JP2006007023A - Method for producing exhaust gas purifying catalyst and exhaust gas purifying catalyst - Google Patents
Method for producing exhaust gas purifying catalyst and exhaust gas purifying catalyst Download PDFInfo
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Abstract
Description
本発明は、排ガス浄化用触媒や大気汚染物質浄化用触媒等として利用される、ＬｎＭＯ３（Ｌｎ：希土類金属）型複合酸化物を含む排ガス浄化触媒の製造方法及び上記複合酸化物を含む排ガス浄化触媒に係り、特に、浄化性能及び耐熱性能を向上させた、自動車用触媒として好適な排ガス浄化触媒の開発技術に関する。 The present invention relates to a method for producing an exhaust gas purification catalyst containing an LnMO 3 (Ln: rare earth metal) type composite oxide, which is used as an exhaust gas purification catalyst, an air pollutant purification catalyst, or the like, and an exhaust gas purification containing the composite oxide. In particular, the present invention relates to a technology for developing an exhaust gas purification catalyst suitable for an automobile catalyst, which has improved purification performance and heat resistance performance.
自動車等の内燃機関に用いられる排ガス浄化触媒については、その浄化性能等の向上に関し、種々の提案がなされている。例えば、排ガス中に含まれる、一酸化炭素（ＣＯ）、炭化水素（ＨＣ）、及び窒素酸化物（ＮＯｘ）等の浄化に、ペロブスカイト型構造の複合酸化物が有効であることが知られている（特許文献１，２参照）。また、ペロブスカイト型複合酸化物は、多様な元素を組み合わせて形成することができる。このため、この複合酸化物の中には、単独の金属元素と酸素とからなる酸化物によっては発揮し得ない、特異な性質を有するものも存在する。この特異な性質は、例えば、複合酸化物自体を高活性な触媒として用いる場合に得られるだけでなく、複合酸化物を、貴金属等の活性成分を担持する担体として用いる場合や、貴金属を固溶させる担体として用いる場合にも得られ、これにより、貴金属の劣化が抑制されることも知られている（特許文献３〜６参照）。 Various proposals have been made regarding exhaust gas purification catalysts used in internal combustion engines such as automobiles for improving purification performance and the like. For example, it is known that a complex oxide having a perovskite structure is effective for purifying carbon monoxide (CO), hydrocarbon (HC), nitrogen oxide (NOx), etc. contained in exhaust gas. (See Patent Documents 1 and 2). Further, the perovskite complex oxide can be formed by combining various elements. For this reason, some of these composite oxides have unique properties that cannot be exhibited by an oxide composed of a single metal element and oxygen. This unique property is obtained not only when the composite oxide itself is used as a highly active catalyst, but also when the composite oxide is used as a carrier supporting an active component such as a noble metal, It is also obtained when used as a carrier to be supported, and it is also known that this suppresses the deterioration of noble metals (see Patent Documents 3 to 6).
しかしながら、一般に、ペロブスカイト型複合酸化物は、８００℃以上という高温条件下で生成されるため、比表面積が小さいという欠点がある。このため、ペロブスカイト型複合酸化物が活性点である場合には、活性点の数が少ないという問題がある。また、ペロブスカイト型複合酸化物を貴金属を担持する担体として用いる場合には、貴金属を十分に分散させて保持することが困難であるという問題がある。 However, in general, perovskite-type composite oxides are generated under high temperature conditions of 800 ° C. or higher, and thus have a drawback that the specific surface area is small. For this reason, when the perovskite complex oxide is an active point, there is a problem that the number of active points is small. Further, when the perovskite complex oxide is used as a carrier for supporting a noble metal, there is a problem that it is difficult to sufficiently disperse and hold the noble metal.
このため、ペロブスカイト型複合酸化物をアルミナの高比表面積担体と共存させて用いることが提案されている（特許文献７参照）。特許文献７によれば、ペロブスカイト型複合酸化物をアルミナと混合することにより、比表面積を十分に保持することができる。しかしながら、特許文献７に記載された技術は、ペロブスカイト型複合酸化物粉末を高温焼成により一旦合成し、その後アルミナと物理的に混合させる手段をとるため、ペロブスカイト型複合酸化物自体を高比表面積化する効果に乏しいのが現状である。 For this reason, it has been proposed to use a perovskite complex oxide in combination with a high specific surface area support of alumina (see Patent Document 7). According to Patent Document 7, the specific surface area can be sufficiently maintained by mixing the perovskite complex oxide with alumina. However, the technique described in Patent Document 7 uses a means of once synthesizing perovskite-type composite oxide powder by high-temperature firing and then physically mixing with alumina, so that the perovskite-type composite oxide itself has a high specific surface area. The current situation is that it is not effective.
また、アルミナの担体に、ペロブスカイト型複合酸化物の構成元素の前駆体塩及びその他の材料を水溶液として含浸担持することにより、担体上にペロブスカイト型複合酸化物を十分に分散させるという技術も開示されている（特許文献８，９参照）。しかしながら、これらの技術については、ペロブスカイト型複合酸化物を含浸、乾燥させる工程で、被担持体が担体の表面上に分散して生成するだけではなく、被担持体同士が互いに凝集するおそれがあるため、高分散化が不十分である。 Also disclosed is a technique for sufficiently dispersing the perovskite type composite oxide on the support by impregnating and supporting the precursor salt of the constituent elements of the perovskite type composite oxide and other materials as an aqueous solution on the support of alumina. (See Patent Documents 8 and 9). However, in these techniques, in the step of impregnating and drying the perovskite complex oxide, the supported bodies are not only dispersed and formed on the surface of the carrier, but also the supported bodies may aggregate with each other. Therefore, high dispersion is insufficient.
本発明は、以上のような種々の事情に鑑みてなされたものであり、被担持体を担体へ高分散化させることにより、従来技術に比して浄化性能及び耐熱性能を向上させた排ガス浄化触媒の製造方法及びこの製造方法により得られた排ガス浄化触媒を提供することが目的としている。 The present invention has been made in view of the various circumstances as described above, and the exhaust gas purification has improved purification performance and heat resistance performance as compared with the prior art by highly dispersing the support to the carrier. It is an object to provide a method for producing a catalyst and an exhaust gas purification catalyst obtained by this production method.
本発明者等は、従来技術に比して浄化性能及び耐熱性能が高い排ガス浄化触媒について、鋭意研究を重ねた。その結果、アルミナの高比表面積担体上にペロブスカイト型複合酸化物を高分散状態で存在させるには、いわゆる含浸法を用いることが好適であるとの知見を得た。ここで、含浸法とは、細孔中へ触媒成分を浸み込ませて細孔壁に固定し、乾燥、焼成して活性成分を担持する方法である。また、発明者等は、上記含浸法の中でも、特に、Incipience Wetness法（以下、単に「ＩＷ法」と称する場合がある。）を用いることが一層好適であるとの知見を得た。ここで、ＩＷ法とは、以下の手順を経て実施される担持方法である。即ち、先ず、被担持体の成分を含有する金属硝酸塩水溶液を多孔質な担持体である粉末にゆっくりと加える。これにより、上記水溶液は担体の気孔内に吸収されるが、粉末粒子の外側では乾燥状態が保持されるため、粉末状の担体は乾燥状態のごとく流動する。次いで、このように気孔に水溶液が吸収され、さらに上記吸収が飽和状態に達すると、粉末粒子の外側部分にぬれが発生し、粉末粒子同士が互いに結合して塊を形成する。なお、初期段階において、粉末粒子の外側が乾燥状態を保持しているにもかかわらず、気孔が水溶液で充填されている状況が、Incipience Wetnessと称される所以であり、このような状況は、粉末粒子を振動させたり、攪拌したりすることで、容易に判断することができる。 The inventors of the present invention have made extensive studies on an exhaust gas purification catalyst having higher purification performance and heat resistance performance than the conventional technology. As a result, it has been found that it is preferable to use a so-called impregnation method in order to allow the perovskite complex oxide to be present in a highly dispersed state on a high specific surface area support of alumina. Here, the impregnation method is a method in which a catalyst component is immersed in pores, fixed to the pore walls, dried and fired to carry the active component. Further, the inventors have found that it is more preferable to use the Incipience Wetness method (hereinafter sometimes simply referred to as “IW method”) among the above impregnation methods. Here, the IW method is a loading method performed through the following procedure. That is, first, a metal nitrate aqueous solution containing a component to be supported is slowly added to a powder that is a porous support. As a result, the aqueous solution is absorbed in the pores of the carrier, but since the dry state is maintained outside the powder particles, the powdery carrier flows like a dry state. Next, when the aqueous solution is absorbed into the pores as described above and the absorption reaches a saturated state, wetting occurs in the outer portion of the powder particles, and the powder particles are bonded to each other to form a lump. In the initial stage, the situation where the pores are filled with an aqueous solution despite the fact that the outside of the powder particles is kept dry is the reason called Incipience Wetness. It can be easily determined by vibrating or stirring the powder particles.
ペロブスカイト型複合酸化物は、一般に、ＡＢＯ３という示性式で表され、Ａとしては、希土類元素、アルカリ土類元素又はアルカリ金属を適用することができ、Ｂとしては、遷移金属元素又はＡｌを適用することができる。アルミナからなる担体は、粒子内部に無数の細孔を有するため比表面積が大きい。よって、細孔の内部に選択的にペロブスカイト型複合酸化物を担持することができれば、ペロブスカイト型複合酸化物の比表面積を大きく向上させることができる。発明者等の研究の結果、上記含浸法、特にＩＷ法を用いた場合には、ペロブスカイト型複合酸化物を、担体の細孔中のみに選択的に含浸担持させることができることが判明した。具体的には、以下の手段により、好適な含浸担持を実現することができる。先ず、担体が有する細孔容積を予め把握し、その容積と同体積の、被担持体の成分を含有する前駆体塩水溶液を調製する。次いで、これを担体粉末に吸収させることにより、前駆体塩水溶液を担体の細孔内部のみに含浸させる。さらに、このように選択的に前駆体塩水溶液を担持した担体を乾燥、焼成することにより、細孔の内部のみにペロブスカイト型複合酸化物を担持させることができる。 The perovskite type complex oxide is generally represented by a formula of ABO 3 , and as A, a rare earth element, an alkaline earth element or an alkali metal can be applied, and as B, a transition metal element or Al can be used. Can be applied. Since the support made of alumina has innumerable pores inside the particles, the specific surface area is large. Therefore, if the perovskite complex oxide can be selectively supported inside the pores, the specific surface area of the perovskite complex oxide can be greatly improved. As a result of the inventors' research, it has been found that when the above impregnation method, particularly the IW method is used, the perovskite complex oxide can be selectively impregnated and supported only in the pores of the support. Specifically, suitable impregnation support can be realized by the following means. First, the pore volume of the carrier is grasped in advance, and a precursor salt aqueous solution containing the component of the supported body having the same volume as that volume is prepared. Next, the carrier powder is absorbed to impregnate the precursor salt aqueous solution only inside the pores of the carrier. Further, by selectively drying and firing the carrier carrying the precursor salt aqueous solution selectively as described above, the perovskite complex oxide can be supported only in the pores.
このように、ペロブスカイト型複合酸化物は、担体の細孔内に担持された状態で排ガス浄化触媒として用いることができる。発明者等は、さらに、ペロブスカイト型複合酸化物と貴金属とをともに被担持体とすることで、これらの相互作用により一層高度な浄化性能及び耐熱性能を得ることができるとの知見を得た。この場合、ペロブスカイト型複合酸化物をアルミナの細孔内部にのみ担持するため、上記相互作用を発揮させるためには、貴金属もアルミナの細孔内部にのみ担持させる必要がある。そこで、担体であるアルミナの細孔内部にペロブスカイト型複合酸化物のみを担持させる場合と同様に、アルミナの細孔容積と同体積の、ペロブスカイト型複合酸化物の前駆体塩水溶液及び貴金属塩水溶液を調製し、アルミナにペロブスカイト型複合酸化物を担持した後、貴金属塩水溶液をペロブスカイト型複合酸化物が担持されたアルミナ粉末に吸収させ、乾燥、焼成を行う。これにより、貴金属とペロブスカイト型複合酸化物とを相互作用し易い位置関係に配置することができる。本発明は、以上のような知見に基づくものである。 Thus, the perovskite complex oxide can be used as an exhaust gas purification catalyst in a state of being supported in the pores of the carrier. Further, the inventors have found that by using both the perovskite complex oxide and the noble metal as a support, higher purification performance and heat resistance performance can be obtained by their interaction. In this case, since the perovskite complex oxide is supported only inside the pores of alumina, it is necessary to support the precious metal only inside the pores of alumina in order to exert the above interaction. Therefore, as in the case where only the perovskite type complex oxide is supported inside the pores of alumina as the support, the precursor salt aqueous solution and the noble metal salt aqueous solution of the perovskite type complex oxide having the same volume as the pore volume of alumina are used. After preparing and supporting the perovskite type complex oxide on alumina, the noble metal salt aqueous solution is absorbed into the alumina powder supporting the perovskite type complex oxide, followed by drying and firing. As a result, the noble metal and the perovskite complex oxide can be arranged in a positional relationship that facilitates interaction. The present invention is based on the above findings.
即ち、本発明の排ガス浄化触媒の製造方法は、アルミナからなる担持体と、上記担持体に担持され、ＬｎＭＯ３（Ｌｎ：希土類金属）で表されるペロブスカイト型複合酸化物を含む被担持体とを備える排ガス浄化触媒を製造するにあたり、アルミナの細孔内に触媒成分を含有する溶液を浸み込ませ、細孔壁に固定させる工程を経る方法（含浸法）により排ガス浄化触媒を得ることを特徴としている。なお、このような排ガス浄化触媒の製造方法においては、上記含浸法のうち、ＩＷ法を用いることが望ましい。 That is, the method for producing an exhaust gas purifying catalyst of the present invention includes a support made of alumina, a support that is supported on the support and includes a perovskite complex oxide represented by LnMO 3 (Ln: rare earth metal), and In the production of an exhaust gas purification catalyst comprising a catalyst, an exhaust gas purification catalyst is obtained by a method (impregnation method) through a step of impregnating a solution containing a catalyst component into the pores of alumina and fixing it to the pore walls. It is a feature. In such a method for producing an exhaust gas purification catalyst, it is desirable to use the IW method among the above impregnation methods.
また、本発明の排ガス浄化触媒は、上記方法を実施することにより得られるものであり、アルミナからなる担持体と、上記担持体に担持され、ＬｎＭＯ３（Ｌｎ：希土類金属）で表されるペロブスカイト型複合酸化物を含む被担持体とを備え、上記含浸法により製造されたことを特徴としている。なお、このような排ガス浄化触媒においては、上記ＬｎＭＯ３（Ｌｎ：希土類金属）において、少なくともＭが遷移金属及びＡｌのうちの少なくとも一種であることが望ましい。 The exhaust gas purifying catalyst of the present invention is obtained by carrying out the above method, and is a support made of alumina, and a perovskite supported by the support and represented by LnMO 3 (Ln: rare earth metal). It is characterized by being manufactured by the above impregnation method. In such an exhaust gas purification catalyst, it is desirable that at least M is at least one of a transition metal and Al in the LnMO 3 (Ln: rare earth metal).
本発明によれば、含浸法（特にＩＷ法）を用いることにより、通常は低比表面積であるペロブスカイト型複合酸化物を、アルミナに高分散状態に担持することにより、高比表面積とすることができる。このため、本発明の排ガス浄化触媒に用いるアルミナの平均細孔径が約２０ｎｍであることを考慮し、担持されるＬａＦｅＯ３の一次粒子径が最も大きい場合で約２０ｎｍであると仮定すると、計算上約４０ｍ２／ｇ以上の比表面積を有することになる。通常の方法で作製したＬａＦｅ０３の比表面積は１０ｍ２／ｇであるため、本発明によれば、ＬａＦｅ０３の比表面積を従来の約４倍とすることができる。従って、本発明の排ガス浄化触媒によれば、優れた浄化性能を実現することができる。 According to the present invention, by using an impregnation method (particularly, the IW method), a perovskite-type composite oxide, which usually has a low specific surface area, is supported on alumina in a highly dispersed state, whereby a high specific surface area can be obtained. it can. Therefore, considering that the average pore diameter of alumina used in the exhaust gas purification catalyst of the present invention is about 20 nm, and assuming that the primary particle diameter of LaFeO 3 supported is about 20 nm is the largest, It will have a specific surface area of about 40 m 2 / g or more. Since the specific surface area of LaFeO 3 produced by a normal method is 10 m 2 / g, according to the present invention, the specific surface area of LaFeO 3 can be increased to about 4 times that of the conventional method. Therefore, according to the exhaust gas purification catalyst of the present invention, excellent purification performance can be realized.
また、ペロブスカイト型複合酸化物は、高温にさらされると凝集し、比表面積が低下する。しかしながら、本発明の方法により製造された触媒であれば、ペロブスカイト型複合酸化物がアルミナの細孔内に担持されるため、上記酸化物の易動度が低く、凝集が著しく低減される。従って、本発明の排ガス浄化触媒によれば、優れた耐熱性を実現することができる。 Further, the perovskite complex oxide aggregates when exposed to a high temperature, and the specific surface area decreases. However, in the case of the catalyst produced by the method of the present invention, the perovskite type complex oxide is supported in the pores of alumina, so the mobility of the oxide is low and the aggregation is remarkably reduced. Therefore, according to the exhaust gas purification catalyst of the present invention, excellent heat resistance can be realized.
さらに、含浸法によってアルミナにペロブスカイト型複合酸化物を担持する際に、貴金属をペロブスカイト型複合酸化物と組み合わせてアルミナに担持した場合には、アルミナによる貴金属の高分散化による効果と、ペロブスカイト型複合酸化物及び貴金属による相互作用による効果とのいずれもが効率的に得られ、一層優れた浄化性能及び耐熱性能を実現することができる。 Furthermore, when supporting a perovskite type composite oxide on alumina by the impregnation method, if the noble metal is supported on alumina in combination with the perovskite type composite oxide, the effect of high dispersion of the noble metal by alumina and the perovskite type composite oxide are supported. Both of the effects of the interaction between the oxide and the noble metal can be obtained efficiently, and more excellent purification performance and heat resistance performance can be realized.
以下、実施例により本発明を具体的に説明する。
〔担持方法の比較〕
本発明の排ガス浄化触媒の製造方法は、被担持体を含浸法を用いてアルミナに担持するものである。実施例１では、含浸法の中でも、特に、ＩＷ法による担持方法が、従来の含浸法（蒸発乾固法（ＮＩＴ法）や物理混合法）による担持方法に比して優れていることを実証する。
（発明例１〜３：ＩＷ法）
ポリ塩化ビニデンフィルム上に所定量のアルミナを配置し、１ｇのアルミナ（細孔容積０．６９ｃｍ３）に対して、１．４８ｍｏｌ／１のＬａ，Ｍｎ硝酸塩水溶液を０．３１ｃｍ３マイクロピペットによってアルミナに滴下し、アルミナをフィルムに包んで十分に溶液を含浸させた。その後、６５０℃（発明例１）、７５０℃（発明例２）、８５０℃（発明例３）でそれぞれ５時間焼成した。これにより、１０ｗｔ％ＬａＦｅＯ３／Ａ１２Ｏ３（発明例１〜３）をそれぞれ得た。
Hereinafter, the present invention will be described specifically by way of examples.
[Comparison of loading methods]
In the method for producing an exhaust gas purifying catalyst of the present invention, a support is supported on alumina using an impregnation method. In Example 1, among the impregnation methods, in particular, it is proved that the supporting method by the IW method is superior to the supporting method by the conventional impregnation method (evaporation-drying method (NIT method) or physical mixing method). To do.
(Invention Examples 1-3: IW method)
A predetermined amount of alumina is arranged on a polyvinylidene chloride film, and 1.48 mol / 1 La, Mn nitrate aqueous solution is 0.31 cm 3 micropipette with respect to 1 g of alumina (pore volume 0.69 cm 3 ). The solution was dropped on alumina, and the alumina was wrapped in a film and sufficiently impregnated with the solution. Thereafter, each was fired at 650 ° C. (Invention Example 1), 750 ° C. (Invention Example 2), and 850 ° C. (Invention Example 3) for 5 hours. Thereby, 10 wt% LaFeO 3 / A1 2 O 3 (Invention Examples 1 to 3) was obtained.
（比較例１〜３：ＮＩＴ法）
硝酸ランタン六水和物の前駆体塩水溶液と、硝酸マンガン四水和物の前駆体塩水溶液とを混合し、混合水溶液に、所定量のアルミナを浸す。この際、水溶液中の水の量はアルミナ細孔容積に比して大過剰量とする。これを蒸発乾固させ、次いで、１１０℃で１２時間乾燥させ、６５０℃（比較例１）、７５０℃（比較例２）、８５０℃（比較例３）でそれぞれ５時間焼成し、１０ｗｔ％ＬａＦｅＯ３／Ａ１２Ｏ３（比較例１〜３）をそれぞれ得た。
(Comparative Examples 1-3: NIT method)
A precursor salt aqueous solution of lanthanum nitrate hexahydrate and a precursor salt aqueous solution of manganese nitrate tetrahydrate are mixed, and a predetermined amount of alumina is immersed in the mixed aqueous solution. At this time, the amount of water in the aqueous solution is set to a large excess amount compared to the alumina pore volume. This was evaporated to dryness, then dried at 110 ° C. for 12 hours, calcined at 650 ° C. (Comparative Example 1), 750 ° C. (Comparative Example 2), and 850 ° C. (Comparative Example 3) for 5 hours, respectively, and 10 wt% LaFeO 3 / A1 2 O 3 (Comparative Examples 1 to 3) were obtained.
（比較例４〜６：物理混合法）
硝酸ランタン六水和物の前駆体塩水溶液と、硝酸マンガン四水和物の前駆体塩水溶液との混合水溶液、及び炭酸アンモニウムにアンモニア水を加えた沈殿剤水溶液を作製した。次いで、沈殿剤水溶液に前駆体塩の混合水溶液を滴下し、生成した沈殿物を吸引ろ過して洗浄した後、１１０℃で１２時間乾燥させ、６５０℃（比較例４）、７５０℃（比較例５）、８５０℃（比較例６）でそれぞれ５時間焼成し、ＬａＦｅＯ３（比較例４〜６）をそれぞれ得た。これらをアルミナとともに乳鉢を用いて物理混合し、１０ｗｔ％ＬａＦｅＯ３／Ａ１２Ｏ３（比較例４〜６）をそれぞれ得た。
(Comparative Examples 4 to 6: physical mixing method)
A mixed aqueous solution of a precursor salt aqueous solution of lanthanum nitrate hexahydrate and a precursor salt aqueous solution of manganese nitrate tetrahydrate, and a precipitant aqueous solution in which ammonia water was added to ammonium carbonate were prepared. Next, a mixed aqueous solution of the precursor salt is dropped into the precipitant aqueous solution, and the generated precipitate is filtered by suction and washed, and then dried at 110 ° C. for 12 hours, 650 ° C. (Comparative Example 4), 750 ° C. (Comparative Example) 5) and baked at 850 ° C. (Comparative Example 6) for 5 hours, respectively, to obtain LaFeO 3 (Comparative Examples 4 to 6). These were physically mixed using alumina and a mortar to obtain 10 wt% LaFeO 3 / A1 2 O 3 (Comparative Examples 4 to 6).
（比較例７〜９：ＩＷ法）
ＩＷ法を用い、ペロブスカイトが生成していない場合について検討するため、発明例１〜３と同様の方法で、焼成温度を６５０℃（比較例７）、７５０℃（比較例８）、８５０℃（比較例９）として、Ｆｅ２Ｏ３／Ａ１２Ｏ３（比較例７〜９）をそれぞれ得た。
(Comparative Examples 7-9: IW method)
In order to examine the case where no perovskite is generated using the IW method, the firing temperature is 650 ° C. (Comparative Example 7), 750 ° C. (Comparative Example 8), 850 ° C. As Comparative Example 9), Fe 2 O 3 / A1 2 O 3 (Comparative Examples 7 to 9) were obtained.
以上に述べた、発明例１〜３及び比較例１〜９の各排ガス浄化触媒の製造条件等を表１に示す。また、発明例１〜３及び比較例１〜９の各排ガス浄化触媒の浄化性能に関する結果を図１に示す。 Table 1 shows the manufacturing conditions and the like of the exhaust gas purification catalysts of Invention Examples 1 to 3 and Comparative Examples 1 to 9 described above. Moreover, the result regarding the purification performance of each exhaust gas purification catalyst of invention examples 1-3 and comparative examples 1-9 is shown in FIG.
図１から明らかなように、担持方法については、ＩＷ法、ＮＩＴ法及び物理混合法のうち、ＩＷ法を採用した場合（発明例１〜３）に、焼成温度のいかんに関わらず、優れた結果を示すことが判明した。また、ＩＷ法を採用した場合であっても、被担持体が本発明の範囲（ＬｎＭＯ３（Ｌｎ：希土類金属）で表されるペロブスカイト型複合酸化物）を逸脱する場合（比較例７〜９）には、各発明例程度に優れた結果が得られないことも判明した。従って、本発明の製造方法で採用した担持方法（含浸法、特にはＩＷ法）や被担持体が、他の担持方法（ＮＩＴ法や物理混合法）や他の被担持体に比して優れていることが実証された。 As is clear from FIG. 1, the supporting method is excellent regardless of the firing temperature when the IW method (Invention Examples 1 to 3) is adopted among the IW method, the NIT method, and the physical mixing method. It was found to show results. Further, even when the IW method is adopted, the supported body deviates from the scope of the present invention (perovskite complex oxide represented by LnMO 3 (Ln: rare earth metal)) (Comparative Examples 7 to 9). It was also found that the results excellent in each invention example were not obtained. Therefore, the supporting method (impregnation method, particularly IW method) and the supported body employed in the production method of the present invention are superior to other supporting methods (NIT method and physical mixing method) and other supported bodies. It was proved that.
〔ＬａＦｅＯ３の担持量の比較〕
次に、実施例２では、Ａ１２Ｏ３へのＬａＦｅＯ３の担持量が、プロパン転化率へどのように影響するかについて調査した。
（発明例４，５：ＩＷ法）
発明例３と同様の方法、即ちＩＷ法を用い、焼成温度を８５０℃として、５ｗｔ％ＬａＦｅＯ３／Ａ１２Ｏ３（発明例４）、２０ｗｔ％ＬａＦｅＯ３／Ａ１２Ｏ３（発明例５）をそれぞれ得た。
[Comparison of LaFeO 3 loading]
Next, in Example 2, it was investigated how the amount of LaFeO 3 supported on A1 2 O 3 affects the propane conversion.
(Invention Examples 4 and 5: IW method)
The same method as that of Invention Example 3, that is, using the IW method and setting the firing temperature to 850 ° C., 5 wt% LaFeO 3 / A1 2 O 3 (Invention Example 4), 20 wt% LaFeO 3 / A1 2 O 3 (Invention Example 5) Respectively.
（比較例１０，１１：ＮＩＴ法）
比較例３と同様の方法、即ちＮＩＴ法を用い、焼成温度を８５０℃として、５ｗｔ％ＬａＦｅＯ３／Ａ１２Ｏ３（比較例１０）、１０ｗｔ％ＬａＦｅＯ３／Ａ１２Ｏ３（比較例１１）をそれぞれ得た。
(Comparative Examples 10 and 11: NIT method)
The same method as in Comparative Example 3, that is, using the NIT method and setting the firing temperature to 850 ° C., 5 wt% LaFeO 3 / A1 2 O 3 (Comparative Example 10), 10 wt% LaFeO 3 / A1 2 O 3 (Comparative Example 11) Respectively.
以上に述べた、発明例３〜５及び比較例３，１０，１１の各排ガス浄化触媒の製造条件等を表２に示す。また、発明例３〜５及び比較例３，１０，１１の各排ガス浄化触媒の浄化性能（プロパン転化率）に関する結果を図２に示す。 Table 2 shows the manufacturing conditions and the like of the exhaust gas purifying catalysts of Invention Examples 3 to 5 and Comparative Examples 3, 10, and 11 described above. Moreover, the result regarding the purification | cleaning performance (propane conversion rate) of each exhaust gas purification catalyst of invention examples 3-5 and comparative examples 3,10,11 is shown in FIG.
図２によれば、ＬａＦｅＯ３の担持量の増加に伴い浄化性能が向上することが判明した。また、ＬａＦｅＯ３の担持量が同じであれば、ＮＩＴ法に比してＩＷを用いた場合が、より優れた浄化性能を発揮することも判明した。 According to FIG. 2, it has been found that the purification performance improves with an increase in the amount of LaFeO 3 supported. It has also been found that if the amount of LaFeO 3 supported is the same, the use of IW as compared to the NIT method exhibits better purification performance.
〔担持方法（及び担持量）と排ガス浄化触媒の結晶構造との関係〕
排ガス浄化触媒には、ペロブスカイト構造の複合酸化物が好適であり、アルミナを担体とした場合についても、ペロブスカイト型複合酸化物の被担持体が確実に担持されていることが有利である。このため、実施例３では、上記の各担持方法（１Ｗ法、ＮＩＴ法及び物理混合法）と排ガス浄化触媒の結晶構造との関係、及び担持量と排ガス浄化触媒の結晶構造との関係について調査した。
[Relationship between loading method (and loading amount) and crystal structure of exhaust gas purification catalyst]
A composite oxide having a perovskite structure is suitable for the exhaust gas purification catalyst, and even when alumina is used as a carrier, it is advantageous that the supported body of the perovskite composite oxide is securely supported. For this reason, in Example 3, the relationship between each of the above-mentioned supporting methods (1W method, NIT method and physical mixing method) and the crystal structure of the exhaust gas purification catalyst, and the relationship between the supported amount and the crystal structure of the exhaust gas purification catalyst were investigated. did.
図３は、実施例１で得た発明例３（ＩＷ法）、比較例３（ＮＩＴ法）及び比較例６（物理混合法）の各排ガス浄化触媒について、ＸＲＤパターンを示すグラフである。図３によれば、物理混合法では、被担持体の結晶化を裏付けるピークが明確に確認されている。これは比表面積が極めて小さいことを意味しており、好ましくない。なお、ＮＩＴ法及びＩＷ法については、被担持体の結晶化は確認されないが、ペロブスカイト型複合酸化物が担持されているか否かの判断はできない。以上により、物理混合法では、好適なペロブスカイト型複合酸化物を担持させることができないことが実証された。 FIG. 3 is a graph showing XRD patterns for the exhaust gas purification catalysts of Invention Example 3 (IW method), Comparative Example 3 (NIT method), and Comparative Example 6 (physical mixing method) obtained in Example 1. According to FIG. 3, in the physical mixing method, the peak that supports the crystallization of the support is clearly confirmed. This means that the specific surface area is extremely small, which is not preferable. In the NIT method and the IW method, crystallization of the support is not confirmed, but it cannot be determined whether or not the perovskite complex oxide is supported. From the above, it was proved that a suitable perovskite complex oxide cannot be supported by the physical mixing method.
図４は、担持量を変化させてＩＷ法によりＡ１２Ｏ３へＬａＦｅＯ３を担持させた各触媒について、ＸＲＤパターンを示すグラフである。図４によれば、いずれの担持量においても、ペロブスカイト型複合酸化物であるＬａＦｅＯ３のピークは見られず、ペロブスカイト型複合酸化物の担持は確認できない。そこで、２０ｗｔ％のＬａＦｅＯ３／Ａ１２Ｏ３のラマン分光分析を行った結果を図５に示す。比較のため、ＬａＦｅＯ３、Ｆｅ２Ｏ３、及びＡ１２Ｏ３のラマンスペクトルを図５に併記した。これらの結果によれば、２０ｗｔ％のＬａＦｅＯ３／Ａ１２Ｏ３では、ＬａＦｅＯ３と同じ波数領域にピークが存在しており、ＬａＦｅＯ３が生成していることが確認できる。また、Ｆｅ２Ｏ３のピークは、２０ｗｔ％のＬａＦｅＯ３／Ａ１２Ｏ３には存在しないことから、２０ｗｔ％のＬａＦｅＯ３／Ａ１２Ｏ３では全てのＦｅがペロブスカイト型複合酸化物であるＬａＦｅＯ３となっていることが判る。従って、担持量２０ｗｔ％のＬａＦｅＯ３／Ａ１２Ｏ３では、アルミナの細孔内にペロブスカイト型複合酸化物が細かな結晶として高分散化した状態で確実に担持されており、排ガス浄化触媒として優れた性能を示すといえる。 FIG. 4 is a graph showing an XRD pattern for each catalyst in which LaFeO 3 is supported on A1 2 O 3 by the IW method while changing the supported amount. According to FIG. 4, no peak of LaFeO 3 that is a perovskite complex oxide is observed at any loading amount, and the loading of the perovskite complex oxide cannot be confirmed. Therefore, FIG. 5 shows the result of Raman spectroscopic analysis of 20 wt% LaFeO 3 / A1 2 O 3 . For comparison, Raman spectra of LaFeO 3 , Fe 2 O 3 , and A1 2 O 3 are also shown in FIG. According to these results, 20 wt% LaFeO 3 / A1 2 O 3 has a peak in the same wave number region as LaFeO 3, and it can be confirmed that LaFeO 3 is generated. Further, the peak of Fe 2 O 3, since not present in 20 wt% of LaFeO 3 / A1 2 O 3, is 20 wt% of LaFeO 3 / A1 2 in O 3 all Fe is perovskite-type composite oxide LaFeO It turns out that it is 3 . Therefore, in LaFeO 3 / A1 2 O 3 with a loading amount of 20 wt%, the perovskite complex oxide is reliably supported in a highly dispersed state as fine crystals in the pores of alumina, and is excellent as an exhaust gas purification catalyst. It can be said that it shows the performance.
以上説明したように、本発明によれば、含浸法によってＬｎＭＯ３（Ｌｎ：希土類金属）型複合酸化物を担持体に担持することにより、自動車用触媒として十分な浄化性能及び耐熱性能を確保することができる。よって、本発明は、自動車用触媒等に使用することができる点で有望である。 As described above, according to the present invention, the LnMO 3 (Ln: rare earth metal) type composite oxide is supported on the support by the impregnation method, thereby ensuring sufficient purification performance and heat resistance performance as an automobile catalyst. be able to. Therefore, the present invention is promising in that it can be used for automobile catalysts and the like.
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|---|---|---|---|---|
| WO2008004687A1 (en) * | 2006-07-03 | 2008-01-10 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst |
| JP2009154077A (en) * | 2007-12-26 | 2009-07-16 | Nagoya Institute Of Technology | Ceramic catalyst material and exhaust purifying method using the same |
| US11219520B2 (en) | 2017-03-14 | 2022-01-11 | Shape Memory Medical, Inc. | Shape memory polymer foams to seal space around valves |
| US11597792B2 (en) | 2017-10-30 | 2023-03-07 | The Texas A&M University System | Radiopaque thermoplastic polymer |
-
2004
- 2004-06-23 JP JP2004184833A patent/JP4204520B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008004687A1 (en) * | 2006-07-03 | 2008-01-10 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst |
| JP2008012382A (en) * | 2006-07-03 | 2008-01-24 | Toyota Motor Corp | Catalyst for purifying exhaust gas |
| US8999878B2 (en) | 2006-07-03 | 2015-04-07 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst |
| JP2009154077A (en) * | 2007-12-26 | 2009-07-16 | Nagoya Institute Of Technology | Ceramic catalyst material and exhaust purifying method using the same |
| US11219520B2 (en) | 2017-03-14 | 2022-01-11 | Shape Memory Medical, Inc. | Shape memory polymer foams to seal space around valves |
| US11597792B2 (en) | 2017-10-30 | 2023-03-07 | The Texas A&M University System | Radiopaque thermoplastic polymer |
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| Publication number | Publication date |
|---|---|
| JP4204520B2 (en) | 2009-01-07 |
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