前記第１金属上に第２金属が還元析出されてなる合
金触媒を、排気ガス通路付担体に担持する際に、前記合
金触媒を分散したスラリーを、所定のｐＨ範囲で前記排
気ガス通路付担体にコートすることを特徴とする排気ガ
ス浄化用触媒の製造方法。6. An alloy catalyst comprising a first metal supported on a metal oxide carrier and a second metal reduced and deposited on the first metal, wherein the alloy catalyst is supported on an exhaust gas passage carrier. A method for producing an exhaust gas purifying catalyst, comprising coating a slurry in which a catalyst is dispersed on the carrier with an exhaust gas passage in a predetermined pH range.
ガス通路付担体にコートした後、前記スラリーをマイク
ロ波によって乾燥させる請求項６に記載の排気ガス浄化
用触媒の製造方法。7. The method for producing an exhaust gas purifying catalyst according to claim 6, wherein the slurry containing the alloy catalyst is coated on the carrier with exhaust gas passages, and then the slurry is dried by microwave.
ずれか１項の方法によって得られた合金触媒を使用する
請求項６又は７に記載の排気ガス浄化用触媒の製造方
法。8. The method for producing an exhaust gas purifying catalyst according to claim 6, wherein the alloy catalyst obtained by the method according to claim 1 is used as the alloy catalyst.
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