JP5871257B2 - Exhaust purification catalyst, method of using exhaust purification catalyst, and method of manufacturing exhaust purification catalyst - Google Patents
Exhaust purification catalyst, method of using exhaust purification catalyst, and method of manufacturing exhaust purification catalyst Download PDFInfo
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- 238000000746 purification Methods 0.000 title claims description 72
- 238000000034 method Methods 0.000 title claims description 33
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- 239000004332 silver Substances 0.000 claims description 103
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 100
- 229910052725 zinc Inorganic materials 0.000 claims description 99
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 92
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Description
本発明は、酸素を含有する排出ガス中で窒素酸化物を浄化する排気浄化用触媒、排気浄化用触媒の使用方法及び排気浄化用触媒の製造方法に関するものである。 The present invention relates to an exhaust purification catalyst that purifies nitrogen oxides in an exhaust gas containing oxygen, a method of using the exhaust purification catalyst, and a method of manufacturing the exhaust purification catalyst.
ディーゼルエンジンやガスタービンの燃焼排ガス中においては、多量の酸素が含まれているため、窒素酸化物（以下、「NOx」と記すこともある）は、酸素が含まれている条件で選択的に還元することにより除去される。そのNOxの浄化方法としては、（イ）アンモニアもしくは尿素を外部から供給する選択的接触還元法や（ロ）NOx吸蔵還元法が実用化されているが、インフラを含む尿素供給体制の整備や触媒に含まれる貴金属量が多いことから大きなコスト要因となっている。 Since combustion engine exhaust gas from diesel engines and gas turbines contains a large amount of oxygen, nitrogen oxides (hereinafter sometimes referred to as “NO x ”) are selectively used under conditions that contain oxygen. It is removed by reducing to. As the NO x purification method, (b) selective catalytic reduction method that supplies ammonia or urea from the outside and (b) NO x storage reduction method has been put into practical use. And the amount of noble metals contained in the catalyst is a large cost factor.
一方、上記（イ）や（ロ）とは異なり、（ハ）酸化性雰囲気において炭化水素類を還元剤としてNOxを還元する方法が提案されている。これによれば、比較的安価な銀、コバルトなどの金属や少量の白金などの貴金属を含むアルミナなどの金属酸化物や種々の金属を担持させたゼオライトが触媒として用いられ（非特許文献１、特許文献１〜４参照）、中でも特に銀を担持したγアルミナ触媒が比較的高い活性を有している。 On the other hand, unlike (a) and (b) above, (c) a method of reducing NOx using hydrocarbons as a reducing agent in an oxidizing atmosphere has been proposed. According to this, a relatively inexpensive metal such as silver or cobalt or a metal oxide such as alumina containing a small amount of noble metal such as platinum or zeolite carrying various metals is used as a catalyst (Non-patent Document 1, In particular, the γ-alumina catalyst supporting silver has a relatively high activity.
ところで、NOx選択還元を行う方法として、燃料等の高級炭化水素を反応性の高い低級炭化水素に変換した後、その低級炭化水素をNOx選択還元に利用するものがいくつか提案されている。例えば特許文献５においては、排出ガスが流れる主管に対して分岐する分岐管内に燃料の一部を供給し、その燃料をその分岐管内に配置される触媒をもって反応性の高い水素や低級炭化水素に分解し、その低級炭化水素等を主管に供給することにより、その低級炭化水素等を利用してNOx選択還元触媒によりNOxを浄化する方法が提案されている。また、特許文献６には、排気系に配置される１つの触媒を、前段部と、該前段部よりも下流側に配置される後段部とに分け、前段部には、高級炭化水素を低級炭化水素に分解する部分酸化触媒を配置し、後段部には、前段部において得られた低級炭化水素を利用してNOxを還元するNOx選択還元触媒を配置するものが提案されている。
これらによれば、燃料の一部を利用して、低級炭化水素を得ることができ、その低級炭化水素を、NOxに対する還元剤として、NOx選択還元触媒に供給することができる。
As a method of performing the NO x selective reduction, after converting the higher hydrocarbons such as fuel with high reactivity lower hydrocarbons have been proposed several utilizes the lower hydrocarbon to the NO x selective reduction . For example, in
According to these, by using a part of the fuel, it is possible to obtain a lower hydrocarbon, the lower hydrocarbon, as a reducing agent for NO x, it can be supplied to the NO x selective reduction catalyst.
しかし、上述のようなNOxの浄化方法においては、前者（特許文献５）に関しては、排気系の主管に対して分岐管を設けると共に、その分岐管及び主管に特有の触媒をそれぞれ設けなければならず、複雑な構造にならざるを得ない。また、後者（特許文献６）に関しては、１つの触媒といえども、実質的には、その触媒は前段部と後段部とに分かれる構造となり、触媒として複雑なものとならざるを得ない。このため、燃料等の高級炭化水素を反応性の高い低級炭化水素に変換した後、その低級炭化水素をNOx選択還元に利用しようとした場合、触媒構造ないしは触媒利用構造が複雑にならざるを得ない。 However, in the purification method of the NO x as described above, with respect to the former (Patent Document 5), provided with a branch pipe with respect to the exhaust system of the main pipe, to be provided each specific catalyst in its branch pipe and main pipe It must be a complicated structure. Regarding the latter (Patent Document 6), even if it is a single catalyst, the catalyst is substantially divided into a front part and a rear part, and the catalyst must be complicated. Therefore, after converting the higher hydrocarbons such as fuel with high reactivity lower hydrocarbon, if you try to use the lower hydrocarbon to the NO x selective reduction catalyst structures or catalyst utilization structure choice but complicated I don't get it.
これに対して、上記触媒構造等を簡素化すべく、高級炭化水素を低級炭化水素に変化させる炭化水素分解触媒と、その炭化水素分解触媒により分解される低級炭化水素を還元剤としてNOxを還元するNOx選択還元触媒と、を１つの触媒形態（例えば混合状態のもの）とすることが考えられる。
しかし、炭化水素分解触媒とNOx選択還元触媒とを無闇に混合状態としても、その１つの触媒形態をとる触媒は、前述の特許文献５，６のようにはNOxの浄化性能を高めることができない。
Reducing contrast, in order to simplify the catalyst structure and the like, and hydrocarbon cracking catalyst for changing the higher hydrocarbons to lower hydrocarbons, the NO x lower hydrocarbon which is decomposed by the hydrocarbon cracking catalyst as a reducing agent It is conceivable that the NOx selective reduction catalyst to be made into one catalyst form (for example, in a mixed state).
However, even if the hydrocarbon cracking catalyst and the NO x selective reduction catalyst are mixed in a dark state, the catalyst in one catalyst form can improve the NO x purification performance as in
本発明は、上記事情に鑑みてなされたもので、その第１の技術的課題は、高級炭化水素から低級炭化水素を生成すると共に、その低級炭化水素を還元剤として窒素酸化物を還元する排気浄化用触媒において、触媒構造等の簡素化を図ると共に、窒素酸化物の浄化性能を極力高めることにある。
第２の技術的課題は、上記排気浄化用触媒を利用した排気浄化用触媒の使用方法を提供することにある。
第３の技術的課題は、上記排気浄化用触媒を製造する排気浄化用触媒の製造方法を提供することにある。
The present invention has been made in view of the above circumstances, and a first technical problem thereof is an exhaust gas that generates lower hydrocarbons from higher hydrocarbons and reduces nitrogen oxides using the lower hydrocarbons as reducing agents. In purifying catalysts, it is intended to simplify the catalyst structure and the like, and to improve the purification performance of nitrogen oxides as much as possible.
A second technical problem is to provide a method for using an exhaust purification catalyst using the exhaust purification catalyst.
A third technical problem is to provide a method for producing an exhaust purification catalyst for producing the exhaust purification catalyst.
上記第１の技術的課題を達成するために本発明(請求項１に係る発明)にあっては、
低級炭化水素を用いて窒素酸化物を還元する第１触媒成分と、
前記第１触媒成分の活性温度領域において、少なくとも、前記低級炭化水素を高級炭化水素から生成する第２触媒成分と、
が、分散した状態で含有されている、
ことを特徴とする排気浄化用触媒とした構成としてある。この請求項１の好ましい態様としては、請求項２〜９に記載のとおりである。
In order to achieve the first technical problem, the present invention (the invention according to claim 1)
A first catalyst component for reducing nitrogen oxides using lower hydrocarbons;
A second catalyst component that generates at least the lower hydrocarbon from a higher hydrocarbon in the active temperature region of the first catalyst component;
Is contained in a dispersed state,
The exhaust gas purifying catalyst is characterized by the above. Preferred embodiments of the first aspect are as described in the second to ninth aspects.
前記第２の技術的課題を達成するために本発明(請求項１０に係る発明)にあっては、
過剰な酸素と共に窒素酸化物をも含有する排気ガス中に排気浄化用触媒を配置し、該排気浄化用触媒により、低級炭化水素を還元剤として、窒素酸化物を還元する排気浄化用触媒の使用方法において、
前記排気浄化用触媒として、低級炭化水素を用いて窒素酸化物を還元する第１触媒成分と、前記第１触媒成分の活性温度領域において、少なくとも、前記低級炭化水素を高級炭化水素から生成する第２触媒成分と、が含有されているものを用い、
前記排気ガス中に、前記排気浄化用触媒の上流側において、前記低級炭化水素よりも高級とされた高級炭化水素を供給する構成としてある。
In order to achieve the second technical problem, the present invention (the invention according to claim 10),
Use of an exhaust purification catalyst in which an exhaust purification catalyst is disposed in an exhaust gas containing nitrogen oxides together with excess oxygen, and the exhaust purification catalyst reduces nitrogen oxides using lower hydrocarbons as a reducing agent. In the method
A first catalyst component that reduces nitrogen oxides using lower hydrocarbons as the exhaust purification catalyst, and a first catalyst component that generates at least the lower hydrocarbons from higher hydrocarbons in the active temperature region of the first catalyst component. Using two catalyst components,
In the exhaust gas, higher hydrocarbons that are higher than the lower hydrocarbons are supplied upstream of the exhaust purification catalyst.
前記第３の技術的課題を達成するために本発明(請求項１１に係る発明)にあっては、
低級炭化水素を用いて窒素酸化物を還元する第１触媒成分と、
前記第１触媒成分の活性温度領域において、少なくとも、前記低級炭化水素を高級炭化水素から生成する第２触媒成分と、を用意し、
前記第１触媒成分と前記第２触媒成分とを混合する、
ことを特徴とする排気浄化用触媒の製造方法とした構成としてある。
In order to achieve the third technical problem in the present invention (the invention according to claim 11),
A first catalyst component for reducing nitrogen oxides using lower hydrocarbons;
A second catalyst component for producing at least the lower hydrocarbon from a higher hydrocarbon in the active temperature region of the first catalyst component;
Mixing the first catalyst component and the second catalyst component;
The exhaust gas purification catalyst manufacturing method is characterized by the above.
また、前記第３の技術的課題を達成するために本発明(請求項１２に係る発明)にあっては、
第１担持成分と、第２担持成分と、共通担体成分とを用意し、
前記共通担体成分に前記第１担持成分を担持して、該共通担体成分と該第１担持成分とにより、低級炭化水素を用いて窒素酸化物を還元成分に還元する第１触媒成分を構成し、
前記共通担体成分に前記第２担持成分を担持して、該共通担体成分と該第２担持成分とにより、前記第１触媒成分の活性温度領域において、少なくとも、前記低級炭化水素を高級炭化水素から生成する第２触媒成分を構成する、
ことを特徴とする排気浄化用触媒の製造方法とした構成としてある。
In order to achieve the third technical problem, the present invention (the invention according to claim 12)
Preparing a first carrier component, a second carrier component, and a common carrier component;
The first carrier component is supported on the common carrier component, and the common carrier component and the first carrier component constitute a first catalyst component for reducing nitrogen oxides to a reducing component using lower hydrocarbons. ,
The second carrier component is supported on the common carrier component, and at least the lower hydrocarbon is converted from the higher hydrocarbon in the active temperature region of the first catalyst component by the common carrier component and the second carrier component. Constituting a second catalyst component to be produced;
The exhaust gas purification catalyst manufacturing method is characterized by the above.
本発明（請求項１に係る発明）によれば、当該排気浄化用触媒においては、第１触媒成分と第２触媒成分とが分散状態で含有されて、１つの触媒形態（単一層）とされていることから、触媒自体を簡素化できるだけでなく、その１つの触媒形態を利用することにより、触媒利用構造の簡素化（複数の触媒を１つの触媒にすること）を図って、利用形態の制約を大幅に緩和することができる。
他方、排気系に当該排気浄化用触媒を配置すると共にその排気系に高級炭化水素を供給することにより、第２触媒成分は、第１触媒成分の活性温度領域において、少なくとも、高級炭化水素から低級炭化水素を生成し、その低級炭化水素を第１触媒成分に供給する。第１触媒成分は、その低級炭化水素を還元剤として有効に利用し、窒素酸化物を還元成分に効果的に還元する。このように、第１、第２触媒成分は、共通の活性温度領域において、互いが有機的に協働し、窒素酸化物の浄化性能を極力高める。
この場合、第１触媒成分により生成された還元成分については、第２触媒成分の特性（吸着機能）、第１触媒成分と第２触媒成分とが分散状態とされて互いに近接配置状態にあること等に基づき、直ちに、第１触媒成分から脱離して第２触媒成分に吸着され、その吸着された還元成分は、その各要素の結合力が極めて弱いことと、極性を有していること等に基づき、窒素酸化物、酸素、水等のアタックを受けて、順次、迅速に窒素にまで還元される。
したがって、高級炭化水素から低級炭化水素を生成すると共に、その低級炭化水素を還元剤として窒素酸化物を還元する排気浄化用触媒において、触媒構造等の簡素化を図ることができると共に、窒素酸化物の浄化性能を極力高めることができる。
According to the present invention (the invention according to claim 1), in the exhaust purification catalyst, the first catalyst component and the second catalyst component are contained in a dispersed state to form one catalyst form (single layer). Therefore, not only the catalyst itself can be simplified, but also by utilizing one catalyst form, the structure of utilizing the catalyst can be simplified (a plurality of catalysts can be made into one catalyst). Restrictions can be greatly relaxed.
On the other hand, by disposing the exhaust purification catalyst in the exhaust system and supplying higher hydrocarbons to the exhaust system, the second catalyst component is at least lower than the higher hydrocarbons in the active temperature region of the first catalyst component. Hydrocarbon is produced and the lower hydrocarbon is fed to the first catalyst component. The first catalyst component effectively uses the lower hydrocarbon as a reducing agent, and effectively reduces nitrogen oxides to the reducing component. As described above, the first and second catalyst components organically cooperate with each other in the common activation temperature region, and the nitrogen oxide purification performance is enhanced as much as possible.
In this case, with respect to the reducing component generated by the first catalyst component, the characteristics (adsorption function) of the second catalyst component, the first catalyst component and the second catalyst component are in a dispersed state, and are close to each other. And the like, immediately desorbed from the first catalyst component and adsorbed by the second catalyst component, and the adsorbed reducing component has a very weak binding force of each element and has a polarity, etc. Based on the above, it is attacked by nitrogen oxides, oxygen, water, etc., and is successively reduced to nitrogen quickly.
Therefore, in an exhaust purification catalyst that generates lower hydrocarbons from higher hydrocarbons and reduces nitrogen oxides using the lower hydrocarbons as a reducing agent, the catalyst structure and the like can be simplified, and nitrogen oxides can be achieved. The purification performance of can be increased as much as possible.
請求項２に係る発明によれば、第２触媒成分が、担体成分と、該担体成分に担持されて低級炭化水素を高級炭化水素から生成する担持成分と、を備え、担体成分として、酸性酸化物が用いられていることから、担体成分に関する知見に基づき、第１触媒成分と協働させることにより、NOx浄化性能を高める上で好ましいものにできる。 According to the invention of claim 2, the second catalyst component includes a support component and a support component that is supported on the support component and generates lower hydrocarbons from higher hydrocarbons. Since the product is used, based on the knowledge about the carrier component, it can be made preferable to enhance the NO x purification performance by cooperating with the first catalyst component.
請求項３に係る発明によれば、第２触媒成分における担体成分としての酸性酸化物が、ゼオライト又はアルミナであることから、酸性酸化物の知見に基づき、第１触媒成分と協働させることにより、NOx浄化性能を高める上で具体的に好ましいものにできる。 According to the invention of claim 3, since the acidic oxide as the carrier component in the second catalyst component is zeolite or alumina, based on the knowledge of the acidic oxide, by cooperating with the first catalyst component In particular, it can be made preferable for enhancing the NO x purification performance.
請求項４に係る発明によれば、第２触媒成分における担持成分が、亜鉛、コバルト、タングステン、インジウム、ガリウム、マンガン、バリウムのうちのいずれか１種又は複数種であることから、第２触媒成分における担体成分を酸性酸化物とする状況の下での担持成分の知見に基づき、第１触媒成分と協働させることにより、NOx浄化性能を高める上で好ましいものにできる。 According to the invention according to claim 4, since the supported component in the second catalyst component is any one or more of zinc, cobalt, tungsten, indium, gallium, manganese, and barium, the second catalyst based carrier component in the component to the findings of the bearing components under conditions that the acidic oxide, by cooperating with the first catalyst component can be in the preferable in enhancing the the NO x purification performance.
請求項５に係る発明によれば、酸性酸化物がゼオライトであることから、第２触媒成分における担持成分を亜鉛、コバルト、タングステン、インジウム、ガリウム、マンガン、バリウムのうちのいずれか１種又は複数種とする状況の下での担体成分の知見に基づき、第１触媒成分と協働させることにより、NOx浄化性能を高める上で好ましいものにできる。
According to the invention of
請求項６に係る発明によれば、ゼオライトの種類が、その各活性温度領域を判断要素として、排気ガスの温度に応じたものとされていることから、ゼオライトの種類に応じた活性温度特性に関する知見を利用して、排気ガス温度に適したゼオライトを選択し、窒素酸化物を的確に浄化できる。 According to the invention according to claim 6, since the type of zeolite is determined according to the temperature of the exhaust gas using each active temperature region as a determination factor, it relates to the active temperature characteristics according to the type of zeolite. Utilizing the knowledge, it is possible to select the zeolite suitable for the exhaust gas temperature and to purify the nitrogen oxide accurately.
請求項７に係る発明によれば、第１触媒成分が、担体成分としてのアルミナに銀が担持された銀担持触媒成分であり、第１触媒成分と第２触媒成分との含有割合は、排気ガス温度が低い側に位置するほど、第１触媒成分の含有割合が第２触媒成分の含有割合よりも大きくなるように設定されていることから、第１及び第２触媒成分の含有割合に応じた活性温度領域に関する知見を利用して、当該排気浄化用触媒を、排気ガス温度に応じて的確に用いることができる。 According to the invention of claim 7, the first catalyst component is a silver-supported catalyst component in which silver is supported on alumina as a carrier component, and the content ratio of the first catalyst component and the second catalyst component is the exhaust gas. Since the content ratio of the first catalyst component is set to be larger than the content ratio of the second catalyst component as the gas temperature is lower, the content ratio of the first and second catalyst components depends on the content ratio. The exhaust purification catalyst can be accurately used according to the exhaust gas temperature by utilizing the knowledge about the active temperature region.
請求項８に係る発明によれば、第１触媒成分が、担体成分としてのアルミナに銀が担持された銀担持触媒成分であることから、その窒素酸化物に対する高い還元能力を第１触媒成分として効果的に利用できる。このため、第１触媒成分と第２触媒成分とを有効に機能させて、窒素酸化物の浄化性能を効果的に向上させることができる。 According to the eighth aspect of the invention, since the first catalyst component is a silver-supported catalyst component in which silver is supported on alumina as a support component, its high reducing ability with respect to nitrogen oxides is used as the first catalyst component. It can be used effectively. For this reason, the 1st catalyst component and the 2nd catalyst component can be functioned effectively, and the purification performance of nitrogen oxides can be improved effectively.
請求項９に係る発明によれば、第１触媒成分と第２触媒成分との含有重量比が、５０：５０〜８８：１２であることから、第１及び第２触媒成分の含有重量割合に応じた活性温度領域に関する知見に基づき、好ましい所定の温度範囲である３００℃〜６００℃で、高い窒素酸化物の浄化性能を確保できる。
ここで、第１触媒成分と第２触媒成分との含有重量比が、５０：５０〜８８：１２としているのは、この混合比の範囲で有効性を確認できるからである。
According to the ninth aspect of the present invention, since the content weight ratio of the first catalyst component and the second catalyst component is 50:50 to 88:12, the content weight ratio of the first and second catalyst components is increased. Based on the knowledge about the corresponding active temperature region, high nitrogen oxide purification performance can be secured at a preferable predetermined temperature range of 300 ° C. to 600 ° C.
Here, the reason why the weight ratio of the first catalyst component and the second catalyst component is 50:50 to 88:12 is that the effectiveness can be confirmed within the range of the mixing ratio.
請求項１０に係る発明によれば、１つの触媒形態（単一層）とされる当該排気浄化用触媒が排気系に用いられることから、その１つの触媒形態を利用することにより、触媒利用構造の簡素化（複数の触媒を１つの触媒にすること）を図ることができる。
その一方、排気系に当該排気浄化用触媒を配置すると共にその排気系に高級炭化水素を供給することにより、前述の請求項１の作用同様、高級炭化水素から低級炭化水素を生成すること、その低級炭化水素を還元剤として窒素酸化物を還元すること等を行わせることができることになり、窒素酸化物の還元処理（一連の各過程）を円滑且つ迅速に行わせることができる。
これにより、当該排気浄化用触媒を利用した排気浄化用触媒の使用方法を提供できる。
According to the invention of claim 10, since the exhaust purification catalyst in a single catalyst form (single layer) is used in the exhaust system, the catalyst utilization structure can be obtained by utilizing the single catalyst form. Simplification (making a plurality of catalysts into one catalyst) can be achieved.
On the other hand, by arranging the exhaust purification catalyst in the exhaust system and supplying higher hydrocarbons to the exhaust system, it is possible to produce lower hydrocarbons from higher hydrocarbons as in the operation of claim 1 above, Reduction of nitrogen oxides using lower hydrocarbons as a reducing agent can be performed, and reduction treatment (a series of steps) of nitrogen oxides can be performed smoothly and quickly.
Thereby, the usage method of the exhaust gas purification catalyst using the exhaust gas purification catalyst can be provided.
請求項１１に係る発明によれば、低級炭化水素を用いて窒素酸化物を還元する第１触媒成分と、第１触媒成分の活性温度領域において、少なくとも、低級炭化水素を高級炭化水素から生成する第２触媒成分と、を用意し、第１触媒成分と前記第２触媒成分とを混合することから、当該製造方法により、前述の請求項１に係る排気浄化用触媒を得ることができる。 According to the eleventh aspect of the present invention, at least the lower hydrocarbon is produced from the higher hydrocarbon in the active temperature region of the first catalyst component that reduces the nitrogen oxide using the lower hydrocarbon and the first catalyst component. Since the second catalyst component is prepared and the first catalyst component and the second catalyst component are mixed, the exhaust purification catalyst according to the first aspect of the present invention can be obtained by the manufacturing method.
請求項１２に係る発明によれば、第１担持成分と、第２担持成分と、共通担体成分とを用意し、共通担体成分に第１担持成分を担持して、該共通担体成分と該第１担持成分とにより、低級炭化水素を用いて窒素酸化物を還元成分に還元する第１触媒成分を構成し、共通担体成分に第２担持成分を担持して、該共通担体成分と該第２担持成分とにより、第１触媒成分の活性温度領域において、少なくとも、低級炭化水素を高級炭化水素から生成する第２触媒成分を構成することから、当該排気浄化用触媒（材料）においても、第１、第２触媒成分を分散状態にしつつ含有させることができる。このため、この場合においても、当該製造方法により、前述の請求項１に係る排気浄化用触媒を得ることができる。 According to the invention of claim 12, the first carrier component, the second carrier component, and the common carrier component are prepared, the first carrier component is carried on the common carrier component, and the common carrier component and the first carrier component are prepared. The first supported component constitutes a first catalyst component for reducing nitrogen oxides to a reduced component using lower hydrocarbons, the second supported component is supported on the common carrier component, and the common carrier component and the second Since the supported component constitutes at least a second catalyst component that generates lower hydrocarbons from higher hydrocarbons in the active temperature range of the first catalyst component, the exhaust purification catalyst (material) also includes the first catalyst component. The second catalyst component can be contained in a dispersed state. Therefore, even in this case, the exhaust purification catalyst according to claim 1 can be obtained by the manufacturing method.
以下、本発明の実施形態を詳細に説明する。
本実施形態に係る排気浄化用触媒は、図１の概念図に示すように、第１触媒成分と第２触媒成分とが分散した状態で含有されている。
Hereinafter, embodiments of the present invention will be described in detail.
As shown in the conceptual diagram of FIG. 1, the exhaust purification catalyst according to the present embodiment contains the first catalyst component and the second catalyst component in a dispersed state.
１．前記第１触媒成分は、図１に示すように、主として、低級炭化水素（図１中では低級HCとして示す）を還元剤として用いて窒素酸化物を選択的に還元する機能を有している。
（１）具体的には、第１触媒成分は、その活性サイト（図１参照）において、低級炭化水素（常温常圧下において、ガスとして存在する炭化水素：Ｃの数にして４程度まで）を還元剤として利用することにより、窒素酸化物（NOx）、例えばNOを、還元成分（反応中間体）としての含窒素化合物（NCO、NHx、CN、RNO2等）に還元する機能を発揮する。この場合、第１触媒成分の活性温度領域は、エンジンの排気ガス温度である約１５０〜６５０℃で、中でもNOx排出量が高い２５０〜６００℃で効果を示す。
1. As shown in FIG. 1, the first catalyst component mainly has a function of selectively reducing nitrogen oxides using a lower hydrocarbon (shown as lower HC in FIG. 1) as a reducing agent. .
(1) Specifically, the first catalyst component contains lower hydrocarbons (hydrocarbons present as gas under normal temperature and normal pressure: up to about 4 as the number of C) at the active site (see FIG. 1). By using as a reducing agent, it functions to reduce nitrogen oxides (NO x ), such as NO, to nitrogen-containing compounds (NCO, NH x , CN, RNO 2 etc.) as reducing components (reaction intermediates) To do. In this case, the activation temperature range of the first catalyst component is about 150 to 650 ° C. which is the exhaust gas temperature of the engine, and the effect is particularly high at 250 to 600 ° C. where the NO x emission amount is high.
（２）より具体的には、第１触媒成分は、担体成分と、その担体に担持される担持成分（第１担持成分）とを備える構成とされている。
(i)上記担持成分は、主として、低級炭化水素を用いて、NOxであるNOを還元成分（反応中間体）としての含窒素化合物(NCO、NHx、CN、RNO2等）に効果的に還元する観点から選択されており、本実施形態においては、担持成分として銀（Ag）が選択されている（後述の図２、図３等参照）。この銀に関しては、上記機能を良好に果たす観点から、その含有量（銀を担持した後述のアルミナ、ゼオライトもしくはセリアにおける銀の含有量）は、銀の金属形態の換算で、Ag及び担体を含む全体に対して0.1〜20wt%、好ましくは2〜8wt%に設定されている。
(2) More specifically, the first catalyst component includes a carrier component and a carrier component (first carrier component) carried on the carrier.
(i) the support elements, primarily using the lower hydrocarbon, nitrogen-containing compounds to NO is NO x as the reducing component (reaction intermediate) effective (NCO, NH x, CN, RNO 2 , etc.) In this embodiment, silver (Ag) is selected as the supporting component (see FIGS. 2 and 3 described later). With respect to this silver, the content (the content of silver in the alumina, zeolite or ceria described later carrying silver) contains Ag and a carrier in terms of silver metal form from the viewpoint of performing the above functions satisfactorily. The total content is set to 0.1 to 20 wt%, preferably 2 to 8 wt%.
(ii)上記担体成分としては、酸性酸化物が用いられている。具体的には、その酸性酸化物として、アルミナ(Al2O3)、ゼオライト、セリア(CeO2)等を用いることができる。担体成分として酸性酸化物（アルミナ等）を用いるのは、銀担持触媒成分等が高級炭化水素を用いてNOを還元する際に中間生成物としてアンモニア（NH3）を発生することに着目し、そのアンモニア（NH3）を担体成分としての酸性酸化物に吸収し、その吸収されたアンモニアに基づいてNOの還元性能を高めるためである（図１参照）。
上記担体成分であるアルミナ、セリア等の耐熱、耐水性金属酸化物に関しては、従来公知の方法やアルコキシド化合物を用いるゾルゲル法など、いかなる方法で合成されたものをも使用することができ、ゼオライト等の多孔質結晶で耐熱・耐水性金属酸化物に関しては、天然に存在するものでも、水熱合成法などにより合成されるものでも、いかなる方法により用意されたものをも用いることができる。
(ii) An acidic oxide is used as the carrier component. Specifically, alumina (Al 2 O 3 ), zeolite, ceria (CeO 2 ) or the like can be used as the acidic oxide. The use of acidic oxides (alumina, etc.) as the carrier component focuses on the generation of ammonia (NH 3 ) as an intermediate product when the silver-supported catalyst component, etc. reduces NO using higher hydrocarbons, This is because the ammonia (NH 3 ) is absorbed by the acidic oxide as the carrier component, and NO reduction performance is enhanced based on the absorbed ammonia (see FIG. 1).
With respect to heat-resistant and water-resistant metal oxides such as alumina and ceria which are the carrier components, those synthesized by any method such as a conventionally known method or a sol-gel method using an alkoxide compound can be used, such as zeolite. With respect to the heat-resistant and water-resistant metal oxides of the above-mentioned porous crystals, those that exist naturally, those that are synthesized by a hydrothermal synthesis method, or those prepared by any method can be used.
(iii)上記第１触媒成分においては、担体成分に対する担持成分の担持方法については、特に制限はない。金属化合物の水溶液に担体を浸漬する含浸法や、CVD法、析出沈殿法などを用いることができる。また、担体成分としてのアルミナに担持成分として銀を担持した第１触媒成分については、高級炭化水素を用いてNOを直接、還元することもできる。 (iii) In the first catalyst component, there is no particular limitation on the method of supporting the supporting component on the support component. An impregnation method in which a carrier is immersed in an aqueous solution of a metal compound, a CVD method, a precipitation method, or the like can be used. Further, for the first catalyst component in which silver is supported on the alumina as the support component, NO can be directly reduced using higher hydrocarbons.
２．前記第２触媒成分は、図１に示すように、第１触媒成分の活性温度領域において、高級炭化水素（図１中では高級HCとして示す）から低級炭化水素を生成（高級炭化水素を低級炭化水素に分解）する低級炭化水素生成機能を有している。
（１）第２触媒成分において、低級炭化水素生成機能を有するようにしているのは、生成した低級炭化水素を還元剤として第１触媒成分に供給するためである。この低級炭化水素生成機能は、高級炭化水素に対する第２触媒成分の電子供与性により、酸化的に低級炭化水素に分解する作用に基づき実現される。ここで、当該排気浄化用触媒が車両の排気ガス中のNOxを浄化する場合（車両に搭載される場合）には、高級炭化水素としては、その車両の燃料等が用いられる。通常、車両等（例えばディーゼル車等）において、低級炭化水素を搭載することは安全性等の観点から好ましくなく、車両等の燃料を分解して低級炭化水素を得ることが現実的だからである。
（２）第２触媒成分が、前述の第１触媒成分の活性温度領域（約１５０〜６５０℃）において機能するようにしているのは、１つの触媒形態（例えば混合状態）をとる場合、第２触媒成分（特に担持成分）が、第１触媒成分が機能している環境下において、高い機能を発揮する必要があるからである（後述の図２、図３等参照）。
2. As shown in FIG. 1, the second catalyst component generates lower hydrocarbons from higher hydrocarbons (shown as higher HC in FIG. 1) in the active temperature range of the first catalyst component (lower hydrocarbons are lower carbonized). It has a lower hydrocarbon generation function that decomposes into hydrogen.
(1) The reason why the second catalyst component has a lower hydrocarbon generating function is to supply the generated lower hydrocarbon to the first catalyst component as a reducing agent. This lower hydrocarbon generation function is realized based on the action of oxidatively decomposing into lower hydrocarbons by the electron donating property of the second catalyst component with respect to the higher hydrocarbons. Here, when the exhaust purification catalyst purifies NO x in the exhaust gas of the vehicle (when mounted on the vehicle), the fuel of the vehicle or the like is used as the higher hydrocarbon. Usually, it is not preferable to install lower hydrocarbons in vehicles and the like (for example, diesel vehicles) from the viewpoint of safety and the like, and it is realistic to decompose the fuel of vehicles and the like to obtain lower hydrocarbons.
(2) The second catalyst component functions in the activation temperature range (about 150 to 650 ° C.) of the first catalyst component described above when the catalyst is in one catalyst form (for example, mixed state). This is because the two catalyst components (particularly the supported component) need to exhibit a high function in an environment where the first catalyst component is functioning (see FIGS. 2 and 3 described later).
（３）上記第２触媒成分は、上記機能を効果的に果たすべく、本実施形態においては、担体成分と、その担体成分に担持される担持成分（第２担持成分）とを備える構成とされている。 (3) In order to effectively perform the above function, the second catalyst component includes a carrier component and a carrier component (second carrier component) carried on the carrier component in the present embodiment. ing.
(i)第２触媒成分の担持成分としては、その自己の能力に基づき、第１触媒成分の活性温度領域において、低級炭化水素生成機能を発揮するものが用いられている。このため、本実施形態においては、このような担持成分として、亜鉛、コバルト、タングステン、インジウム、ガリウム、マンガン、バリウムのうちのいずれか１種又は複数種が選択されている。 (i) As the supporting component of the second catalyst component, a component that exhibits a lower hydrocarbon generating function in the active temperature region of the first catalyst component is used based on its own ability. For this reason, in this embodiment, any one or more of zinc, cobalt, tungsten, indium, gallium, manganese, and barium are selected as such supporting components.
この場合、担持成分を１種だけでなく複数種用いることができるが、これは、担持成分を複数種用いたとしても、上記低級炭化水素生成機能等に関し、温度ごとに異なる成分が有効であるため、互いの存在が大きな阻害要因とならないからである。
このような担持成分に関しては、上記機能を良好に果たす観点から、その担持成分の含有量（担持成分（金属）を担持したアルミナもしくはゼオライトにおける金属の含有量）は、金属形態の換算で、担持成分及び担体を含む全体に対して0.1〜20wt%、好ましくは2〜8wt%に設定されている。このような含有量は、たとえば、各々の成分を含有する金属化合物の水溶液に担体を浸漬して、水洗、乾燥した後、それを空気中で焼成することにより調製される。
In this case, not only one type but also a plurality of types of supported components can be used. However, even if a plurality of types of supported components are used, different components for each temperature are effective with respect to the lower hydrocarbon generating function and the like. For this reason, the presence of each other does not become a major obstacle.
With respect to such a supporting component, the content of the supporting component (the content of the metal in alumina or zeolite supporting the supporting component (metal)) is supported in terms of the metal form from the viewpoint of performing the above functions satisfactorily. It is set to 0.1 to 20 wt%, preferably 2 to 8 wt% with respect to the total including the components and the carrier. Such content is prepared, for example, by immersing the carrier in an aqueous solution of a metal compound containing each component, washing with water and drying, and then firing it in air.
(ii)第２触媒成分の担体成分としては、酸性酸化物が用いられている。具体的には、その酸性酸化物としては、ゼオライト、アルミナ等を用いることができる。このように第２触媒成分の担体成分として酸性酸化物が用いられている理由は、主として、前述したように、酸性酸化物がアンモニアを蓄積し易いからである。すなわち、高級炭化水素を還元剤として第１触媒成分によりNOxを還元したときに、還元性の高い中間生成物としてアンモニア（NH3）が発生されることから、そのアンモニアを酸性酸化物に蓄積させることにより、そのアンモニアをもって、第１触媒成分（Ag担持触媒）によるNOx（NO）の還元効果を高めようとしているのである（図１参照）。本実施形態においては、特に担体成分（酸性酸化物）としてゼオライトが選択されているが、これは、酸性酸化物の中でも、ゼオライトが、上記効果が高いからである（後述の図４参照）。 (ii) An acidic oxide is used as the carrier component of the second catalyst component. Specifically, zeolite, alumina, or the like can be used as the acidic oxide. The reason why the acidic oxide is used as the carrier component of the second catalyst component as described above is mainly because the acidic oxide easily accumulates ammonia as described above. That is, when NO x is reduced by the first catalyst component using higher hydrocarbon as a reducing agent, ammonia (NH 3) is generated as an intermediate product having high reducibility, so that the ammonia is accumulated in the acidic oxide. Thus, the ammonia is used to enhance the NO x (NO) reduction effect of the first catalyst component (Ag-supported catalyst) (see FIG. 1). In the present embodiment, zeolite is particularly selected as the carrier component (acidic oxide), because zeolite is the most effective among acidic oxides (see FIG. 4 described later).
(iii)この第２触媒成分においても、担体成分に対する担持成分の担持方法については、特に制限はなく、金属化合物の水溶液に担体を浸漬する含浸法や、CVD法、析出沈殿法などを用いることができる。また、上記第２触媒成分については、還元剤（炭化水素等）を用いてNOを直接、還元することもできる。 (iii) In this second catalyst component as well, there are no particular restrictions on the method of supporting the support component on the support component, and an impregnation method, a CVD method, a precipitation method, or the like that immerses the support in an aqueous solution of a metal compound is used. Can do. Further, with respect to the second catalyst component, NO can be directly reduced using a reducing agent (hydrocarbon or the like).
３．前記第１触媒成分と前記第２触媒成分とは分散した状態で含有されている。
（１）第１触媒成分と第２触媒成分とが分散した状態で含有されている第１の理由は、当該排気浄化用触媒自体の簡素化（１つの触媒形態化）を図ると共に、その１つの触媒形態を利用することにより、触媒利用構造の簡素化（複数の触媒を１つの触媒にすること等）を図るためである。これにより、利用形態の制約（例えば、ベースとしてのハニカムに塗り分けること等）を大幅に緩和することができ、工程・コストの削減が見込め、工業的に価値の高いものにできる。
（２）勿論この場合、第２触媒成分として、第１触媒成分の活性温度領域において機能を発揮するものが用いられていることから、第１触媒成分と第２触媒成分とが分散した状態で含有されても、第１、第２触媒成分のいずれもが同時に適切に機能することになる。
（３）第１触媒成分と第２触媒成分とが分散した状態で含有されている第２の理由は、第１触媒成分と第２触媒成分とを互いにできるだけ近接配置状態として、第２触媒成分により生成された低級炭化水素を第１触媒成分に供給し易くすると共に、第２触媒成分の担体（酸性酸化物）に蓄積されたアンモニア（第１触媒成分のNOx還元に伴って生成される副生物）を第１触媒成分に効果的に作用させるためである。これにより、NOx浄化性能を高めることができることになる（後述の図８参照）。
3. The first catalyst component and the second catalyst component are contained in a dispersed state.
(1) The first reason why the first catalyst component and the second catalyst component are contained in a dispersed state is to simplify the exhaust purification catalyst itself (form a single catalyst) and This is for simplifying the catalyst utilization structure (eg, making a plurality of catalysts into one catalyst) by utilizing one catalyst form. As a result, restrictions on the form of use (for example, coating the honeycomb as a base separately) can be relieved, and the reduction of the process and cost can be expected, and it can be industrially highly valuable.
(2) Of course, in this case, as the second catalyst component, the one that exhibits a function in the active temperature region of the first catalyst component is used, so that the first catalyst component and the second catalyst component are in a dispersed state. Even if contained, both the first and second catalyst components function properly at the same time.
(3) The second reason that the first catalyst component and the second catalyst component are contained in a dispersed state is that the first catalyst component and the second catalyst component are arranged as close as possible to each other, so that the second catalyst component It is generated with a lower hydrocarbon produced thereby easily supplied to the first catalyst component, in the NO x reduction of accumulated ammonia (first catalyst component to the carrier of the second catalyst component (acidic oxide) by This is because the by-product) effectively acts on the first catalyst component. As a result, the NO x purification performance can be improved (see FIG. 8 described later).
（４）上記第１触媒成分と第２触媒成分とが分散した状態で含有されている態様には、第１触媒成分と第２触媒成分とが物理的に混合されている態様の他に、第１、第２触媒成分に対する共通担体成分（第１又は第２触媒成分の担体成分）を用意し、その共通担体成分に、第１触媒成分の担持成分（第１担持成分：銀等）と第２触媒成分の担持成分（第２担持成分）とを同時又は順次、担持させる態様も含まれる。 (4) In the aspect in which the first catalyst component and the second catalyst component are contained in a dispersed state, in addition to the aspect in which the first catalyst component and the second catalyst component are physically mixed, A common carrier component for the first and second catalyst components (a carrier component of the first or second catalyst component) is prepared, and the common carrier component includes a carrier component for the first catalyst component (first carrier component: silver or the like) A mode in which the supporting component (second supporting component) of the second catalyst component is supported simultaneously or sequentially is also included.
４．当該排気浄化用触媒は、第１触媒成分と第２触媒成分とが分散した状態で含有されている態様の下で、粉状、粒体状、ペレット状、ハニカム状など、種々の形状、構造にして使用することができる。特に当該排気浄化用触媒を成形して使用する場合には、成形時に通常使用される粘結剤すなわちポリビニルアルコールなど、あるいは滑剤すなわち黒鉛、ワックス、脂肪酸類、カーボンワックスなどを使用することもできる。そして、このような排気浄化用触媒は、ディーゼル車や定置式ディーゼル機関等のディーゼル排ガス、リーンバーンガソリン車等の排気ガスをはじめ、各種燃焼設備等の排ガスの処理に用いられ、これら排気ガス中からNOxを除去するに際しては、酸素を含む酸化雰囲気中、燃料等、高級炭化水素を存在させる状態下で、上記排気浄化用触媒に排気ガスが接触させられる。
ここで、酸化雰囲気とは、存在する燃料等、高級炭化水素を完全に酸化してCO2に変換するのに必要な酸素量よりも過剰な酸素が含まれる雰囲気である。
4). The exhaust purification catalyst has various shapes and structures, such as powder, granules, pellets, and honeycombs, in a state where the first catalyst component and the second catalyst component are contained in a dispersed state. Can be used. In particular, when the exhaust purification catalyst is molded and used, a binder that is usually used at the time of molding, that is, polyvinyl alcohol, or the like, or a lubricant, that is, graphite, wax, fatty acids, carbon wax, or the like, can also be used. Such exhaust purification catalysts are used for the treatment of exhaust gas from various combustion facilities, including diesel exhaust from diesel vehicles and stationary diesel engines, exhaust gas from lean burn gasoline vehicles, etc. When NO x is removed from the exhaust gas, the exhaust gas is brought into contact with the exhaust gas purification catalyst in the presence of higher hydrocarbons such as fuel in an oxidizing atmosphere containing oxygen.
Here, the oxidizing atmosphere is an atmosphere that contains oxygen more than the amount of oxygen necessary to completely oxidize higher hydrocarbons such as existing fuel and convert them to CO 2 .
５．当該排気浄化用触媒は、NOxの接触還元除去方法（使用方法）を行うべく、その排気浄化用触媒を収納した反応器が酸化雰囲気中の排気系（排気通路）に配置され、その反応器（排気浄化用触媒）に対してデカンなどの高級炭化水素、NOx含有排ガスが通される。
ここで、高級炭化水素としては、種類に特に制限はなく、デカンのみならず、ディーゼル燃料、ガソリン、バイオディーゼル燃料等、高級炭化水素全般が用いることができる。また、この高級炭化水素の量については、特に制限はない。ただし、高級炭化水素を必要な理論量より過剰としたとき、還元反応がより進行されるので、一般には、高級炭化水素は過剰に存在させることが好ましく、具体的には、NOxの還元除去に必要な理論量の約1.5倍〜１４倍量、好ましくは約２〜８倍量とすることが適している。
勿論この場合、燃料そのものを触媒に噴射することにより供給する他に、エンジン運転を制御することにより発生させたものを供給するようにしてもよい。
反応温度については、エンジンの排気ガス温度である約１５０〜６５０℃となる。当該排気浄化用触媒は、この反応温度の下で、前述の自己の活性温度領域に基づき効果を示すことになる。
反応圧力については、特に制限されず、加圧下でも減圧下でも反応は進行することになる。しかし、通常の排気圧で排ガスを触媒層（反応器）へ導入し反応を進行させることが、簡便さの観点から好ましい。
空間速度については、特に制限されないが、約１０，０００〜５００，０００ｈ-1、好ましくは約４０，０００〜３００，０００ｈ-1とするのがよい。
5. The exhaust purifying catalyst, in order to perform the catalytic reduction method for removing NO x (usage), a reactor that accommodates the exhaust gas purifying catalyst is disposed in an exhaust system of an oxidizing atmosphere (exhaust passage), the reactor Higher hydrocarbons such as decane and NO x containing exhaust gas are passed through (exhaust gas purification catalyst).
Here, the type of the higher hydrocarbon is not particularly limited, and not only decane but also higher hydrocarbons such as diesel fuel, gasoline, biodiesel fuel, etc. can be used. Moreover, there is no restriction | limiting in particular about the quantity of this higher hydrocarbon. However, since the reduction reaction proceeds more when higher hydrocarbons are made in excess of the required theoretical amount, it is generally preferable that the higher hydrocarbons exist in excess, specifically, NO x reduction and removal. It is suitable that the amount is about 1.5 to 14 times, preferably about 2 to 8 times the theoretical amount necessary for the above.
Of course, in this case, in addition to supplying the fuel itself by injecting it to the catalyst, the fuel generated by controlling the engine operation may be supplied.
The reaction temperature is about 150 to 650 ° C., which is the exhaust gas temperature of the engine. The exhaust purification catalyst exhibits an effect based on the above-described self-activation temperature region under the reaction temperature.
The reaction pressure is not particularly limited, and the reaction proceeds even under pressure and under reduced pressure. However, it is preferable from the viewpoint of simplicity to introduce the exhaust gas into the catalyst layer (reactor) at a normal exhaust pressure to advance the reaction.
The space velocity is not particularly limited, but is preferably about 10,000 to 500,000 h −1 , preferably about 40,000 to 300,000 h −1 .
このような当該排気浄化用触媒の使用方法により、当該排気浄化用触媒においては、第２触媒成分が高級炭化水素（例えば燃料）を低級炭化水素に分解し、その低級炭化水素は第１触媒成分に供給される。第１触媒成分は、その低級炭化水素を還元剤として、NO(NOx)を還元し、還元成分（NCO等）を発生させる。この還元成分については、この後、第２触媒成分の吸着機能（親和性）に基づき、第１触媒成分の活性サイトから直ちに脱離され、その脱離した還元成分は第２触媒成分の担持成分に吸着される。そして、この吸着された還元成分は、NO，O2，H2Oのアタックを受けてN2に直ちに還元され、還元成分を吸着していた吸着点は、次の新たな還元成分を受け入れる吸着点として準備される。
したがって、第１触媒成分における活性サイトNO(NOx)を受け入れる部位）については次の新たなNO(NOx)を、また、第２触媒成分については次のNO(NOx)の新たな還元成分を吸着する状態となり、１つの触媒形態をとる場合であっても、NO(NOx)の還元処理（一連の各過程）を円滑且つ迅速に行われる。
According to such a method of using the exhaust purification catalyst, in the exhaust purification catalyst, the second catalyst component decomposes higher hydrocarbons (for example, fuel) into lower hydrocarbons, and the lower hydrocarbons are converted into the first catalyst components. To be supplied. The first catalyst component reduces NO (NO x ) using the lower hydrocarbon as a reducing agent to generate a reducing component (NCO or the like). Thereafter, the reducing component is immediately desorbed from the active site of the first catalyst component based on the adsorption function (affinity) of the second catalyst component, and the desorbed reducing component is the supported component of the second catalyst component. To be adsorbed. Then, the adsorbed reducing component is immediately reduced to N 2 by receiving an attack of NO, O 2 and H 2 O, and the adsorption point that adsorbed the reducing component adsorbs the next new reducing component. Prepared as a point.
Therefore, the next new NO (NO x ) is received for the active site NO (NO x ) in the first catalyst component, and the next NO (NO x ) is newly reduced for the second catalyst component. Even when the component is adsorbed and takes one catalyst form, the reduction process (a series of steps) of NO (NO x ) can be performed smoothly and rapidly.
６．当該排気浄化用触媒は、次のようにして製造される。
（１）先ず、前記第１触媒成分と前記第２触媒成分とを個々に作成する。この場合、各触媒成分を作成するに当たっては、各担持成分を含有する金属化合物の水溶液に担体を浸漬して、水洗、乾燥した後、それを空気中で焼成すること等が行われる。
（２）次に、第１触媒成分と第２触媒成分とを物理的に混合する。これにより、第１触媒成分と第２触媒成分とは分散された状態となり、当該排気浄化用触媒が得られる。
6). The exhaust purification catalyst is manufactured as follows.
(1) First, the first catalyst component and the second catalyst component are individually prepared. In this case, in preparing each catalyst component, the carrier is immersed in an aqueous solution of a metal compound containing each supported component, washed with water, dried, and then fired in air.
(2) Next, the first catalyst component and the second catalyst component are physically mixed. As a result, the first catalyst component and the second catalyst component are dispersed, and the exhaust purification catalyst is obtained.
（３）特に、第１、第２触媒成分をそれぞれ作成してから物理的に混合を行う場合には、十分な接触を図るため、各成分を水もしくはなんらかの溶媒に展開しスラリー状で混合することが好ましい。
原料となる銀などの金属化合物については、水に可溶な化合物であればいずれのものを原料としてもよいが、通常は残存陰イオンを空気中の焼成処理によって比較的低温で分解除去される硝酸塩を用いる。含浸法で調製する場合、室温〜100℃で1〜24時間、一般的には80℃で1〜3時間、原料金属溶液を浸析することにより行う。調製後の触媒成分は、通常、乾燥後、空気中で焼成する。
(3) In particular, when the first and second catalyst components are prepared and then physically mixed, in order to achieve sufficient contact, the components are developed in water or some solvent and mixed in the form of a slurry. It is preferable.
Any metal compound such as silver may be used as a raw material as long as it is soluble in water, but usually the remaining anions are decomposed and removed at a relatively low temperature by a baking treatment in air. Use nitrate. When preparing by the impregnation method, it is carried out by leaching the raw metal solution at room temperature to 100 ° C. for 1 to 24 hours, generally at 80 ° C. for 1 to 3 hours. The catalyst component after preparation is usually calcined in air after drying.
（４）当該排気浄化用触媒の別の製造方法としては、同一の共通担体成分（例えば第１触媒成分の担体成分）に、銀（第１触媒成分の担持成分）と亜鉛などの金属（第２触媒）とを同時もしくは逐次に担持するようにしてもよい。このような構成からなるものにおいても、それらを触媒材料とすることにより、第１、第２触媒成分が分散した状態で含有されたものとなる。 (4) As another method for producing the exhaust gas purification catalyst, the same common carrier component (for example, the carrier component of the first catalyst component), silver (the carrier component of the first catalyst component), and a metal such as zinc (the first catalyst component) 2 catalysts) may be supported simultaneously or sequentially. Even in such a configuration, by using them as catalyst materials, the first and second catalyst components are contained in a dispersed state.
７．以下に、上記内容を裏付ける実施例について説明する。
（実施例で用いる触媒構成成分、触媒成分及び触媒の調製）
〔触媒構成成分の調製〕
・ゾルゲル法によるアルミナ［A］の調製
アルミニウムs-ブトキシド (Al(OC4H9)4)
200gに、室温にて蒸留水75mlを攪拌しつつ滴下して加水分解することにより沈殿を生成させ、ホットプレートで80℃に加温して20時間熟成を続けた。得られた沈殿を空気中110℃で一昼夜乾燥後、空気中500℃で5時間焼成した。得られたアルミナの表面積は350m2/gであった。
・アルミナ担持銀触媒［A1］の調製（Ag/Al 2 O 3 ）
硝酸銀（AgNO3）を蒸留水に溶解した水溶液に、上記のアルミナ［A］5gを加え、80℃に保温したホットプレート上で撹拌しながら余分な水分を除去した後、110℃で一昼夜乾燥後、空気中600℃で3時間焼成して、アルミナ担持銀触媒［A1］を得た。このとき触媒に対する銀の含有量は、銀金属（Ag）換算で4wt%とした。
・アルミナ担持亜鉛触媒［A2］の調製（Zn/Al 2 O 3 ）
硝酸亜鉛(Zn(NO3)2)を蒸留水に溶解した水溶液に、上記のアルミナ［A］5gを加え、80℃に保温したホットプレート上で撹拌しながら余分な水分を除去した後、110℃で一昼夜乾燥後、空気中600℃で3時間焼成して、アルミナ担持亜鉛触媒［A2］を得た。このとき触媒に対する亜鉛の含有量は、亜鉛金属（Zn）換算で4wt%とした。
・アルミナ担持銀亜鉛共含浸触媒［A3］の調製（Ag-Zn/Al 2 O 3 （co-imp））
硝酸銀（AgNO3）および硝酸亜鉛(Zn(NO3)2)を蒸留水に溶解した水溶液に、上記のアルミナ［A］ 5gを加え、80℃に保温したホットプレート上で撹拌しながら余分な水分を除去した後、110℃で一昼夜乾燥後、空気中600℃で3時間焼成して、アルミナ担持銀亜鉛共含浸触媒［A2］を得た。このとき触媒に対する銀および亜鉛の含有量は、銀金属（Ag）および亜鉛金属(Zn)換算で各々4wt%とした。
・アルミナ担持銀亜鉛逐次含浸触媒［A4］の調製（Ag/Zn/Al 2 O 3 （SI））
硝酸銀（AgNO3）を蒸留水に溶解した水溶液に、上記のアルミナ担持亜鉛触媒［A2］を加え、80℃に保温したホットプレート上で撹拌しながら余分な水分を除去した後、110℃で一昼夜乾燥後、空気中600℃で3時間焼成して、アルミナ担持銀亜鉛逐次含浸触媒［A4］を得た。このとき触媒に対する銀の含有量は、銀金属（Ag）換算で4wt%とした。
・アルミナ担持銀とアルミナ担持亜鉛の物理混合触媒［A5］の調製（Ag/Al 2 O 3 +Zn/Al 2 O 3 ）
アルミナ担持銀触媒［A1］12mgとアルミナ担持銀亜鉛逐次含浸触媒［A4］5mgを物理的に混合し、アルミナ担持銀とアルミナ担持亜鉛の物理混合触媒［A5］を得た。
7). Examples that support the above will be described below.
(Preparation of catalyst component, catalyst component and catalyst used in Examples)
(Preparation of catalyst components)
・ Preparation of alumina [A] by sol-gel method Aluminum s-butoxide (Al (OC 4 H 9 ) 4 )
To 200 g, 75 ml of distilled water was added dropwise at room temperature with stirring to hydrolyze to form a precipitate, which was heated to 80 ° C. on a hot plate and aged for 20 hours. The obtained precipitate was dried in air at 110 ° C. for a whole day and night and then calcined in air at 500 ° C. for 5 hours. The surface area of the obtained alumina was 350 m 2 / g.
・ Preparation of alumina supported silver catalyst [A1] (Ag / Al 2 O 3 )
Add 5 g of the above alumina [A] to an aqueous solution of silver nitrate (AgNO 3 ) dissolved in distilled water, remove excess water while stirring on a hot plate kept at 80 ° C., and then dry at 110 ° C. overnight. And calcining in air at 600 ° C. for 3 hours to obtain an alumina-supported silver catalyst [A1]. At this time, the silver content relative to the catalyst was 4 wt% in terms of silver metal (Ag).
・ Preparation of alumina supported zinc catalyst [A2] (Zn / Al 2 O 3 )
To the aqueous solution in which zinc nitrate (Zn (NO 3 ) 2 ) was dissolved in distilled water, 5 g of the above alumina [A] was added, and after removing excess moisture while stirring on a hot plate kept at 80 ° C., 110 After drying overnight at 0 ° C., it was calcined at 600 ° C. for 3 hours in air to obtain an alumina-supported zinc catalyst [A2]. At this time, the zinc content relative to the catalyst was 4 wt% in terms of zinc metal (Zn).
・ Preparation of alumina-supported silver-zinc co-impregnated catalyst [A3] (Ag-Zn / Al 2 O 3 (co-imp))
Add 5 g of the above alumina [A] to an aqueous solution of silver nitrate (AgNO 3 ) and zinc nitrate (Zn (NO 3 ) 2 ) in distilled water and stir on a hot plate kept at 80 ° C. to remove excess water. Then, after drying at 110 ° C. for a whole day and night, it was calcined in air at 600 ° C. for 3 hours to obtain an alumina-supported silver-zinc co-impregnated catalyst [A2]. At this time, the contents of silver and zinc in the catalyst were 4 wt% in terms of silver metal (Ag) and zinc metal (Zn), respectively.
・ Preparation of alumina-supported silver-zinc sequential impregnation catalyst [A4] (Ag / Zn / Al 2 O 3 (SI))
To the aqueous solution in which silver nitrate (AgNO 3 ) is dissolved in distilled water, the above-mentioned alumina-supported zinc catalyst [A2] is added, and excess water is removed while stirring on a hot plate kept at 80 ° C., and then overnight at 110 ° C. After drying, it was calcined in air at 600 ° C. for 3 hours to obtain an alumina-supported silver-zinc sequential impregnation catalyst [A4]. At this time, the silver content relative to the catalyst was 4 wt% in terms of silver metal (Ag).
・ Preparation of physical mixed catalyst [A5] of alumina supported silver and alumina supported zinc (Ag / Al 2 O 3 + Zn / Al 2 O 3 )
12 mg of alumina-supported silver catalyst [A1] and 5 mg of alumina-supported silver-zinc sequential impregnation catalyst [A4] were physically mixed to obtain a physically mixed catalyst of alumina-supported silver and alumina-supported zinc [A5].
・水素型ZSM-5触媒 [B]の調製
市販のアンモニウム型ZSM-5（東ソー製 HSZ-830-NHA SiO2/Al2O3=28）を、空気中600℃で5時間焼成して、水素型ZSM-5触媒［B］を得た。
・ZSM-5担持銀触媒［B1］の調製（Ag/ZSM-5）
[B]に対して銀重量が4wt%となるよう濃度を調整した硝酸銀水溶液に［B］を加え、80℃に保温したホットプレート上で撹拌しながら余分な水分を除去した後、110℃で一昼夜乾燥後、空気中600℃で3時間焼成して、ZSM-5担持銀触媒［B1］を得た。
・他のZSM-5担持金属触媒［B2~B9］の調製(Cu/ZSM-5,Zn/ZSM-5,Co/ZSM-5,W/ZSM-5，In/ZSM-5,Ga/ZSM-5,Mn/ZSM-5およびBa/ZSM-5)
上記、ZSM-5担持銀触媒［B1］と同様の方法で、硝酸銀水溶液の代わりに硝酸銅、硝酸亜鉛、硝酸コバルト、硝酸タングステン、硝酸インジウム、硝酸ガリウム、硝酸マンガンおよび硝酸バリウムの各水溶液を用い、担持する金属の重量が4wt%となるように調製し、ZSM-5担持銅触媒［B2］、ZSM-5担持亜鉛触媒［B3］、ZSM-5担持コバルト触媒［B4］、ZSM-5担持タングステン触媒［B5］、ZSM-5担持インジウム触媒［B6］、ZSM-5担持ガリウム触媒［B7］、ZSM-5担持マンガン触媒［B8］、およびZSM-5担持バリウム触媒［B9］を得た。
・種々の担体に担持した亜鉛触媒［C3,D3,E3,F3,G3,H3,I3,J3］の調製（Zn/SiO 2 、Zn/TiO 2 、Zn/ZrO 2 、Zn/CeO 2 、Zn/MOR、Zn/USY、Zn/BETA、Zn/FER）
各々、市販のシリカ（富士シリシア製 Cariact G10）、チタニア（Rhone-Paulence-G5）、ジルコニア（日揮触媒化成製）、セリア（第一稀元素化学製 HS）、モルデナイト（東ソー製 HSZ-640HOA-SiO2/Al2O3=18.3）、USY型ゼオライト（東ソー製 HSZ-350HUA- SiO2/Al2O3
=10.4）、ベータ型ゼオライト（東ソー製 HSZ-930NHA-SiO2/Al2O3=27）、フェリエライト（東ソー製 HSZ-720-KOA- SiO2/Al2O3=17.7）に対して亜鉛重量が4wt%となるよう濃度を調整した硝酸亜鉛水溶液を含浸し、110℃で一昼夜乾燥後、空気中600℃で3時間焼成することで、シリカ担持亜鉛触媒［C3］、チタニア担持亜鉛触媒［D3］、ジルコニア担持亜鉛触媒［E3］、セリア担持亜鉛触媒［F3］、モルデナイト担持亜鉛触媒［G3］、USY担持亜鉛触媒［H3］、ベータ担持亜鉛触媒［I3］、およびフェリエライト担持亜鉛触媒［J3］を得た。
-Preparation of hydrogen-type ZSM-5 catalyst [B] Commercially available ammonium-type ZSM-5 (HSZ-830-NHA SiO 2 / Al 2 O 3 = 28 manufactured by Tosoh) was calcined at 600 ° C in air for 5 hours, Hydrogen type ZSM-5 catalyst [B] was obtained.
・ Preparation of ZSM-5 supported silver catalyst [B1] (Ag / ZSM-5)
[B] was added to an aqueous silver nitrate solution whose concentration was adjusted to 4 wt% with respect to [B], and excess water was removed while stirring on a hot plate kept at 80 ° C. After drying for a whole day and night, it was calcined in air at 600 ° C. for 3 hours to obtain a ZSM-5-supported silver catalyst [B1].
・ Preparation of other ZSM-5 supported metal catalysts [B2 ~ B9] (Cu / ZSM-5, Zn / ZSM-5, Co / ZSM-5, W / ZSM-5, In / ZSM-5, Ga / ZSM -5, Mn / ZSM-5 and Ba / ZSM-5)
In the same manner as the ZSM-5 supported silver catalyst [B1], copper nitrate, zinc nitrate, cobalt nitrate, tungsten nitrate, indium nitrate, gallium nitrate, manganese nitrate, and barium nitrate are used in place of the silver nitrate aqueous solution. , Prepared so that the weight of the supported metal is 4 wt%, ZSM-5 supported copper catalyst [B2], ZSM-5 supported zinc catalyst [B3], ZSM-5 supported cobalt catalyst [B4], ZSM-5 supported A tungsten catalyst [B5], a ZSM-5 supported indium catalyst [B6], a ZSM-5 supported gallium catalyst [B7], a ZSM-5 supported manganese catalyst [B8], and a ZSM-5 supported barium catalyst [B9] were obtained.
Preparation of zinc catalysts [C3, D3, E3, F3, G3, H3, I3, J3] supported on various supports (Zn / SiO 2 , Zn / TiO 2 , Zn / ZrO 2 , Zn / CeO 2 , Zn / MOR, Zn / USY, Zn / BETA, Zn / FER)
Commercially available silica (Cariact G10 manufactured by Fuji Silysia), titania (Rhone-Paulence-G5), zirconia (manufactured by JGC Catalysts & Chemicals), ceria (manufactured by Daiichi Rare Element Chemicals), mordenite (HSZ-640HOA-SiO manufactured by Tosoh) 2 / Al 2 O 3 = 18.3), USY-type zeolite (Tosoh HSZ-350HUA-SiO 2 / Al 2 O 3
= 10.4), zinc for beta-type zeolite (HSZ-930NHA-SiO 2 / Al 2 O 3 = 27 made by Tosoh), ferrierite (HSZ-720-KOA-SiO 2 / Al 2 O 3 = 17.7 made by Tosoh) Impregnated with a zinc nitrate aqueous solution whose concentration was adjusted to 4 wt%, dried at 110 ° C overnight, and calcined in air at 600 ° C for 3 hours, thereby supporting silica-supported zinc catalyst [C3], titania-supported zinc catalyst [ D3], Zirconia supported zinc catalyst [E3], Ceria supported zinc catalyst [F3], Mordenite supported zinc catalyst [G3], USY supported zinc catalyst [H3], Beta supported zinc catalyst [I3], and Ferrierite supported zinc catalyst [ J3] was obtained.
・物理混合触媒の調製
アルミナ担持銀触媒［A1］12mgと水素型ZSM-5触媒[B]、ZSM-5担持銅触媒［B2］、ZSM-5担持亜鉛触媒［B3］、ZSM-5担持コバルト触媒［B4］、ZSM-5担持タングステン触媒［B5］、ZSM-5担持インジウム触媒［B6］、ZSM-5担持ガリウム触媒［B7］、ZSM-5担持マンガン触媒［B8］、ZSM-5担持バリウム触媒［B9］、シリカ担持亜鉛触媒［C3］、チタニア担持亜鉛触媒［D3］、ジルコニア担持亜鉛触媒［E3］、セリア担持亜鉛触媒［F3］モルデナイト担持亜鉛触媒［G3］、USY担持亜鉛触媒［H3］、ベータ担持亜鉛触媒［I3］もしくはフェリエライト担持亜鉛触媒［J3］のいずれか5mgを物理的に混合し、順に、アルミナ担持銀と水素型ZSM-5の物理混合触媒[A1+B]、アルミナ担持銀とZSM-5担持銅の物理混合触媒［A1+B2］、アルミナ担持銀とZSM-5担持亜鉛の物理混合触媒［A1+B3］、アルミナ担持銀とZSM-5担持コバルトの物理混合触媒［A1+B4］、アルミナ担持銀とZSM-5担持タングステンの物理混合触媒［A1+B5］、アルミナ担持銀とZSM-5担持インジウムの物理混合触媒［A1+B6］、アルミナ担持銀とZSM-5担持ガリウムの物理混合触媒［A1+B7］、アルミナ担持銀とZSM-5担持マンガンの物理混合触媒［A1+B8］、アルミナ担持銀とZSM-5担持バリウムの物理混合触媒［A1+B9］、アルミナ担持銀とシリカ担持亜鉛の物理混合触媒［A1+C3］、アルミナ担持銀とチタニア担持亜鉛の物理混合触媒［A1+D3］、アルミナ担持銀とジルコニア担持亜鉛の物理混合触媒［A1+E3］、アルミナ担持銀とセリア担持亜鉛の物理混合触媒［A1+F3］、アルミナ担持銀とモルデナイト担持亜鉛の物理混合触媒［A1+G3］、アルミナ担持銀とUSY担持亜鉛の物理混合触媒［A1+H3］、アルミナ担持銀とベータ担持亜鉛の物理混合触媒［A1+I3］およびアルミナ担持銀とフェリエライト担持亜鉛の物理混合触媒［A1+J3］を得た。
・ Preparation of physical mixed catalyst 12mg alumina supported silver catalyst [A1] and hydrogen type ZSM-5 catalyst [B], ZSM-5 supported copper catalyst [B2], ZSM-5 supported zinc catalyst [B3], ZSM-5 supported cobalt Catalyst [B4], ZSM-5 supported tungsten catalyst [B5], ZSM-5 supported indium catalyst [B6], ZSM-5 supported gallium catalyst [B7], ZSM-5 supported manganese catalyst [B8], ZSM-5 supported barium Catalyst [B9], silica supported zinc catalyst [C3], titania supported zinc catalyst [D3], zirconia supported zinc catalyst [E3], ceria supported zinc catalyst [F3] mordenite supported zinc catalyst [G3], USY supported zinc catalyst [H3] ], 5 mg of either beta-supported zinc catalyst [I3] or ferrierite-supported zinc catalyst [J3] is physically mixed, and in order, a physical mixed catalyst of alumina-supported silver and hydrogen type ZSM-5 [A1 + B], Physical mixed catalyst of silver supported on alumina and copper supported on ZSM-5 [A1 + B2], physical mixed catalyst of silver supported on alumina and zinc supported on ZSM-5 [A1 + B3], physical mixed catalyst of alumina supported silver and ZSM-5 supported cobalt [A1 + B4], physical mixed catalyst of alumina supported silver and ZSM-5 supported tungsten [A1 + B5], alumina supported silver and ZSM- 5. Physical mixed catalyst of supported indium [A1 + B6], Physical mixed catalyst of alumina supported silver and ZSM-5 supported gallium [A1 + B7], Physical mixed catalyst of alumina supported silver and ZSM-5 supported manganese [A1 + B8] , Physical mixed catalyst of alumina supported silver and ZSM-5 supported barium [A1 + B9], Physical mixed catalyst of alumina supported silver and silica supported zinc [A1 + C3], Physical mixed catalyst of alumina supported silver and titania supported zinc [A1 + D3], physical mixed catalyst of alumina supported silver and zirconia supported zinc [A1 + E3], physical mixed catalyst of alumina supported silver and ceria supported zinc [A1 + F3], physical mixed catalyst of silver supported alumina and mordenite supported zinc [ A1 + G3], physical mixed catalyst of silver supported on alumina and zinc supported on USY [A1 + H 3] A physical mixed catalyst [A1 + I3] of alumina-supported silver and zinc-supported zinc and a physical mixed catalyst [A1 + J3] of alumina-supported silver and ferrierite-supported zinc were obtained.
・混合比の異なるアルミナ担持銀ZSM-5担持亜鉛物理混合触媒の調製
アルミナ担持銀触媒[A1]15mgとZSM-5担持亜鉛触媒[B3]2mgを物理混合した触媒および両触媒を8.5mgづつ物理混合した触媒を調製し、88%アルミナ担持銀と12%ZSM-5担持亜鉛の物理混合触媒［A1+B3-88］および50%アルミナ担持銀と50%ZSM-5担持亜鉛の物理混合触媒［A1+B3-50］を得た。
・濃度の異なるZSM-5担持亜鉛触媒の調製
[B]に対して亜鉛重量が5wt%となるよう濃度を調整した硝酸亜鉛水溶液に［B］を加え、80℃に保温したホットプレート上で撹拌しながら余分な水分を除去した後、110℃で一昼夜乾燥後、空気中600℃で3時間焼成して、ZSM-5担持5%亜鉛触媒［B3-5%］を得た。
・総量50mgの物理混合触媒の調製
アルミナ担持銀触媒[A1]17mgとZSM-5担持亜鉛触媒[B3]33mgもしくはZSM-5担持5%亜鉛触媒［B3-5%］33mgを物理混合した触媒を調製し、50mgアルミナ担持銀とZSM-5担持亜鉛の物理混合触媒[50mg-A1+B3]および50mgアルミナ担持銀とZSM-5担持5%亜鉛の物理混合触媒[50mg-A1+B3-5%]を得た。
・ Preparation of Zinc-5 supported Zinc-5 supported physical catalyst with different mixing ratio Alumina-supported silver catalyst [A1] 15 mg and ZSM-5 supported Zinc catalyst [B3] 2 mg Prepared mixed catalyst, physical mixed catalyst of 88% alumina supported silver and 12% ZSM-5 supported zinc [A1 + B3-88] and physical mixed catalyst of 50% alumina supported silver and 50% ZSM-5 supported zinc [ A1 + B3-50] was obtained.
・ Preparation of ZSM-5 supported zinc catalysts with different concentrations
[B] was added to a zinc nitrate aqueous solution whose concentration was adjusted to 5 wt% with respect to [B], and after removing excess water while stirring on a hot plate kept at 80 ° C., 110 ° C. And dried at 600 ° C. in air for 3 hours to obtain a ZSM-5-supported 5% zinc catalyst [B3-5%].
・ Preparation of physical mixed catalyst with a total amount of 50 mg A catalyst in which 17 mg of alumina-supported silver catalyst [A1] and 33 mg of ZSM-5-supported zinc catalyst [B3] or 33 mg of ZSM-5-supported 5% zinc catalyst [B3-5%] were physically mixed Prepared 50 mg alumina supported silver and ZSM-5 supported zinc physical mixed catalyst [50 mg-A1 + B3] and 50 mg alumina supported silver and ZSM-5 supported 5% zinc physical mixed catalyst [50 mg-A1 + B3-5% ]
〔触媒活性評価〕
上記のようにして得られた本発明の触媒17mgを常圧固定床流通式反応装置に充填し、約500ppmの一酸化窒素（以下、「NO」と記す）、約5vol%の酸素、約200ppmのデカン、約1ppmのSO2および約5vol%の水を含むヘリウムバランスの模擬排ガスを毎分100mlの流速(空間速度（SV）=60,000h-1に相当)で流して反応を行い、定常活性は600℃から250℃までステップ状に50℃刻みで降温し、各々の温度において反応後のガスを分析した。反応ガスの分析には主としてガスクロマトグラフ（島津製作所製 GC-8A）を用い、N2、N2O、CO2、COを定量した。ほかの成分は連続式ガスモニター（日本電子 GASMET DT-4000赤外線モニタリング装置）を用いて定量した。
（実施例１）
[Evaluation of catalyst activity]
17 mg of the catalyst of the present invention obtained as described above was charged into an atmospheric pressure fixed bed flow reactor, about 500 ppm nitric oxide (hereinafter referred to as “NO”), about 5 vol% oxygen, about 200 ppm. Helium-balanced simulated exhaust gas containing about 1ppm of SO 2 and about 5vol% water flows at a flow rate of 100ml per minute (corresponding to space velocity (SV) = 60,000h- 1 ), the reaction is performed, and steady activity The temperature decreased from 600 ° C. to 250 ° C. in steps of 50 ° C., and the gas after reaction was analyzed at each temperature. For the analysis of the reaction gas, a gas chromatograph (GC-8A manufactured by Shimadzu Corporation) was mainly used to quantify N 2 , N 2 O, CO 2 , and CO. The other components were quantified using a continuous gas monitor (JEOL GASMET DT-4000 infrared monitoring device).
Example 1
上記の〔触媒構成成分の調製〕で調製したアルミナ担持銀亜鉛共含浸触媒［A3］を触媒として用い、上記の〔触媒活性評価〕に従い、600〜250℃の温度範囲でNO転化に伴い生成する窒素の生成率の評価を行った。評価結果を図２に示した。
（実施例２）
Using the alumina-supported silver-zinc co-impregnated catalyst [A3] prepared in [Preparation of catalyst component] as a catalyst, the catalyst is produced with NO conversion in the temperature range of 600 to 250 ° C. according to the above [Catalyst activity evaluation]. The production rate of nitrogen was evaluated. The evaluation results are shown in FIG.
(Example 2)
実施例１において、触媒としてアルミナ担持銀亜鉛逐次含浸触媒［A4］を用いた以外は、実施例１と同様にしてNOの還元反応を行い、その結果を図２に示した。
（実施例３）
In Example 1, NO reduction reaction was performed in the same manner as in Example 1 except that the alumina-supported silver-zinc sequential impregnation catalyst [A4] was used as the catalyst. The results are shown in FIG.
(Example 3)
実施例１において、触媒としてアルミナ担持銀とアルミナ担持亜鉛の物理混合触媒［A5］を用いた以外は、実施例１と同様にしてNOの還元反応を行い、その結果を図２および図４に示した。
（比較例１）
In Example 1, a NO reduction reaction was carried out in the same manner as in Example 1 except that a physical mixed catalyst [A5] of alumina-supported silver and alumina-supported zinc was used as the catalyst. The results are shown in FIGS. Indicated.
(Comparative Example 1)
実施例１において、触媒としてアルミナ［A］を用いた以外は、実施例１と同様にしてNOの還元反応を行い、その結果を図２および表１に示した。
（比較例２）
In Example 1, NO reduction reaction was performed in the same manner as in Example 1 except that alumina [A] was used as a catalyst. The results are shown in FIG.
(Comparative Example 2)
実施例１において、触媒としてアルミナ担持銀触媒［A1］を用いた以外は、実施例１と同様にしてNOの還元反応を行い、その結果を図２に示した。
（比較例３）
In Example 1, except that the alumina-supported silver catalyst [A1] was used as the catalyst, a NO reduction reaction was carried out in the same manner as in Example 1, and the results are shown in FIG.
(Comparative Example 3)
実施例１において、触媒としてアルミナ担持亜鉛触媒［A2］を用いた以外は、実施例１と同様にしてNOの還元反応を行い、その結果を図２に示した。 In Example 1, except that the alumina-supported zinc catalyst [A2] was used as a catalyst, a NO reduction reaction was carried out in the same manner as in Example 1, and the results are shown in FIG.
図２（NOが分解して生ずる窒素の生成率を示す）によれば、アルミナ[A]およびアルミナ担持亜鉛触媒［A2］を触媒とすると非常に低い性能しか示さないが（比較例１および比較例３）、アルミナ担持銀触媒［A2］を用いた場合には、375〜425℃で30%程度のNO浄化率を示した（比較例２）。銀触媒と亜鉛触媒を複合化させた触媒を用いた実施例は、いずれも比較例の中で最も活性が高い比較例２よりも高い活性を示し、特に350℃付近で顕著な活性向上が認められた。亜鉛と銀を複合化させる方法としては、検討した共含浸法（実施例１）、逐次含浸法（実施例２）、物理混合法（実施例３）いずれの複合化でも全域で比較例２よりも高い活性を示し、複合効果が認められた。この効果は特に350℃〜500℃で顕著にみられた。
（実施例４）
According to FIG. 2 (showing the production rate of nitrogen generated by decomposition of NO), when alumina [A] and alumina-supported zinc catalyst [A2] are used as catalysts, only very low performance is shown (Comparative Example 1 and Comparative Example 1). Example 3) When the alumina-supported silver catalyst [A2] was used, an NO purification rate of about 30% was exhibited at 375 to 425 ° C. (Comparative Example 2). The examples using a catalyst in which a silver catalyst and a zinc catalyst were combined showed higher activity than Comparative Example 2 having the highest activity among the comparative examples, and a remarkable improvement in activity was observed particularly at around 350 ° C. It was. As a method for compounding zinc and silver, compared with Comparative Example 2 in all areas of the compounding of the investigated co-impregnation method (Example 1), sequential impregnation method (Example 2), and physical mixing method (Example 3). Also showed high activity, and a combined effect was observed. This effect was particularly noticeable at 350 ° C to 500 ° C.
Example 4
上記〔触媒構成成分の調製〕で調製したアルミナ担持銀と水素型ZSM-5との物理混合触媒[A1+B]を触媒として用い、上記〔触媒活性評価〕に従い、600〜250℃の温度範囲でNO転化率の評価を行った。評価結果を表１に示した。
（実施例６）
Using the physical mixed catalyst [A1 + B] of alumina-supported silver and hydrogen-type ZSM-5 prepared in [Preparation of catalyst component] as a catalyst, according to the above [Catalyst activity evaluation], a temperature range of 600 to 250 ° C. The NO conversion rate was evaluated. The evaluation results are shown in Table 1.
(Example 6)
実施例４において、触媒として、アルミナ担持銀とZSM-5担持亜鉛との物理混合触媒［A1+B3］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１、図４に示すとともに、同時に生成したエチレン、プロピレンについて図３に示した。
（実施例７）
In Example 4, a NO reduction reaction was performed in the same manner as in Example 4 except that a physical mixed catalyst [A1 + B3] of alumina-supported silver and ZSM-5-supported zinc was used as the catalyst. In addition to Table 1 and FIG. 4, ethylene and propylene produced simultaneously are shown in FIG.
(Example 7)
実施例４において、触媒としてアルミナ担持銀とZSM-5担持コバルトの物理混合触媒［A1+B4］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（実施例８）
In Example 4, a NO reduction reaction was performed in the same manner as in Example 4 except that a physical mixed catalyst [A1 + B4] of silver supported on alumina and cobalt supported on ZSM-5 was used as the catalyst. It was shown to.
(Example 8)
実施例４において、触媒としてアルミナ担持銀とZSM-5担持タングステンの物理混合触媒［A1+B5］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（実施例９）
In Example 4, a NO reduction reaction was carried out in the same manner as in Example 4 except that a physical mixed catalyst [A1 + B5] of silver supported on alumina and tungsten supported on ZSM-5 was used as the catalyst. It was shown to.
Example 9
実施例４において、触媒としてアルミナ担持銀とZSM-5担持インジウムの物理混合触媒［A1+B6］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（実施例１０）
In Example 4, a NO reduction reaction was carried out in the same manner as in Example 4 except that a physical mixed catalyst [A1 + B6] of silver supported on alumina and indium supported on ZSM-5 was used as the catalyst. It was shown to.
(Example 10)
実施例４において、触媒としてアルミナ担持銀とZSM-5担持ガリウムの物理混合触媒［A1+B7］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（実施例１１）
In Example 4, a NO reduction reaction was performed in the same manner as in Example 4 except that a physical mixed catalyst [A1 + B7] of silver supported on alumina and gallium supported on ZSM-5 was used as a catalyst. It was shown to.
(Example 11)
実施例４において、触媒としてアルミナ担持銀とZSM-5担持マンガンの物理混合触媒［A1+B8］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（実施例１２）
In Example 4, a NO reduction reaction was performed in the same manner as in Example 4 except that a physical mixed catalyst [A1 + B8] of silver supported on alumina and manganese supported on ZSM-5 was used as a catalyst. It was shown to.
(Example 12)
実施例４において、触媒としてアルミナ担持銀とZSM-5担持バリウムの物理混合触媒［A1+B9］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（比較例４）
In Example 4, a NO reduction reaction was performed in the same manner as in Example 4 except that a physical mixed catalyst [A1 + B9] of silver supported on alumina and barium supported on ZSM-5 was used as a catalyst. It was shown to.
(Comparative Example 4)
実施例４において、触媒として水素型ZSM-5触媒［B］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（比較例５−１）
In Example 4, NO reduction reaction was performed in the same manner as in Example 4 except that the hydrogen-type ZSM-5 catalyst [B] was used as the catalyst. The results are shown in Table 1.
(Comparative Example 5-1)
実施例４において、触媒として、アルミナ担持銀とZSM-5担持銅との物理混合触媒［A1+B2］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（比較例５−２）
In Example 4, a NO reduction reaction was performed in the same manner as in Example 4 except that a physical mixed catalyst [A1 + B2] of alumina-supported silver and ZSM-5-supported copper was used as the catalyst. It is shown in Table 1.
(Comparative Example 5-2)
実施例４において、触媒としてZSM-5担持銅触媒［B2］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（比較例６）
In Example 4, NO reduction reaction was performed in the same manner as in Example 4 except that the ZSM-5-supported copper catalyst [B2] was used as the catalyst. The results are shown in Table 1.
(Comparative Example 6)
実施例４において、触媒としてZSM-5担持亜鉛触媒［B3］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示すとともに、同時に生成したエチレン、プロピレンについて図３に示した。
（比較例７）
In Example 4, except that the ZSM-5-supported zinc catalyst [B3] was used as a catalyst, a NO reduction reaction was carried out in the same manner as in Example 4, and the results are shown in Table 1, and simultaneously produced ethylene, Propylene is shown in FIG.
(Comparative Example 7)
実施例４において、触媒としてZSM-5担持コバルト触媒［B4］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（比較例８）
In Example 4, NO reduction reaction was performed in the same manner as in Example 4 except that the ZSM-5-supported cobalt catalyst [B4] was used as the catalyst. The results are shown in Table 1.
(Comparative Example 8)
実施例４において、触媒としてZSM-5担持タングステン触媒［B5］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（比較例９）
In Example 4, NO reduction reaction was performed in the same manner as in Example 4 except that the ZSM-5-supported tungsten catalyst [B5] was used as the catalyst. The results are shown in Table 1.
(Comparative Example 9)
実施例４において、触媒としてZSM-5担持インジウム触媒［B6］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（比較例１０）
In Example 4, NO reduction reaction was performed in the same manner as in Example 4 except that the ZSM-5-supported indium catalyst [B6] was used as the catalyst. The results are shown in Table 1.
(Comparative Example 10)
実施例４において、触媒としてZSM-5担持ガリウム触媒［B7］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（比較例１１）
In Example 4, NO reduction reaction was performed in the same manner as in Example 4 except that the ZSM-5-supported gallium catalyst [B7] was used as the catalyst. The results are shown in Table 1.
(Comparative Example 11)
実施例４において、触媒としてZSM-5担持マンガン触媒［B8］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。
（比較例１２）
In Example 4, NO reduction reaction was performed in the same manner as in Example 4 except that the ZSM-5-supported manganese catalyst [B8] was used as the catalyst. The results are shown in Table 1.
(Comparative Example 12)
実施例４において、触媒としてZSM-5担持バリウム触媒［B9］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を表１に示した。 In Example 4, NO reduction reaction was performed in the same manner as in Example 4 except that the ZSM-5-supported barium catalyst [B9] was used as the catalyst. The results are shown in Table 1.
表１から明らかなように、実施例ごとに有効性を生ずる温度範囲に差はあるが、混合触媒の実施例４〜１２は、その物理混合前の触媒構成成分単独からなる比較例１、比較例４〜１２と比べ高いNO転化率を示す温度がある。特に実施例６のアルミナ担持銀とZSM-5担持亜鉛の物理混合触媒［A1+B3］は検討した250〜600℃の全温度域において元となるアルミナ担持銀触媒[A1]（比較例１）もしくはZSM-5担持亜鉛触媒［B3］（比較例６）より高いNO除去活性を示した。混合による活性向上効果は特に450℃〜600℃の恒温領域で顕著であり、表１のカッコで示したエチレン、プロピレンの生成温度領域とよく一致している。
As can be seen from Table 1, although there are differences in the temperature range in which the effectiveness is produced for each example, Examples 4 to 12 of the mixed catalyst are comparative examples 1 and 1 consisting of the catalyst components alone before the physical mixing. There is a temperature that shows a high NO conversion compared to Examples 4-12. In particular, the physical mixed catalyst [A1 + B3] of alumina-supported silver and ZSM-5-supported zinc in Example 6 was the original alumina-supported silver catalyst [A1] in the entire temperature range of 250 to 600 ° C. (Comparative Example 1). Alternatively, the NO removal activity was higher than that of the ZSM-5 supported zinc catalyst [B3] (Comparative Example 6). The activity improvement effect by mixing is particularly remarkable in a constant temperature region of 450 ° C. to 600 ° C., which is in good agreement with the formation temperature regions of ethylene and propylene shown in parentheses in Table 1.
図３に、図２の窒素生成と同時に定量したエチレン（図３Ａ）およびプロピレン（図３Ｂ）の生成量を示す。アルミナ担持銀触媒［A1］（比較例２）を用いた場合にはエチレンおよびプロピレンの生成はいずれもほとんど認められないが、アルミナ担持亜鉛触媒［A2］（比較例３）を用いると400℃以上でエチレンおよびプロピレンの生成が認められ、ZSM-5担持亜鉛触媒［B3］（比較例６）ではより多い量のエチレンおよびプロピレンの生成が認められる。一方、アルミナ担持銀とZSM-5担持亜鉛の物理混合触媒［A1+B3］（実施例３）では、比較例２と同様ほとんどエチレンおよびプロピレンの生成が認められない。[B3]上で生成したエチレン、プロピレン等の活性が高い低級炭化水素を利用したNO選択還元反応が［A1］上で進行することにより、NO浄化率が向上したものであると考察している。また、混合状態では、このような安定なガスとして生成するものに限らず、より不安定で検出できない活性還元剤種として供給された還元剤もNO還元に利用されると推定される。 FIG. 3 shows the production amounts of ethylene (FIG. 3A) and propylene (FIG. 3B) quantified simultaneously with the nitrogen production of FIG. When the alumina-supported silver catalyst [A1] (Comparative Example 2) is used, ethylene and propylene are hardly formed, but when the alumina-supported zinc catalyst [A2] (Comparative Example 3) is used, it is 400 ° C. or higher. The formation of ethylene and propylene was observed in ZSM-5, and a larger amount of ethylene and propylene was observed in the ZSM-5 supported zinc catalyst [B3] (Comparative Example 6). On the other hand, in the physical mixed catalyst of alumina-supported silver and ZSM-5-supported zinc [A1 + B3] (Example 3), almost no formation of ethylene and propylene was observed as in Comparative Example 2. It is considered that the NO purification rate is improved by the progress of NO selective reduction reaction using lower hydrocarbons such as ethylene and propylene produced on [B3] on [A1]. . In the mixed state, it is presumed that the reducing agent supplied as an active reducing agent species that is not stable and cannot be detected is also used for NO reduction.
（比較例１３）
実施例４において、触媒としてアルミナ担持銀とシリカ担持亜鉛の物理混合触媒［A1+C3］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図４に示した。
(Comparative Example 13)
In Example 4, a NO reduction reaction was performed in the same manner as in Example 4 except that a physical mixed catalyst [A1 + C3] of silver supported on alumina and zinc supported on silica was used as the catalyst. The results are shown in FIG. It was.
（比較例１４）
実施例４において、触媒としてアルミナ担持銀とチタニア担持亜鉛の物理混合触媒［A1+D3］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図４に示した。
(Comparative Example 14)
In Example 4, a NO reduction reaction was performed in the same manner as in Example 4 except that a physical mixed catalyst [A1 + D3] of alumina-supported silver and titania-supported zinc was used as the catalyst. The results are shown in FIG. It was.
（比較例１５）
実施例４において、触媒としてアルミナ担持銀とジルコニア担持亜鉛の物理混合触媒［A1+E3］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図４に示した。
(Comparative Example 15)
In Example 4, a NO reduction reaction was performed in the same manner as in Example 4 except that a physical mixed catalyst [A1 + E3] of silver supported on alumina and zinc supported on zirconia was used as the catalyst. The results are shown in FIG. It was.
（比較例１６）
実施例４において、触媒としてアルミナ担持銀とセリア担持亜鉛の物理混合触媒［A1+F3］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図４に示した。
(Comparative Example 16)
In Example 4, a NO reduction reaction was carried out in the same manner as in Example 4 except that a physical mixed catalyst [A1 + F3] of silver supported on alumina and zinc supported on ceria was used as a catalyst. The results are shown in FIG. It was.
図４から明らかなように、亜鉛担持触媒とアルミナ担持銀触媒の物理混合により、比較例１のアルミナ担持銀触媒［A1］単独の結果より活性が向上したのは、アルミナ担持銀アルミナ担持亜鉛物理混合触媒［A5］（実施例３）もしくはアルミナ担持銀ZSM-5担持亜鉛物理混合触媒［A1+B3］（実施例６）を用いた場合であり、アルミナ担持銀触媒とシリカ、チタニア、ジルコニアおよびセリア担持亜鉛触媒との物理混合では（比較例１１〜１４）物理混合による活性の向上は認められなかった。 As can be seen from FIG. 4, the activity of the alumina-supported silver alumina-supported zinc catalyst is improved by the physical mixing of the zinc-supported catalyst and the alumina-supported silver catalyst. A mixed catalyst [A5] (Example 3) or an alumina-supported silver ZSM-5-supported zinc physical mixed catalyst [A1 + B3] (Example 6) was used. The alumina-supported silver catalyst and silica, titania, zirconia, and In the physical mixing with the ceria-supported zinc catalyst (Comparative Examples 11 to 14), no improvement in activity due to the physical mixing was observed.
（実施例１３）
実施例４において、触媒としてアルミナ担持銀モルデナイト担持亜鉛物理混合触媒［A1+G3］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図５に示した。
(Example 13)
In Example 4, NO reduction reaction was performed in the same manner as in Example 4 except that the alumina-supported silver mordenite-supported zinc physical mixed catalyst [A1 + G3] was used as the catalyst. The results are shown in FIG.
（実施例１４）
実施例４において、触媒としてアルミナ担持銀USY担持亜鉛物理混合触媒［A1+H3］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図５に示した。
(Example 14)
In Example 4, NO reduction reaction was performed in the same manner as in Example 4 except that the alumina-supported silver USY-supported zinc physical mixed catalyst [A1 + H3] was used as the catalyst. The results are shown in FIG.
（実施例１５）
実施例４において、触媒としてアルミナ担持銀ベータ担持亜鉛物理混合触媒［A1+I3］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図５に示した。
(Example 15)
In Example 4, a NO reduction reaction was performed in the same manner as in Example 4 except that the alumina-supported silver beta-supported zinc physical mixed catalyst [A1 + I3] was used as the catalyst. The results are shown in FIG.
（実施例１６）
実施例４において、触媒としてアルミナ担持銀フェリエライト担持亜鉛物理混合触媒［A1+J3］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図５に示した。
(Example 16)
In Example 4, the NO reduction reaction was performed in the same manner as in Example 4 except that the alumina-supported silver ferrierite-supported zinc physical mixed catalyst [A1 + J3] was used as the catalyst. The results are shown in FIG. .
図５から明らかなように、亜鉛担持ゼオライト触媒とアルミナ担持銀触媒の物理混合は、ZSM-5担持亜鉛物理混合触媒［A1+B3］（実施例６）だけではなく、アルミナ担持銀モルデナイト担持亜鉛物理混合触媒［A1+G3］、アルミナ担持銀USY担持亜鉛物理混合触媒［A1+H3］、アルミナ担持銀ベータ担持亜鉛物理混合触媒［A1+I3］およびアルミナ担持銀フェリエライト担持亜鉛物理混合触媒［A1+J3］でも、担体となるゼオライトの種類により活性が向上する温度領域は異なるが、比較例１のアルミナ担持銀触媒［A1］単独の結果より活性が向上する反応条件があり、亜鉛担持ゼオライト触媒一般に本効果が認められることが考えられる。 As is clear from FIG. 5, the physical mixing of the zinc-supported zeolite catalyst and the alumina-supported silver catalyst is not limited to ZSM-5-supported zinc physical mixed catalyst [A1 + B3] (Example 6), but also alumina-supported silver mordenite-supported zinc. Physical mixed catalyst [A1 + G3], alumina supported silver USY supported zinc physical mixed catalyst [A1 + H3], alumina supported silver beta supported zinc physical mixed catalyst [A1 + I3] and alumina supported silver ferrierite supported zinc physical mixed catalyst [ In A1 + J3], the temperature range in which the activity is improved depends on the type of zeolite used as a support, but there are reaction conditions in which the activity is improved from the result of the alumina-supported silver catalyst [A1] alone in Comparative Example 1, and the zinc-supported zeolite It is considered that this effect is generally recognized in catalysts.
（実施例１７）
実施例４において、触媒として50%アルミナ担持銀と50%ZSM-5担持亜鉛の物理混合触媒［A1+B3-50］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図６に示した。
(Example 17)
In Example 4, a NO reduction reaction was performed in the same manner as in Example 4 except that a physical mixed catalyst [A1 + B3-50] of 50% alumina-supported silver and 50% ZSM-5-supported zinc was used as the catalyst. The results are shown in FIG.
（実施例１８）
実施例４において、触媒として88%アルミナ担持銀と12%ZSM-5担持亜鉛の物理混合触媒［A1+B3-88］を用いた以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図６に示した。
(Example 18)
In Example 4, a NO reduction reaction was performed in the same manner as in Example 4 except that a physical mixed catalyst [A1 + B3-88] of 88% alumina-supported silver and 12% ZSM-5-supported zinc was used as the catalyst. The results are shown in FIG.
図６から明らかなように、ZSM-5担持亜鉛とアルミナ担持銀触媒の物理混合の混合比を変えて反応を行ったところ、50%アルミナ担持銀ZSM-5担持亜鉛物理混合触媒［A1+B3-50］、88%アルミナ担持銀ZSM-5担持亜鉛物理混合触媒［A1+B3-88］いずれも、比較例１のアルミナ担持銀触媒［A1］単独の結果より高い活性を示した。ただし、380〜500℃の温度域では混合比が70:30のアルミナ担持銀ZSM-5担持亜鉛物理混合触媒［A1+B3］（実施例６）が最も高い活性を示し、より温度が低い〜360℃では88%アルミナ担持銀12%ZSM-5担持亜鉛物理混合触媒［A1+B3-88］が最も高い活性を示しており、温度ごとに混合比には最適値があることが考えられる。 As is apparent from FIG. 6, the reaction was carried out while changing the mixing ratio of the physical mixture of ZSM-5-supported zinc and alumina-supported silver catalyst, and 50% alumina-supported silver ZSM-5-supported zinc physical mixture catalyst [A1 + B3 -50], 88% alumina-supported silver ZSM-5-supported zinc physical mixed catalyst [A1 + B3-88] both showed higher activity than the result of the alumina-supported silver catalyst [A1] of Comparative Example 1 alone. However, in the temperature range of 380 to 500 ° C., the alumina-supported silver ZSM-5-supported zinc physical mixed catalyst [A1 + B3] (Example 6) having a mixing ratio of 70:30 shows the highest activity, and the temperature is lower. At 360 ° C, 88% alumina-supported silver 12% ZSM-5-supported zinc physical mixed catalyst [A1 + B3-88] showed the highest activity, and it is considered that the mixing ratio has an optimum value for each temperature.
（実施例１９）
実施例４において、触媒として50mgアルミナ担持銀とアルミナ担持亜鉛の物理混合触媒［50mg-A1+B3］を用い〔触媒活性評価〕において50mgの触媒を充填した以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図７に示した。
(Example 19)
In Example 4, a physical mixed catalyst [50 mg-A1 + B3] of 50 mg alumina-supported silver and alumina-supported zinc was used as the catalyst, and 50 mg of the catalyst was charged in [Catalyst activity evaluation]. The reduction reaction of NO was performed, and the results are shown in FIG.
（実施例２０）
実施例４において、触媒として50mgアルミナ担持銀とアルミナ担持5%亜鉛の物理混合触媒［50mg-A1+B3-5%］を用い〔触媒活性評価〕において50mgの触媒を充填した以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図７に示した。
(Example 20)
In Example 4, a physical mixed catalyst [50 mg-A1 + B3-5%] of 50 mg alumina-supported silver and alumina-supported 5% zinc was used as the catalyst, except that 50 mg of catalyst was charged in [Catalyst activity evaluation]. The NO reduction reaction was carried out in the same manner as in Example 4, and the results are shown in FIG.
図７から明らかなように、触媒の使用量を増やし、また亜鉛の担持量を上げた、50mgアルミナ担持銀とZSM-5担持亜鉛の物理混合触媒［50mg-A1+B3］や50mgアルミナ担持銀とZSM-5担持5%亜鉛の物理混合触媒［50mg-A1+B3-5%］を使用することにより、触媒活性を向上させることができる。 As is clear from FIG. 7, a physical mixed catalyst [50 mg-A1 + B3] of 50 mg alumina-supported silver and ZSM-5-supported zinc and 50 mg alumina-supported silver increased in the amount of catalyst used and increased in the amount of zinc supported. And a ZSM-5-supported 5% zinc physical mixed catalyst [50 mg-A1 + B3-5%] can improve the catalytic activity.
（実施例２１）
実施例４において、触媒として17mgのZSM-5担持亜鉛触媒［B3］を上層に、17mgのアルミナ担持銀触媒［A1］下層に混ざらないように注意深く充填した以外は、実施例４と同様にしてNOの還元反応を行い、その結果を図８に示した。
(Example 21)
In Example 4, 17 mg of ZSM-5-supported zinc catalyst [B3] was used as a catalyst in the upper layer, and 17 mg of alumina-supported silver catalyst [A1] was charged carefully so as not to mix with the lower layer. The reduction reaction of NO was performed, and the results are shown in FIG.
図８から明らかなように、ZSM-5担持亜鉛[B3]とアルミナ担持銀[A1]を２層に配置した触媒（実施例２１：◆）は、高温で若干比較例１（○）のアルミナ担持銀触媒［A1］単独の結果より高い活性を示す温度域はあるもののその効果はそれほど顕著ではない。一方、アルミナ担持銀とZSM-5担持亜鉛の物理混合触媒［A1+B3］（実施例６：▲）はこれに比べてはるかに高い活性を示した。 As is apparent from FIG. 8, the catalyst (Example 21: ◆) in which ZSM-5-supported zinc [B3] and alumina-supported silver [A1] are arranged in two layers is slightly higher in alumina than in Comparative Example 1 (◯) at high temperatures. Although there is a temperature range showing higher activity than the result of the supported silver catalyst [A1] alone, the effect is not so remarkable. On the other hand, the physical mixed catalyst [A1 + B3] (Example 6: ▲) of alumina-supported silver and ZSM-5-supported zinc showed much higher activity.
本発明の触媒は、過剰酸素を含む排出ガス中のNOxおよび未燃燃料等炭化水素の低減に有効な活性を示すものであり、排ガス規制強化が進められつつあるディーゼル車あるいはディーゼル車と同じく排ガス中に酸素が存在しNOxの還元無害化が難しいリーンバーンガソリン車、さらには燃焼器の排ガス処理技術として利用されることが期待される。
The catalyst of the present invention exhibits an effective activity for reducing hydrocarbons such as NO x and unburned fuel in exhaust gas containing excess oxygen, and is similar to a diesel vehicle or a diesel vehicle whose exhaust gas regulations are being strengthened. reductive detoxification of oxygen is present NO x is difficult lean burn gasoline car exhaust gas, more are expected to be utilized as an exhaust gas processing technique of the combustor.
Claims (8)
前記第１触媒成分の活性温度領域において、少なくとも、前記低級炭化水素を高級炭化水素から生成する第２触媒成分と、
が、分散した状態で含有されている、
排気浄化用触媒であって、
前記第１触媒成分が、担体成分としてのアルミナに銀が担持された銀担持触媒成分であり、
前記第２触媒成分が、担体成分としてのアルミナに亜鉛が担持された亜鉛担持触媒成分であるか、または、担体成分としてのゼオライトに亜鉛、コバルト、タングステン、インジウム、ガリウム、マンガン、バリウムのうちのいずれか１種又は複数種が担持された金属担持触媒成分である、
ことを特徴とする排気浄化用触媒。 A first catalyst component for reducing nitrogen oxides using lower hydrocarbons;
A second catalyst component that generates at least the lower hydrocarbon from a higher hydrocarbon in the active temperature region of the first catalyst component;
Is contained in a dispersed state,
An exhaust purification catalyst,
The first catalyst component is a silver-supported catalyst component in which silver is supported on alumina as a carrier component;
The second catalyst component is a zinc-supported catalyst component in which zinc is supported on alumina as a support component, or a zeolite as a support component is selected from zinc, cobalt, tungsten, indium, gallium, manganese, and barium. It is a metal-supported catalyst component on which any one or more are supported,
An exhaust purification catalyst characterized by that.
前記第２触媒成分における担体成分が、ゼオライトである、
ことを特徴とする排気浄化用触媒。 In claim 1,
The carrier component in the second catalyst component is zeolite.
An exhaust purification catalyst characterized by that.
前記ゼオライトの種類が、その各活性温度領域を判断要素として、前記排気の温度に応じたものとされている、
ことを特徴とする排気浄化用触媒。 In claim 2,
The type of the zeolite is determined according to the temperature of the exhaust, with each active temperature region as a determination factor.
An exhaust purification catalyst characterized by that.
前記第１触媒成分と前記第２触媒成分との含有割合は、前記排気温度が低い側に位置するほど、該第１触媒成分の含有割合が該第２触媒成分の含有割合よりも大きくなるように設定されている、
ことを特徴とする排気浄化用触媒。 In claim 2,
The content ratio between the first catalyst component and the second catalyst component is such that the content ratio of the first catalyst component is larger than the content ratio of the second catalyst component as the exhaust gas temperature is located on the lower side. Set to
An exhaust purification catalyst characterized by that.
前記第１触媒成分と前記第２触媒成分との含有重量比が、５０：５０〜８８：１２である、
ことを特徴とする排気浄化用触媒。 In claim 1,
The weight ratio of the first catalyst component and the second catalyst component is 50:50 to 88:12,
An exhaust purification catalyst characterized by that.
前記排気中に、前記排気浄化用触媒の上流側において、前記低級炭化水素よりも高級とされた高級炭化水素を供給する、
ことを特徴とする、請求項１〜５のいずれか一項に記載の排気浄化用触媒の使用方法。 The exhaust gas purification catalyst according to any one of claims 1 to 5 is disposed in an exhaust gas that also contains nitrogen oxides together with excess oxygen, and the lower gas hydrocarbon is used as a reducing agent by the exhaust gas purification catalyst. In the usage method of the exhaust gas purification catalyst according to any one of claims 1 to 5, wherein nitrogen oxides are reduced.
In the exhaust, higher hydrocarbons higher than the lower hydrocarbons are supplied upstream of the exhaust purification catalyst.
The method for using an exhaust purification catalyst according to any one of claims 1 to 5, wherein the exhaust purification catalyst is used.
前記第１触媒成分の活性温度領域において、少なくとも、前記低級炭化水素を高級炭化水素から生成する第２触媒成分と、を用意し、
前記第１触媒成分と前記第２触媒成分とを混合する、
ことを特徴とする、請求項１〜５のいずれか一項に記載の排気浄化用触媒の製造方法。 A first catalyst component for reducing nitrogen oxides using lower hydrocarbons;
A second catalyst component for producing at least the lower hydrocarbon from a higher hydrocarbon in the active temperature region of the first catalyst component;
Mixing the first catalyst component and the second catalyst component;
The method for producing an exhaust gas purification catalyst according to any one of claims 1 to 5, wherein
前記共通担体成分に前記第１担持成分を担持して、該共通担体成分と該第１担持成分とにより、低級炭化水素を用いて窒素酸化物を還元成分に還元する第１触媒成分を構成し、
前記共通担体成分に前記第２担持成分を担持して、該共通担体成分と該第２担持成分とにより、前記第１触媒成分の活性温度領域において、少なくとも、前記低級炭化水素を高級炭化水素から生成する第２触媒成分を構成する、
ことを特徴とする、請求項１または５に記載の排気浄化用触媒の製造方法。 Preparing a first carrier component, a second carrier component, and a common carrier component;
The first carrier component is supported on the common carrier component, and the common carrier component and the first carrier component constitute a first catalyst component for reducing nitrogen oxides to a reducing component using lower hydrocarbons. ,
The second carrier component is supported on the common carrier component, and at least the lower hydrocarbon is converted from the higher hydrocarbon in the active temperature region of the first catalyst component by the common carrier component and the second carrier component. Constituting a second catalyst component to be produced;
The method for producing an exhaust purification catalyst according to claim 1 or 5, wherein
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