JP6010325B2 - Exhaust gas purifying catalyst, catalyst supporting structure, and production method thereof - Google Patents
Exhaust gas purifying catalyst, catalyst supporting structure, and production method thereof Download PDFInfo
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Description
本発明は、排ガス浄化用として好ましく用いることができる触媒および触媒担持構造体ならびにこれらの製造方法に関する。 The present invention relates to a catalyst that can be preferably used for exhaust gas purification, a catalyst-supporting structure, and a method for producing them.
自動車等から排出される排ガス中の一酸化炭素（ＣＯ）、未燃炭化水素（ＨＣ）、窒素酸化物（ＮＯX）等を浄化するために用いることができる触媒として、比較的大きな比表面積を有する担体粒子の表面に白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）などの活性金属を担持させたものが、従来、開発されている。このような触媒では、排ガス中の浄化対象と活性金属との接触効率を高めて触媒能を向上させるために、活性金属をできるだけ均一に分散させて担持させる。しかしながら、継続して使用すると活性金属の凝集が起こり、触媒能は低下する。 Carbon monoxide in exhaust gas discharged from an automobile or the like (CO), unburnt hydrocarbons (HC), as a catalyst that can be used to purify nitrogen oxides (NO X) or the like, a relatively large specific surface area Conventionally developed are those in which an active metal such as platinum (Pt), palladium (Pd), rhodium (Rh) is supported on the surface of the carrier particles. In such a catalyst, the active metal is dispersed and supported as uniformly as possible in order to increase the contact efficiency between the purification target in the exhaust gas and the active metal to improve the catalytic performance. However, if it is continuously used, active metal agglomerates and the catalytic ability decreases.
これに対して特許文献１には、貴金属粒子と、前記貴金属粒子と接触し、当該貴金属粒子の移動を抑制する第１の化合物と、前記貴金属粒子と前記第１の化合物を内包し、貴金属粒子の移動を抑制すると共に第１の化合物同士の接触に伴う第１の化合物の凝集を抑制する第２の化合物とからなり、前記第１の化合物は、前記貴金属粒子を担持し、かつ、この貴金属粒子を担持した第１の化合物の単体又は集合体を、前記第２の化合物により隔てられた区画内に含み、かつ、前記第１の化合物が、希土類元素を含む複合物であることを特徴とする排気ガス浄化用触媒が記載されている。そして、特許文献１には、本発明に係る排気ガス浄化用触媒によれば、貴金属粒子が担持される第１の化合物が希土類元素を含む複合物であり、この貴金属粒子と第１の化合物とを第２の化合物で覆うことにより、貴金属粒子の移動と同時に第１の化合物同士の凝集も抑制するので、製造コストや環境負荷を大きくすることなく、第１の化合物による貴金属粒子の活性向上効果を維持することが可能となると記載されている。 On the other hand, Patent Document 1 includes precious metal particles, a first compound that comes into contact with the precious metal particles and suppresses the movement of the precious metal particles, the precious metal particles and the first compound, And a second compound that suppresses the aggregation of the first compound accompanying the contact between the first compounds, the first compound carrying the noble metal particles and the noble metal. A single substance or aggregate of the first compound carrying particles is included in a compartment separated by the second compound, and the first compound is a composite containing a rare earth element. An exhaust gas purifying catalyst is described. And in patent document 1, according to the exhaust gas purifying catalyst which concerns on this invention, the 1st compound by which a noble metal particle is carry | supported is a composite containing a rare earth element, This noble metal particle, the 1st compound, By covering the surface with the second compound, the movement of the noble metal particles is suppressed simultaneously with the aggregation of the first compounds, so that the effect of improving the activity of the noble metal particles by the first compound without increasing the manufacturing cost and the environmental load. It is described that it is possible to maintain
なお、特許文献１には、第１の化合物と貴金属粒子とが化学結合することで貴金属粒子が移動を抑制されることが記載されている（００１６段落）。また、特許文献１の図１には第２の化合物が粒子状のものであることが示されており、第２の化合物が、貴金属粒子を担持した第１の化合物の周囲に形成され、これにより貴金属粒子を担持した第１の化合物の担体または複数個の集合体が第２の化合物により隔てられた区画内に含まれることが記載されている（００１５段落）。また、特許文献１の実施例では、第２の化合物の前駆体としてベーマイト粉末を用い、これを乾燥および焼成してγアルミナからなる第２の化合物を得たことが記載されている（００５７段落、００５８段落、表２など）。また、第２の化合物により隔てられた区画内に貴金属粒子と第１の化合物とを内包すると記載されている（００１８段落）。さらに、第２の化合物は包摂材であることが記載されている（００３５段落）。
したがって、特許文献１の請求項１には、第２の化合物が貴金属粒子と第１の化合物を内包して貴金属粒子の移動を抑制すると記載されているものの、特許文献１に記載の排気ガス浄化用触媒において第２の化合物は、貴金属粒子が担持した第１の化合物を凝集しないようにするためのスペーサーとしての役割を果たすだけであって、貴金属粒子を担体（第１の化合物）へ積極的に付着させる機能は備えていないといえる。上記のように、特許文献１に記載の排気ガス浄化用触媒において、貴金属粒子は化学結合のみの作用によって、担体の表面についている。
Patent Document 1 describes that the movement of the noble metal particles is suppressed by chemically bonding the first compound and the noble metal particles (paragraph 0016). Further, FIG. 1 of Patent Document 1 shows that the second compound is in the form of particles, and the second compound is formed around the first compound carrying the noble metal particles. Describes that a carrier or a plurality of aggregates of the first compound carrying the noble metal particles is contained in a compartment separated by the second compound (paragraph 0015). Moreover, in the Example of patent document 1, it is described using the boehmite powder as a precursor of a 2nd compound, and drying and baking this, and obtained the 2nd compound which consists of (gamma) alumina (0057 paragraphs). , 0058 paragraph, Table 2, etc.). Further, it is described that the noble metal particles and the first compound are encapsulated in a compartment separated by the second compound (paragraph 0018). Furthermore, it is described that the second compound is an inclusion material (paragraph 0035).
Therefore, claim 1 of Patent Document 1 describes that the second compound contains the noble metal particles and the first compound and suppresses the movement of the noble metal particles, but the exhaust gas purification described in Patent Document 1 In the catalyst for use, the second compound only serves as a spacer for preventing the first compound supported by the noble metal particles from aggregating, and the noble metal particles are actively applied to the support (first compound). It can be said that it does not have a function of attaching to the surface. As described above, in the exhaust gas purifying catalyst described in Patent Document 1, the noble metal particles are attached to the surface of the support only by the action of chemical bonds.
特許文献１に記載のような従来の排ガス浄化用触媒は、継続して使用すると触媒能が低下するので、これを改善する必要があった。これは継続して使用すると貴金属粒子等の活性金属が凝集してしまうと考えられるからである。特許文献１に記載の排ガス浄化用触媒についても、貴金属粒子が担体と離れて凝集し、継続して使用すると触媒能は低下する。また、仮に、貴金属粒子は第２の化合物によって隔てられた区画の外へは移動しないとしても、区画内では移動して凝集するので、長時間、継続して使用すると、やはり同様に、触媒能は低下する。
従来の触媒は、継続して使用した場合に活性金属が凝集するので、凝集することを前提として活性金属の担体への担持量を増加させていた。この場合、コスト面等において不利になる。
The conventional exhaust gas purifying catalyst as described in Patent Document 1 has a need to be improved since the catalytic ability is lowered when continuously used. This is because active metals such as noble metal particles are considered to aggregate when used continuously. Also for the exhaust gas purifying catalyst described in Patent Document 1, the precious metal particles are aggregated away from the carrier, and the catalytic ability is lowered when continuously used. Further, even if the noble metal particles do not move out of the compartments separated by the second compound, they move and aggregate in the compartments. Will decline.
In the conventional catalyst, the active metal aggregates when continuously used. Therefore, the amount of the active metal supported on the carrier is increased on the assumption that the active metal aggregates. This is disadvantageous in terms of cost.
本発明はこのような課題を解決することを目的とする。すなわち、継続して使用しても、その触媒能を維持する触媒およびこれを担持した構造体ならびにこれらの製造方法を提供することを目的とする。 The present invention aims to solve such problems. That is, an object of the present invention is to provide a catalyst that maintains its catalytic ability even if it is continuously used, a structure carrying the catalyst, and a method for producing them.
本発明者は上記課題を解決するため鋭意検討し、本発明を完成させた。
本発明は以下の（i）〜（xix）である。
（i）溶出成分および／またはこれに由来する成分が、担体に担持した活性金属を、前記担体の表面に固定している触媒を含む排ガス浄化用触媒。
（ii）前記溶出成分が、前記担体から溶出したものである、上記（i）に記載の排ガス浄化用触媒。
（iii）比表面積が２．５ｍ2／ｇ以上である、上記（i）または（ii）に記載の排ガス浄化用触媒。
（iv）前記溶出成分がＢａ化合物、Ａｌ化合物およびＢａＡｌ複合酸化物からなる群から選ばれる少なくとも１つである、上記（i）〜（iii）のいずれかに記載の排ガス浄化用触媒。
（v）前記溶出成分がＢａＡｌ2Ｏ4、Ａｌ（ＯＨ）3およびＡｌＯＯＨからなる群から選ばれる少なくとも１つである、上記（i）〜（iv）のいずれかに記載の排ガス浄化用触媒。
（vi）前記担体が、前記溶出成分を含む担体ａと前記溶出成分を含まない担体ｂとからなり、
前記担体ａから溶出し、前記担体ａの表面で固化した前記溶出成分および／またはこれに由来する成分が、前記担体ａに担持した活性金属を前記担体ａの表面に固定している触媒Ａと、
前記担体ａから溶出し、前記担体ｂの表面で固化した前記溶出成分および／またはこれに由来する成分が、前記担体ｂに担持した活性金属を前記担体ｂの表面に固定している触媒Ｂと
を含む、上記（i）〜（v）のいずれかに記載の排ガス浄化用触媒。
（vii）前記担体ｂが、酸化セリウム、バリウムヘキサアルミネートおよびＹＳＺからなる群から選ばれる少なくとも１つを含む、上記（vi）に記載の排ガス浄化用触媒。
（viii）前記担体ｂが酸化セリウムを主成分とし、
前記触媒Ａと前記触媒Ｂとの合計質量に対する前記触媒Ａの質量比（Ａ／（Ａ＋Ｂ）×１００）が１０質量％超８０質量％未満である、上記（vi）または（vii）に記載の排ガス浄化用触媒。
（ix）前記担体ｂがバリウムヘキサアルミネートまたはＹＳＺを主成分とし、
前記触媒Ａと前記触媒Ｂとの合計質量に対する前記触媒Ａの質量比（Ａ／（Ａ＋Ｂ）×１００）が５〜５０質量％である、上記（vi）または（vii）に記載の排ガス浄化用触媒。
（x）前記活性金属が、Ｐｔ、Ｐｄ、Ｒｈ、Ｒｕ、Ｏｓ、Ｉｒ、ＡｕおよびＡｇからなる群から選ばれる少なくとも１つを主成分とする、上記（i）〜（ix）のいずれかに記載の排ガス浄化用触媒。
（xi）排ガス浄化用の三元触媒である、上記（i）〜（x）のいずれかに記載の排ガス浄化用触媒。
（xii）上記（i）〜（xi）のいずれかに記載の排ガス浄化用触媒を表面に有する、触媒担持構造体。
（xiii）前記担体の表面に前記活性金属を担持させる担持工程［α］と、
前記溶出成分を含む材料および前記活性金属を担持させた前記担体を、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程［α］と、
前記溶出成分および／またはこれに由来する成分を前記担体の表面で固化して触媒を得る固化工程［α］と
を備え、上記（i）〜（xi）のいずれかに記載の排ガス浄化用触媒が得られる、排ガス浄化用触媒の製造方法。
（xiv）前記溶出成分を含む前記担体ａの表面に前記活性金属を担持させる担持工程［β］と、
前記活性金属を担持させた前記担体ａを、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程［β］と、
前記溶出成分および／またはこれに由来する成分を前記担体ａの表面で固化して触媒Ａを得る固化工程［β］と
を備え、上記（i）〜（xi）のいずれかに記載の排ガス浄化用触媒が得られる、上記（xiii）に記載の排ガス浄化用触媒の製造方法。
（xv）前記溶出成分を含む前記担体ａおよび前記溶出成分を含まない前記担体ｂの各々の表面に前記活性金属を担持させる担持工程［γ］と、
前記活性金属を担持させた前記担体ａおよび前記活性金属を担持させた前記担体ｂを、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程［γ］と、
前記溶出成分および／またはこれに由来する成分を前記担体ａおよび前記担体ｂの表面で固化して触媒Ａおよび触媒Ｂを得る固化工程［γ］と
を備え、上記（i）〜（xi）のいずれかに記載の排ガス浄化用触媒が得られる、上記（xiii）または（xiv）に記載の排ガス浄化用触媒の製造方法。
（xvi）上記（i）〜（xi）のいずれかに記載の排ガス浄化用触媒または上記（xiii）〜（xv）のいずれかに記載の排ガス浄化用触媒の製造方法によって得られる排ガス浄化用触媒を、構造体の表面に付けて上記（xii）に記載の触媒担持構造体を得る工程を備える、触媒担持構造体の製造方法。
（xvii）前記担体の表面に前記活性金属を担持させる担持工程［α］と、
前記溶出成分を含む材料および前記活性金属を担持させた前記担体を、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程［α］と、
前記活性金属を担持した前記担体を、前記溶出工程によって得られる前記溶媒とともに構造体と接触させ、その後、前記溶媒を除去することで、前記溶出成分および／またはこれに由来する成分を前記担体の表面で固化し、あわせて前記活性金属を担持した前記担体を前記構造体の表面に付ける付着工程［α］と
を備え、上記（xii）に記載の触媒担持構造体が得られる、触媒担持構造体の製造方法。
（xviii）前記溶出成分を含む前記担体ａの表面に前記活性金属を担持させる担持工程［β］と
前記活性金属を担持させた前記担体ａを、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程［β］と、
前記活性金属を担持した前記担体ａを、前記溶出工程によって得られる前記溶媒とともに構造体と接触させ、その後、前記溶媒を除去することで、前記溶出成分および／またはこれに由来する成分を前記担体ａの表面で固化し、あわせて前記活性金属を担持した前記担体ａを前記構造体の表面に付ける付着工程［β］と
を備え、上記（xii）に記載の触媒担持構造体が得られる、上記（xvii）に記載の触媒担持構造体の製造方法。
（xix）前記溶出成分を含む前記担体ａおよび前記溶出成分を含まない前記担体ｂの各々の表面に前記活性金属を担持させる担持工程［γ］と、
前記活性金属を担持させた前記担体ａおよび前記活性金属を担持させた前記担体ｂを、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程［γ］と、
前記活性金属を担持した前記担体ａおよび前記担体ｂを、前記溶出工程によって得られる前記溶媒とともに構造体と接触させ、その後、前記溶媒を除去することで、前記溶出成分および／またはこれに由来する成分を前記担体の表面で固化し、あわせて前記活性金属を担持した前記担体ａおよび前記担体ｂを前記構造体の表面に付ける付着工程［γ］と
を備え、上記（xii）に記載の触媒担持構造体が得られる、上記（xvii）または上記（xviii）に記載の触媒担持構造体の製造方法。
The inventor has intensively studied to solve the above-mentioned problems, and has completed the present invention.
The present invention includes the following (i) to (xix).
(I) An exhaust gas purifying catalyst, wherein the eluted component and / or a component derived therefrom includes a catalyst in which an active metal supported on a carrier is fixed to the surface of the carrier.
(Ii) The exhaust gas purifying catalyst according to (i), wherein the elution component is eluted from the carrier.
(Iii) The exhaust gas-purifying catalyst according to (i) or (ii), wherein the specific surface area is 2.5 m 2 / g or more.
(Iv) The exhaust gas purifying catalyst according to any one of (i) to (iii), wherein the elution component is at least one selected from the group consisting of a Ba compound, an Al compound, and a BaAl composite oxide.
(V) The exhaust gas purifying catalyst according to any one of the above (i) to (iv), wherein the elution component is at least one selected from the group consisting of BaAl 2 O 4 , Al (OH) 3 and AlOOH.
(Vi) The carrier comprises a carrier a containing the eluting component and a carrier b not containing the eluting component,
A catalyst A in which the elution component eluted from the carrier a and solidified on the surface of the carrier a and / or a component derived therefrom fixes the active metal supported on the carrier a to the surface of the carrier a; ,
A catalyst B in which the elution component eluted from the carrier a and solidified on the surface of the carrier b and / or a component derived therefrom fixes the active metal supported on the carrier b to the surface of the carrier b; The exhaust gas-purifying catalyst according to any one of (i) to (v), comprising:
(Vii) The exhaust gas-purifying catalyst according to (vi), wherein the carrier b includes at least one selected from the group consisting of cerium oxide, barium hexaaluminate, and YSZ.
(Viii) the carrier b is mainly composed of cerium oxide,
The mass ratio of the catalyst A to the total mass of the catalyst A and the catalyst B (A / (A + B) × 100) is more than 10 mass% and less than 80 mass%, according to the above (vi) or (vii) Exhaust gas purification catalyst.
(Ix) The carrier b is mainly composed of barium hexaaluminate or YSZ,
For exhaust gas purification according to (vi) or (vii) above, wherein the mass ratio of the catalyst A to the total mass of the catalyst A and the catalyst B (A / (A + B) × 100) is 5 to 50 mass%. catalyst.
(X) The active metal according to any one of the above (i) to (ix), wherein the active metal is mainly composed of at least one selected from the group consisting of Pt, Pd, Rh, Ru, Os, Ir, Au, and Ag. The catalyst for exhaust gas purification as described.
(Xi) The exhaust gas purifying catalyst according to any one of the above (i) to (x), which is a three-way catalyst for exhaust gas purifying.
(Xii) A catalyst-carrying structure having the exhaust gas-purifying catalyst according to any one of (i) to (xi) on the surface.
(Xiii) a supporting step [α] for supporting the active metal on the surface of the carrier;
An elution step [α] in which the material containing the elution component and the carrier loaded with the active metal are brought into contact with a solvent that dissolves the elution component to elute at least a part of the elution component into the solvent;
The exhaust gas purifying catalyst according to any one of the above (i) to (xi), comprising a solidification step [α] that solidifies the eluted component and / or a component derived therefrom on the surface of the carrier to obtain a catalyst. A process for producing an exhaust gas purifying catalyst.
(Xiv) a supporting step [β] for supporting the active metal on the surface of the carrier a containing the eluting component;
An elution step [β] in which the carrier a carrying the active metal is brought into contact with a solvent that dissolves the elution component to elute at least a part of the elution component into the solvent;
The exhaust gas purification according to any one of (i) to (xi), comprising a solidification step [β] for solidifying the eluted component and / or a component derived therefrom on the surface of the carrier a to obtain a catalyst A A method for producing an exhaust gas purifying catalyst as described in (xiii) above, wherein a catalyst for use is obtained.
(Xv) a supporting step [γ] for supporting the active metal on the surface of each of the carrier a containing the eluting component and the carrier b not containing the eluting component;
An elution step of bringing the carrier a carrying the active metal and the carrier b carrying the active metal into contact with a solvent that dissolves the elution component to elute at least a part of the elution component into the solvent [Γ]
A solidifying step [γ] in which the eluted component and / or a component derived therefrom is solidified on the surface of the carrier a and the carrier b to obtain the catalyst A and the catalyst B, and the above (i) to (xi) The method for producing an exhaust gas purifying catalyst according to (xiii) or (xiv) above, wherein the exhaust gas purifying catalyst according to any one of the above is obtained.
(Xvi) Exhaust gas purification catalyst according to any one of (i) to (xi) or an exhaust gas purification catalyst obtained by the method for producing an exhaust gas purification catalyst according to any of (xiii) to (xv) Is attached to the surface of the structure to obtain the catalyst-supporting structure according to the above (xii).
(Xvii) a supporting step [α] for supporting the active metal on the surface of the carrier;
An elution step [α] in which the material containing the elution component and the carrier loaded with the active metal are brought into contact with a solvent that dissolves the elution component to elute at least a part of the elution component into the solvent;
The carrier carrying the active metal is brought into contact with the structure together with the solvent obtained by the elution step, and then the solvent is removed, so that the eluted component and / or the component derived therefrom can be removed from the carrier. A catalyst-carrying structure comprising the attachment step [α] solidifying on the surface and attaching the carrier carrying the active metal to the surface of the structure, wherein the catalyst-carrying structure according to (xii) is obtained. Body manufacturing method.
(Xviii) a supporting step [β] for supporting the active metal on the surface of the carrier a containing the eluting component, and the carrier a supporting the active metal with a solvent for dissolving the eluting component; An elution step [β] for eluting at least part of the elution component into a solvent;
The carrier a carrying the active metal is brought into contact with the structure together with the solvent obtained by the elution step, and then the solvent is removed to remove the eluted component and / or a component derived therefrom. an adhesion step [β] that solidifies on the surface of a, and attaches the carrier a supporting the active metal to the surface of the structure, thereby obtaining the catalyst-supporting structure according to (xii) above. The method for producing a catalyst-supporting structure according to (xvii) above.
(Xix) a supporting step [γ] for supporting the active metal on the surface of each of the carrier a containing the eluting component and the carrier b not containing the eluting component;
An elution step of bringing the carrier a carrying the active metal and the carrier b carrying the active metal into contact with a solvent that dissolves the elution component to elute at least a part of the elution component into the solvent [Γ]
The carrier a and the carrier b carrying the active metal are brought into contact with the structure together with the solvent obtained by the elution step, and then the solvent is removed to thereby derive the elution component and / or the same. A catalyst as described in (xii) above, comprising solidifying components on the surface of the carrier and attaching the carrier a and the carrier b carrying the active metal to the surface of the structure. The method for producing a catalyst-supporting structure according to (xvii) or (xviii) above, wherein a support structure is obtained.
本発明によれば、継続して使用しても、その触媒能を維持する触媒を提供することができる。また、この触媒を担持した構造体ならびにこれらの製造方法を提供することができる。本発明の排ガス浄化用触媒は活性金属が凝集し難いので、活性金属の担持量を少なくしても、長期間、活性が継続する。 According to the present invention, it is possible to provide a catalyst that maintains its catalytic ability even when used continuously. Moreover, the structure which supported this catalyst, and these manufacturing methods can be provided. Since the active metal hardly aggregates in the exhaust gas purifying catalyst of the present invention, the activity continues for a long period of time even if the amount of active metal supported is reduced.
本発明について説明する。
本発明は、溶出成分および／またはこれに由来する成分が、前記担体に担持した活性金属を、前記担体の表面に固定している触媒を含む排ガス浄化用触媒である。
このような触媒を、以下では「本発明の排ガス浄化用触媒」ともいう。
本発明の排ガス浄化用触媒は、自動車等の排ガス浄化のために好ましく用いることができ、排ガス浄化用の三元触媒としても好ましく用いることができるものであるが、その用途は排ガス浄化に限定されるものではない。その他の用途にも用いることができる。例えば、ＶＯＣおよび炭化水素の燃焼に用いることができる。
The present invention will be described.
The present invention is an exhaust gas purifying catalyst in which an elution component and / or a component derived therefrom includes a catalyst in which an active metal supported on the carrier is fixed to the surface of the carrier.
Hereinafter, such a catalyst is also referred to as “the exhaust gas purifying catalyst of the present invention”.
The exhaust gas purification catalyst of the present invention can be preferably used for exhaust gas purification of automobiles and the like, and can also be preferably used as a three-way catalyst for exhaust gas purification, but its use is limited to exhaust gas purification. It is not something. It can also be used for other purposes. For example, it can be used for VOC and hydrocarbon combustion.
初めに、本発明の排ガス浄化用触媒が含む前記触媒について、概念断面図を用いて説明する。
図１は前記触媒の概略断面図である。なお、図１（ａ）、（ｂ）および（ｃ）は、いずれも本発明の排ガス浄化用触媒が含む、溶出成分および／またはこれに由来する成分（以下では「溶出成分および／またはこれに由来する成分」を「溶出由来成分」ともいう）が前記担体に担持した活性金属を前記担体の表面に固定している触媒を示すものである。また、図１（ｂ）は、図１（ａ）に対して溶出由来成分が少ない態様を示しており、図１（ｃ）は、逆に溶出由来成分が多く、活性金属を覆っている態様を示している。なお、本発明の排ガス浄化用触媒が含む前記触媒において、１つの担体の表面に存在する溶出由来成分の態様は１種類でなくてよい。例えば、図１（ａ）、（ｂ）および（ｃ）に示される態様の溶出由来成分が混在するものであってよい。
First, the catalyst included in the exhaust gas purifying catalyst of the present invention will be described using a conceptual cross-sectional view.
FIG. 1 is a schematic sectional view of the catalyst. 1 (a), (b) and (c) are all components of the eluted component and / or components derived from the exhaust gas purifying catalyst of the present invention (hereinafter referred to as “eluted component and / or this). The “derived component” is also referred to as “elution-derived component”) indicates a catalyst in which the active metal supported on the carrier is fixed on the surface of the carrier. Moreover, FIG.1 (b) has shown the aspect with few elution origin components with respect to FIG.1 (a), and FIG.1 (c) conversely has many elution origin components and the aspect which has covered the active metal. Is shown. In the catalyst included in the exhaust gas purifying catalyst of the present invention, the form of the elution-derived component present on the surface of one carrier may not be one type. For example, the elution origin component of the aspect shown by FIG. 1 (a), (b) and (c) may be mixed.
図１（ａ）〜（ｃ）に示すように、触媒（１）は、担体（２）の表面に活性金属（４）を備えたものである。また、担体（２）の表面に溶出由来成分（６）が存在しており、この溶出由来成分（６）が活性金属（４）を担体（２）の表面に固定し、活性金属（４）の移動を抑制する機能を果たす。従来の触媒は排ガス浄化用触媒等として使用を継続すると、活性金属の凝集が起こり触媒能は低下したが、本発明の排ガス浄化用触媒が含む触媒は、図１に示すように溶出由来成分（６）が活性金属（４）を固定しているので活性金属の凝集が起こり難く、その結果、使用を継続しても触媒能を高位に維持することができる。 As shown in FIGS. 1 (a) to 1 (c), the catalyst (1) has an active metal (4) on the surface of the support (2). Further, the elution-derived component (6) is present on the surface of the carrier (2), and this elution-derived component (6) fixes the active metal (4) to the surface of the carrier (2), and the active metal (4) The function to suppress the movement of. When the conventional catalyst continues to be used as an exhaust gas purifying catalyst or the like, active metal agglomeration occurs and the catalytic ability is reduced. However, the catalyst included in the exhaust gas purifying catalyst of the present invention includes an elution origin component ( 6) fixes the active metal (4), so that the active metal hardly aggregates. As a result, the catalytic ability can be maintained at a high level even if the use is continued.
また、溶出由来成分（６）は、担体（２）と活性金属（４）との隙間を埋めるように固化する傾向があるので、図１（ｂ）に示すように溶出由来成分（６）の量が少ない場合であっても、活性金属（４）を担体（２）の表面へ強固に密着させて固定し、継続して使用しても触媒能を高位に維持する効果が高い。 Further, since the elution-derived component (6) tends to solidify so as to fill the gap between the carrier (2) and the active metal (4), as shown in FIG. 1 (b), the elution-derived component (6) Even when the amount is small, the active metal (4) is firmly fixed to the surface of the carrier (2) and fixed, and even if it is continuously used, the effect of maintaining the catalytic performance at a high level is high.
また、図１（ｃ）に示すように、溶出由来成分（６）が活性金属（４）を覆っている場合でも、溶出由来成分（６）が緻密ではなく、例えば細孔が形成されているような場合であれば、本発明の排ガス浄化用触媒は触媒活性を発揮する。
後述する本発明の触媒の製造方法［α］によって製造された本発明の排ガス浄化用触媒は、溶出由来成分（６）が緻密ではなく細孔が形成される傾向があるので、図１（ｃ）に示すように溶出由来成分（６）が活性金属（４）を覆っていても、本発明の排ガス浄化用触媒は触媒活性を発揮する傾向がある。
In addition, as shown in FIG. 1 (c), even when the elution-derived component (6) covers the active metal (4), the elution-derived component (6) is not dense and, for example, pores are formed. In such a case, the exhaust gas purifying catalyst of the present invention exhibits catalytic activity.
In the exhaust gas-purifying catalyst of the present invention produced by the catalyst production method [α] of the present invention, which will be described later, the elution-derived component (6) is not dense but tends to form pores. ), Even if the elution-derived component (6) covers the active metal (4), the exhaust gas purifying catalyst of the present invention tends to exhibit catalytic activity.
なお、上記のように溶出由来成分とは、溶出成分および／またはこれに由来する成分を意味するが、ここで「これ（溶出成分）に由来する成分」とは、溶出成分が溶媒に含まれる他の成分等と化合等したり、溶出成分が脱水反応したりすることで生じた成分を意味する。例えば、溶出成分がＢａＡｌ2Ｏ4であり、溶媒が水である場合、ＢａＡｌ2Ｏ4は水に溶解してＢａ2+、［Ａｌ（ＯＨ）4］-となった後、溶媒等に含まれる成分と化合等したり、脱水反応したりしてＡｌ（ＯＨ）3などの不溶成分に変化して、担体の表面において固化するものと考えられる。また、例えば溶出成分がＡｌＯＯＨであり、溶媒が水である場合、ＡｌＯＯＨは水に溶解した後、乾燥させると、脱水反応して、Ａｌ（ＯＨ）3などの不溶成分に変化して、担体の表面において固化するものと考えられる。ここに挙げたＡｌ（ＯＨ）3やＡｌ2Ｏ3などが「これ（溶出成分）に由来する成分」に該当する。 In addition, as described above, the elution-derived component means an elution component and / or a component derived therefrom. Here, the “component derived from this (elution component)” includes the elution component in the solvent. It means a component generated by combining with other components or the like, or by dehydrating the eluted component. For example, when the elution component is BaAl 2 O 4 and the solvent is water, BaAl 2 O 4 dissolves in water to become Ba 2+ , [Al (OH) 4 ] −, and then contained in the solvent It is considered that it becomes a insoluble component such as Al (OH) 3 by solidification on the surface of the carrier by combination with a component to be mixed or a dehydration reaction. Further, for example, when the elution component is AlOOH and the solvent is water, the AlOOH dissolves in water and then dried to undergo a dehydration reaction to change into an insoluble component such as Al (OH) 3 , It is thought to solidify on the surface. Al (OH) 3 and Al 2 O 3 listed here correspond to “components derived from this (eluting component)”.
＜担体＞
次に、本発明の排ガス浄化用触媒の一部を構成する担体について説明する。
担体は活性金属を担持するものであれば特に限定されないが、前記溶出成分を含むものであることが好ましい。以下では、前記溶出成分を含む担体を担体ａという。また、前記溶出成分を含まない担体を担体ｂという。本発明の排ガス浄化用触媒において担体は、担体ａを含むことが好ましい。また、本発明の排ガス浄化用触媒において担体は、担体ａを含み、さらに担体ｂを含むことがさらに好ましい。
<Carrier>
Next, the carrier constituting a part of the exhaust gas purifying catalyst of the present invention will be described.
The carrier is not particularly limited as long as it supports an active metal, but preferably contains the elution component. Hereinafter, the carrier containing the elution component is referred to as carrier a. The carrier that does not contain the eluting component is referred to as carrier b. In the exhaust gas purifying catalyst of the present invention, the carrier preferably contains a carrier a. Further, in the exhaust gas purifying catalyst of the present invention, it is more preferable that the carrier includes the carrier a and further includes the carrier b.
＜担体ａ＞
担体ａについて説明する。
担体ａは溶出成分を含み、前記溶出成分を溶解する溶媒と接触することで前記溶出成分の少なくとも一部を溶出するものである。
したがって、担体ａが含む溶出成分の種類は、製造の際に用いる溶媒との関係で決定されるものである。例えば溶媒として水を用いる場合、溶出成分は水溶性成分ということになる。担体ａは前記溶出成分として水溶性成分を含み、かつ溶媒として水を用いることが好ましい。なお、溶媒としては水の他、有機溶媒を用いることもできる。
<Carrier a>
The carrier a will be described.
The carrier a contains an elution component and elutes at least a part of the elution component by contacting with a solvent that dissolves the elution component.
Therefore, the type of elution component contained in the carrier a is determined in relation to the solvent used in the production. For example, when water is used as the solvent, the eluted component is a water-soluble component. The carrier a preferably contains a water-soluble component as the elution component and uses water as the solvent. As the solvent, an organic solvent can be used in addition to water.
担体ａは、溶出成分として、Ｂａ化合物、Ａｌ化合物およびＢａＡｌ複合酸化物からなる群から選ばれる少なくとも１つを含むことが好ましく、ＢａＡｌ2Ｏ4、Ａｌ（ＯＨ）3およびＡｌＯＯＨからなる群から選ばれる少なくとも１つを含むことがより好ましく、ＢａＡｌ2Ｏ4を含むことがさらに好ましい。また、担体ａに含まれるＢａＡｌ2Ｏ4、Ａｌ（ＯＨ）3およびＡｌＯＯＨの合計含有率は５〜１００質量％であることが好ましく、１０〜９５質量％であることがより好ましく、１５〜９０質量％であることがより好ましく、１８〜７１質量％であることがさらに好ましい。また、担体ａは、ＢａＡｌ2Ｏ4を１８〜７１質量％含むことが好ましく、１８〜６３質量％含むことがより好ましく、１８〜５４質量％含むことがさらに好ましい。本発明の排ガス浄化用触媒を継続して使用してもその触媒能がより長期間、維持されるからである。ここで担体ａにおけるＢａＡｌ2Ｏ4の含有率は、Ｂａのすべてが担体ａにおいてＢａＡｌ2Ｏ4となると仮定して算出した値である。また、担体ａに含まれるＢａの含有率はＩＣＰ発光分光分析装置を用いて測定するものとする。
なお、本発明者は、Ｂａのすべてが担体ａにおいてＢａＡｌ2Ｏ4となると仮定して算出した含有率が５４質量％程度を超える場合、実際に担体ａに含まれるＢａの概ねすべてがＢａＡｌ2Ｏ4として存在し、５４質量％程度以下の場合は、Ｂａ含有率が低くなるほど、ＢａはＢａＡｌ12Ｏ19の態様で存在する割合が高くなることをＸ線粉末回折測定を行って確認している。したがって、原料中に含まれるＢａのすべてが担体ａにおいてＢａＡｌ2Ｏ4となると仮定して算出した値が５４質量％以下である場合は、溶媒が水の場合に溶出成分に相当するＢａＡｌ2Ｏ4と溶出成分に相当しないＢａＡｌ12Ｏ19とが混在する状態の担体ａとなる。このように担体ａは、すべてが溶出成分からなるのではなく、溶出成分の他に、さらに溶出成分に相当しない成分も含まれていることが好ましい。
また、担体ａが溶出成分としてＢａＡｌ2Ｏ4、Ａｌ（ＯＨ）3およびＡｌＯＯＨからなる群から選ばれる少なくとも１つを含む場合、溶媒として水を用いることができる。
The carrier a preferably contains at least one selected from the group consisting of Ba compounds, Al compounds and BaAl composite oxides as an elution component, and is selected from the group consisting of BaAl 2 O 4 , Al (OH) 3 and AlOOH. It is more preferable that it contains at least one selected from the group consisting of BaAl 2 O 4 . Further, the total content of BaAl 2 O 4 , Al (OH) 3 and AlOOH contained in the carrier a is preferably 5 to 100% by mass, more preferably 10 to 95% by mass, and 15 to 90%. It is more preferable that it is mass%, and it is further more preferable that it is 18-71 mass%. Further, the carrier a preferably contains 18 to 71% by mass of BaAl 2 O 4 , more preferably 18 to 63% by mass, and further preferably 18 to 54% by mass. This is because even if the exhaust gas purifying catalyst of the present invention is continuously used, its catalytic ability is maintained for a longer period of time. Here, the content of BaAl 2 O 4 in the carrier a is a value calculated on the assumption that all of Ba becomes BaAl 2 O 4 in the carrier a. Moreover, the content rate of Ba contained in the support | carrier a shall be measured using an ICP emission spectroscopy analyzer.
In addition, when the content rate calculated on the assumption that all of Ba becomes BaAl 2 O 4 in the carrier a exceeds about 54% by mass, the present inventor has almost all of Ba actually contained in the carrier a being BaAl 2. When it is present as O 4 and is about 54% by mass or less, it is confirmed by performing X-ray powder diffraction measurement that the proportion of Ba present in the form of BaAl 12 O 19 increases as the Ba content decreases. Yes. Therefore, when the value calculated on the assumption that all of Ba contained in the raw material is BaAl 2 O 4 in the carrier a is 54% by mass or less, BaAl 2 O corresponding to the eluted component when the solvent is water. 4 and the carrier a in a state where BaAl 12 O 19 not corresponding to the eluted component is mixed. As described above, it is preferable that the carrier a is not entirely composed of an elution component, and further includes a component not corresponding to the elution component in addition to the elution component.
When the carrier a contains at least one selected from the group consisting of BaAl 2 O 4 , Al (OH) 3 and AlOOH as an elution component, water can be used as a solvent.
担体ａは、溶媒と接触すると、このような溶出成分を溶出する。溶出した前記溶出成分および／またはこれに由来する成分（溶出由来成分）は担体ａの表面で固化して、図１に示したように、担体ａの表面に活性金属を固定することができる。 When the carrier a comes into contact with the solvent, such an elution component is eluted. The eluted components and / or components derived therefrom (elution-derived components) are solidified on the surface of the carrier a, and the active metal can be fixed on the surface of the carrier a as shown in FIG.
担体ａが、このような溶出成分以外のその他成分を含む場合、その他成分は、Ｂａ、ＡｌおよびＺｒならびにこれらの酸化物であることが好ましく、Ｂａ、Ａｌ、ＺｒおよびＹならびにこれらの酸化物であることがより好ましい。ここで「これらの酸化物」とは、Ｂａ、Ａｌ、Ｚｒ、Ｙの各々の元素の酸化物、すなわちＢａＯ、Ａｌ2Ｏ3、ＺｒＯ2、Ｙ2Ｏ3、ＹＳＺ等であってよく、ＢａＡｌ12Ｏ19、ＢａＺｒＯ3などの複合酸化物であってもよく、これらの酸化物と複合酸化物の両方を含むものであってもよい。ここでＹＳＺはイットリア安定化ジルコニアを意味し、酸化ジルコニウム（ＺｒＯ2）へ、イットリウム（Ｙ）をドープして得られるものである。ＹＳＺにおけるＺｒの含有率は１〜１０原子％であることが好ましく、２〜９原子％であることがより好ましい。 When the carrier a contains other components other than such eluting components, the other components are preferably Ba, Al and Zr and their oxides, and Ba, Al, Zr and Y and their oxides. More preferably. Here, “these oxides” may be Ba, Al, Zr, Y oxides, that is, BaO, Al 2 O 3 , ZrO 2 , Y 2 O 3 , YSZ, etc. It may be a composite oxide such as 12 O 19 or BaZrO 3, or may contain both of these oxides and composite oxides. Here, YSZ means yttria-stabilized zirconia, which is obtained by doping zirconium oxide (ZrO 2 ) with yttrium (Y). The content of Zr in YSZ is preferably 1 to 10 atomic%, and more preferably 2 to 9 atomic%.
担体ａが含んでもよいその他の成分として、アルカリ金属、アルカリ土類、希土類、遷移金属（例えばＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃａ、Ｓｒ、Ｌａ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｎｂ、Ｍｏ、Ｓｉ）が挙げられる。 Other components that the carrier a may contain include alkali metals, alkaline earths, rare earths, transition metals (for example, Li, Na, K, Rb, Cs, Mg, Ca, Sr, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Si).
溶媒と接触して溶出成分を溶出する前の担体ａの平均粒子径（メジアン径）は、０．５〜１５０μｍであることが好ましく、５〜６０μｍであることがより好ましく、１０〜４０μｍであることがより好ましい。
なお、この平均粒子径は、測定対象物（ここでは担体ａ）をヘキサメタリン酸ナトリウム水溶液へ添加し、超音波分散および攪拌によって分散させて、透過率が７０〜９０％となるように調節した後、従来公知のレーザ散乱法（例えばＨＯＲＩＢＡ ＬＡ−９５０Ｖ２）を用いて粒度分布を測定し算出した値を意味するものとする。
本発明において平均粒子径は、特に断りがない限り、このような方法で測定して得た値を意味するものとする。
The average particle diameter (median diameter) of the carrier a before contacting the solvent and eluting the eluted components is preferably 0.5 to 150 μm, more preferably 5 to 60 μm, and more preferably 10 to 40 μm. It is more preferable.
The average particle size is adjusted so that the transmittance is 70 to 90% by adding the object to be measured (here, carrier a) to the sodium hexametaphosphate aqueous solution and dispersing by ultrasonic dispersion and stirring. In addition, it means a value calculated by measuring the particle size distribution using a conventionally known laser scattering method (for example, HORIBA LA-950V2).
In the present invention, the average particle diameter means a value obtained by measurement by such a method unless otherwise specified.
また、溶媒と接触して溶出成分を溶出する前の担体ａの比表面積は、０．１〜２３ｍ2／ｇであることが好ましく、１〜１２ｍ2／ｇであることがより好ましく、０．５〜７ｍ2／ｇであることがより好ましく、０．５〜３ｍ2／ｇであることがさらに好ましい。
なお、比表面積は、次に示す窒素吸着法（ＢＥＴ法）で測定して得た値を意味するものとする。
窒素吸着法について説明する。
まず、測定対象物（ここでは担体ａ）を乾燥させたもの（１．５ｇ）を試料として測定セルに入れ、窒素ガス気流中、２５０℃で４０分間脱ガス処理を行い、その上で試料を窒素３０体積％とヘリウム７０体積％の混合ガス気流中で液体窒素温度に保ち、窒素を試料に平衡吸着させる。次に、上記混合ガスを流しながら試料の温度を徐々に室温まで上昇させ、その間に脱離した窒素の量を検出し、試料の比表面積を測定する。窒素吸着法（ＢＥＴ法）は、例えば従来公知の表面積測定装置を用いて行うことができる。
本発明において比表面積は、特に断りがない限り、ここに示した窒素吸着法（ＢＥＴ法）によって測定した値を意味するものとする。
The specific surface area before the carrier a eluting the contact with component eluted with a solvent is preferably 0.1~23m 2 / g, more preferably 1~12m 2 / g, 0. more preferably 5~7m is 2 / g, still more preferably 0.5-3 m 2 / g.
In addition, specific surface area shall mean the value obtained by measuring with the nitrogen adsorption method (BET method) shown next.
The nitrogen adsorption method will be described.
First, a measurement object (here, carrier a) dried (1.5 g) is placed in a measurement cell as a sample, degassed at 250 ° C. for 40 minutes in a nitrogen gas stream, and the sample is then removed. Liquid nitrogen temperature is maintained in a mixed gas stream of 30% by volume of nitrogen and 70% by volume of helium, and nitrogen is adsorbed on the sample by equilibrium. Next, the temperature of the sample is gradually raised to room temperature while flowing the above mixed gas, the amount of nitrogen desorbed during that time is detected, and the specific surface area of the sample is measured. The nitrogen adsorption method (BET method) can be performed using, for example, a conventionally known surface area measuring device.
In the present invention, the specific surface area means a value measured by the nitrogen adsorption method (BET method) shown here unless otherwise specified.
＜担体ｂ＞
次に、担体ｂについて説明する。
担体ｂは溶出成分を含まない。また、溶出成分の種類は用いる溶媒との関係で決定されるものであるので、例えば溶媒として水を用いる場合、担体ｂは、ＢａＡｌ2Ｏ4、Ａｌ（ＯＨ）3またはＡｌＯＯＨ等の水溶性成分を含まない。
<Carrier b>
Next, the carrier b will be described.
The carrier b does not contain an elution component. In addition, since the type of elution component is determined in relation to the solvent used, for example, when water is used as the solvent, the carrier b is a water-soluble component such as BaAl 2 O 4 , Al (OH) 3, or AlOOH. Not included.
担体ｂは、Ｂａ、ＡｌおよびＺｒならびにこれらの酸化物や、Ｂａ、Ａｌ、ＺｒおよびＹならびにこれらの酸化物を主成分とするものであってよい。
ここで「これらの酸化物」とは、Ｂａ、Ａｌ、Ｚｒ、Ｙの各々の元素の酸化物、すなわちＢａＯ、Ａｌ2Ｏ3、ＺｒＯ2、Ｙ2Ｏ3、ＹＳＺ等であってよく、ＢａＡｌ12Ｏ19、ＢａＺｒＯ3などの複合酸化物であってもよく、これらの酸化物と複合酸化物の両方を含むものであってもよい。
また、ここで主成分とは、含有率が７０質量％以上であることを意味する。具体的には、担体ｂに含まれるＢａ、Ａｌ、ＺｒおよびＹがＢａＯ、Ａｌ2Ｏ3、ＺｒＯ2およびＹ2Ｏ3の態様の酸化物で存在すると仮定して算出した合計含有率は７０質量％以上である。ここで担体ｂに含まれるＢａ、Ａｌ、ＺｒおよびＹの含有率はＩＣＰ発光分光分析装置を用いて測定するものとする。この合計含有率は８０質量％以上であることが好ましく、９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９９質量％以上であることがより好ましく、１００質量％である、すなわち、担体ｂが実質的にＢａ、Ａｌ、ＺｒおよびＹならびにこれらの酸化物からなることがさらに好ましい。ここで「実質的になる」とは、原料や製造過程から不可避的に含まれる不純物は含まれ得ることを意味する。以下に示す本発明の説明において「実質的になる」は、このような意味で用いる。
The carrier b may be composed mainly of Ba, Al, Zr and oxides thereof, Ba, Al, Zr and Y, and oxides thereof.
Here, “these oxides” may be Ba, Al, Zr, Y oxides, that is, BaO, Al 2 O 3 , ZrO 2 , Y 2 O 3 , YSZ, etc. It may be a composite oxide such as 12 O 19 or BaZrO 3, or may contain both of these oxides and composite oxides.
Moreover, a main component means here that a content rate is 70 mass% or more. Specifically, the total content calculated on the assumption that Ba, Al, Zr and Y contained in the support b are present in the oxides of BaO, Al 2 O 3 , ZrO 2 and Y 2 O 3 is 70 It is at least mass%. Here, the contents of Ba, Al, Zr and Y contained in the carrier b are measured using an ICP emission spectroscopic analyzer. The total content is preferably 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, more preferably 99% by mass or more, and 100% by mass. It is further preferred that the carrier b consists essentially of Ba, Al, Zr and Y and their oxides. Here, “substantially” means that impurities inevitably included from the raw materials and the manufacturing process can be included. In the following description of the present invention, “substantially become” is used in this sense.
また、担体ｂは、酸化セリウム、バリウムヘキサアルミネート（ＢａＡｌ12Ｏ19）およびＹＳＺからなる群から選ばれる少なくとも１つを含むものであることが好ましく、これらからなる群から選ばれる少なくとも１つから実質的になることがより好ましい。
担体ｂが酸化セリウムを含む場合、その酸化セリウムは、通常、酸化数が４のＣｅＯ2であるが、酸化数が３のＣｅ2Ｏ3であってもよく、いずれを含んでもよい。
The carrier b preferably contains at least one selected from the group consisting of cerium oxide, barium hexaaluminate (BaAl 12 O 19 ) and YSZ, and is substantially composed of at least one selected from the group consisting of these. More preferably.
When the carrier b contains cerium oxide, the cerium oxide is usually CeO 2 having an oxidation number of 4, but may be Ce 2 O 3 having an oxidation number of 3, or any of them.
担体ｂは、Ｂａ、ＡｌおよびＺｒならびにこれらの酸化物、酸化セリウムならびにＹＳＺ以外に、希土類、遷移金属（例えばＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃａ、Ｓｒ、Ｌａ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｎｂ、Ｍｏ、Ｓｉ）を含んでもよい。 In addition to Ba, Al, and Zr and their oxides, cerium oxide, and YSZ, the support b includes rare earths and transition metals (for example, Li, Na, K, Rb, Cs, Mg, Ca, Sr, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Si).
前記溶出成分が表面に付く前の担体ｂの平均粒子径（メジアン径）は、０．５〜１００μｍであることが好ましく、５〜５０μｍであることがより好ましく、０．５〜１０μｍであることがさらに好ましい。 The average particle diameter (median diameter) of the carrier b before the elution component is attached to the surface is preferably 0.5 to 100 μm, more preferably 5 to 50 μm, and more preferably 0.5 to 10 μm. Is more preferable.
また、前記溶出成分が表面に付く前の担体ｂの比表面積は、０．０５〜２００ｍ2／ｇであることが好ましく、１．５〜１７０ｍ2／ｇであることがより好ましい。 The specific surface area of the carrier b before the elution component is attached to the surface is preferably 0.05~200m 2 / g, more preferably 1.5~170m 2 / g.
＜活性金属＞
次に、活性金属について説明する。活性金属は担体（担体ａ、担体ｂ）の表面に担持している。
<Active metal>
Next, the active metal will be described. The active metal is carried on the surface of the carrier (carrier a, carrier b).
活性金属は触媒能を備える金属であれば特に限定されないが、Ｐｔ、Ｐｄ、Ｒｈ、Ｒｕ、Ｏｓ、Ｉｒ、ＡｕおよびＡｇからなる群から選ばれる少なくとも１つを含むことが好ましい。 The active metal is not particularly limited as long as it has a catalytic ability, but preferably contains at least one selected from the group consisting of Pt, Pd, Rh, Ru, Os, Ir, Au, and Ag.
活性金属の一次粒子の平均粒子径は特に限定されないが、１〜１００ｎｍであることが好ましく、１〜９０ｎｍであることがより好ましい。このような範囲であると容易に製造することができ、また、粒子径が大きすぎる場合と比較して触媒能が高いからである。
活性金属の平均粒子径は、ＴＥＭを用いて拡大写真を得た後、不作為に選んだ数十個の活性金属の直径（投影面積円相当径）を測定し、これを単純平均することで得るものとする。
The average particle diameter of the primary particles of the active metal is not particularly limited, but is preferably 1 to 100 nm, and more preferably 1 to 90 nm. It is because it can manufacture easily with it being such a range, and its catalytic ability is high compared with the case where a particle diameter is too large.
The average particle diameter of the active metal is obtained by measuring the diameter (projected area circle equivalent diameter) of dozens of randomly selected active metals after obtaining an enlarged photograph using TEM and simply averaging the diameters. Shall.
また、担体に担持している活性金属の存在量は、１００質量部の担体に対して０．０１〜２．０質量部であることが好ましく、０．１〜１．０質量部であることがより好ましく、０．１〜０．８質量部であることがさらに好ましい。担体に対して活性金属の量が少なすぎると触媒能が発揮されない傾向があり、逆に多すぎるとコストが高まる割には触媒能が高くならない傾向があるからである。 The amount of the active metal supported on the carrier is preferably 0.01 to 2.0 parts by mass, preferably 0.1 to 1.0 parts by mass with respect to 100 parts by mass of the carrier. Is more preferably 0.1 to 0.8 parts by mass. This is because if the amount of the active metal relative to the support is too small, the catalytic ability tends not to be exhibited, and conversely, if the amount is too large, the catalytic ability tends not to increase for an increase in cost.
＜本発明の排ガス浄化用触媒＞
本発明の排ガス浄化用触媒において前記担体は前記活性金属を表面に担持しており、図１に示したように、さらに担体の表面で固化した溶出由来成分によって、担体の表面に活性金属を固定している。このため活性金属は継続して使用しても凝集し難い。
<Exhaust gas purifying catalyst of the present invention>
In the exhaust gas purifying catalyst of the present invention, the carrier carries the active metal on the surface, and as shown in FIG. 1, the active metal is fixed on the surface of the carrier by elution-derived components solidified on the surface of the carrier. doing. For this reason, the active metal hardly aggregates even if it is continuously used.
また、本発明の排ガス浄化用触媒は、前記溶出成分が前記担体から溶出したものであることが好ましい。本発明の排ガス浄化用触媒における担体は、前記溶出成分を含まないもの（すなわち担体ｂ）からなるものであってよいが、この場合、製造時において、担体ｂの他に、溶出成分を含む材料を用意する必要がある。しかし、前記溶出成分を含む担体（すなわち担体ａ）を用いれば、溶出成分を含む材料を用いる必要がなくなるため（別の言い方をすれば、担体ａが「溶出成分を含む材料」としての機能も果たすため）、製造が容易になるからである。 In the exhaust gas purifying catalyst of the present invention, the eluted component is preferably eluted from the carrier. The carrier in the exhaust gas purifying catalyst of the present invention may be one that does not contain the eluting component (that is, the carrier b). In this case, in production, a material that contains the eluting component in addition to the carrier b. It is necessary to prepare. However, if the carrier containing the eluting component (that is, carrier a) is used, it is not necessary to use a material containing the eluting component (in other words, the carrier a also functions as a “material containing the eluting component”). This is because the manufacturing becomes easier.
本発明の排ガス浄化用触媒の比表面積は、２．５ｍ2／ｇ以上であることが好ましく、２．５〜２００ｍ2／ｇであることがより好ましく、２．５〜１８０ｍ2／ｇであることがより好ましく、２．５〜１７０ｍ2／ｇであることがさらに好ましい。継続して使用してもその触媒能がより長期間、維持されるからである。
なお、比表面積は、前述の窒素吸着法（ＢＥＴ法）で測定して得た値を意味するものとする。
The specific surface area of the exhaust gas purifying catalyst of the present invention is preferably 2.5 m 2 / g or more, more preferably 2.5~200m 2 / g, is 2.5~180m 2 / g Is more preferable, and it is further more preferable that it is 2.5-170 m < 2 > / g. This is because even if it is continuously used, its catalytic ability is maintained for a longer period.
In addition, specific surface area shall mean the value obtained by measuring with the above-mentioned nitrogen adsorption method (BET method).
本発明の排ガス浄化用触媒の平均粒子径（メジアン径）は、０．０５〜１５０μｍであることが好ましく、０．０９〜６０μｍであることがより好ましく、０．０９〜４０μｍであることがより好ましい。なお、この平均粒子径は前述の方法で測定して得た値を意味するものとする。 The average particle diameter (median diameter) of the exhaust gas purifying catalyst of the present invention is preferably 0.05 to 150 μm, more preferably 0.09 to 60 μm, and more preferably 0.09 to 40 μm. preferable. In addition, this average particle diameter shall mean the value obtained by measuring with the above-mentioned method.
本発明の排ガス浄化用触媒において担体は表面に活性金属を有するものであるが、その他に、さらにＴｉ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｙ、Ｚｒ、Ｌａ、Ｃｅ、Ｐｒ、Ｓｉ等を含む粒子等を表面に有してもよい。
ただし、このようなその他のものが、担体の表面に実質的に存在しない、すなわち、原料や製造過程から意図せず混入し、不可避的に存在することになる不純物以外は存在しないことが好ましい。
In the exhaust gas purifying catalyst of the present invention, the carrier has an active metal on the surface, but in addition, Ti, Mn, Fe, Co, Ni, Cu, Y, Zr, La, Ce, Pr, Si, etc. You may have the particle | grains etc. which are included in the surface.
However, it is preferable that such other substances are not substantially present on the surface of the carrier, that is, other than impurities that are inevitably mixed in from the raw materials and the manufacturing process and are inevitably present.
また、本発明の排ガス浄化用触媒は、担体が、前記溶出成分を含む担体ａと前記溶出成分を含まない担体ｂとからなり、前記担体ａから溶出し、前記担体ａの表面で固化した前記溶出成分および／またはこれに由来する成分が、前記担体ａに担持した活性金属を前記担体ａの表面に固定している触媒Ａと、前記担体ａから溶出し、前記担体ｂの表面で固化した前記溶出成分および／またはこれに由来する成分が、前記担体ｂに担持した活性金属を前記担体ｂの表面に固定している触媒Ｂとを含むことが好ましい。 Further, in the exhaust gas purifying catalyst of the present invention, the carrier is composed of the carrier a containing the eluting component and the carrier b not containing the eluting component, and is eluted from the carrier a and solidified on the surface of the carrier a. The elution component and / or the component derived therefrom eluted from the support A with the catalyst A fixing the active metal supported on the support a on the surface of the support a, and solidified on the surface of the support b It is preferable that the eluting component and / or the component derived therefrom include a catalyst B in which an active metal supported on the carrier b is fixed on the surface of the carrier b.
ここで、本発明の排ガス浄化用触媒における触媒Ａおよび触媒Ｂの合計含有率（触媒Ｂを含まない場合は触媒Ａの含有率）が７０質量％以上であることが好ましい。この合計含有率（触媒Ｂを含まない場合は触媒Ａの含有率）は８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることがより好ましく、９９質量％以上であることがより好ましく、１００質量％である、すなわち、本発明の排ガス浄化用触媒が実質的に触媒Ａのみ、または実質的に触媒Ａおよび触媒Ｂからなることがさらに好ましい。 Here, the total content of catalyst A and catalyst B in the exhaust gas purifying catalyst of the present invention (the content of catalyst A when catalyst B is not included) is preferably 70% by mass or more. The total content (content of catalyst A when catalyst B is not included) is preferably 80% by mass or more, more preferably 90% by mass or more, and more preferably 95% by mass or more. 99% by mass or more, more preferably 100% by mass, that is, it is further preferable that the exhaust gas purifying catalyst of the present invention consists essentially of only catalyst A or substantially consists of catalyst A and catalyst B. .
また、本発明の排ガス浄化用触媒は、前記担体ｂが酸化セリウムを主成分とし、前記触媒Ａと前記触媒Ｂとの合計質量に対する前記触媒Ａの質量比（Ａ／（Ａ＋Ｂ）×１００）が１０質量％超８０質量％未満であるものであることが好ましい。この質量比は、２０〜５０質量％であることがより好ましい。
本発明の排ガス浄化用触媒がこのような質量比で触媒Ａおよび触媒Ｂを含む場合、触媒Ａまたは触媒Ｂの単独の場合と比較して、予測できないほど触媒能が優れることを本発明者は見出した。
このように本発明の排ガス浄化用触媒が触媒Ａと酸化セリウムを主成分とする担体ｂを備える触媒Ｂとを特定の比率で含んだ場合に触媒能が非常に優れる理由は、現段階では不明であるが、溶出成分、触媒Ａおよび触媒Ｂの間での相互作用によるものと推定される。
In the exhaust gas purifying catalyst of the present invention, the carrier b is mainly composed of cerium oxide, and the mass ratio of the catalyst A to the total mass of the catalyst A and the catalyst B (A / (A + B) × 100) It is preferable that it is more than 10 mass% and less than 80 mass%. This mass ratio is more preferably 20 to 50% by mass.
When the exhaust gas-purifying catalyst of the present invention contains the catalyst A and the catalyst B at such a mass ratio, the present inventor shows that the catalytic ability is unpredictably superior compared to the case of the catalyst A or the catalyst B alone. I found it.
As described above, the reason why the catalyst performance is so excellent when the exhaust gas purifying catalyst of the present invention includes the catalyst A and the catalyst B including the carrier b mainly composed of cerium oxide in a specific ratio is unknown at this stage. However, it is presumed to be due to the interaction between the eluted component, catalyst A and catalyst B.
本発明の排ガス浄化用触媒は、前記担体ｂがバリウムヘキサアルミネート（ＢａＡｌ12Ｏ19）を主成分とし、前記触媒Ａと前記触媒Ｂとの合計質量に対する前記触媒Ａの質量比（Ａ／（Ａ＋Ｂ）×１００）が５〜５０質量％であるものであることが好ましい。この質量比は、５〜３０質量％であることがより好ましい。
本発明の排ガス浄化用触媒がこのような質量比で触媒Ａおよび触媒Ｂを含む場合、触媒Ａまたは触媒Ｂの単独の場合と比較して、予測できないほど触媒能が優れることを本発明者は見出した。
このように本発明の排ガス浄化用触媒が触媒Ａとバリウムヘキサアルミネートを主成分とする担体ｂを備える触媒Ｂとを特定の比率で含んだ場合に触媒能が非常に優れる理由は、現段階では不明であるが、溶出成分、触媒Ａおよび触媒Ｂの間での相互作用によるものと推定される。
In the exhaust gas purifying catalyst of the present invention, the carrier b is mainly composed of barium hexaaluminate (BaAl 12 O 19 ), and the mass ratio of the catalyst A to the total mass of the catalyst A and the catalyst B (A / ( A + B) × 100) is preferably 5 to 50% by mass. This mass ratio is more preferably 5 to 30% by mass.
When the exhaust gas-purifying catalyst of the present invention contains the catalyst A and the catalyst B at such a mass ratio, the present inventor shows that the catalytic ability is unpredictably superior compared to the case of the catalyst A or the catalyst B alone. I found it.
The reason why the catalyst performance is so excellent when the exhaust gas purifying catalyst of the present invention includes the catalyst A and the catalyst B including the carrier b mainly composed of barium hexaaluminate in a specific ratio is as follows. However, it is estimated that it is due to the interaction between the elution component, catalyst A and catalyst B.
また、本発明の排ガス浄化用触媒は、前記担体ｂがＹＳＺを主成分とし、前記触媒Ａと前記触媒Ｂとの合計質量に対する前記触媒Ａの質量比（Ａ／（Ａ＋Ｂ）×１００）が５〜５０質量％であるものであることが好ましい。この質量比は、５〜３０質量％であることがより好ましい。
本発明の排ガス浄化用触媒がこのような質量比で触媒Ａおよび触媒Ｂを含む場合、触媒Ａまたは触媒Ｂの単独の場合と比較して、予測できないほど触媒能が優れることを本発明者は見出した。
このように本発明の排ガス浄化用触媒が触媒ＡとＹＳＺを主成分とする担体ｂを備える触媒Ｂとを特定の比率で含んだ場合に触媒能が非常に優れる理由は、現段階では不明であるが、溶出成分、触媒Ａおよび触媒Ｂの間での相互作用によるものと推定される。
In the exhaust gas purifying catalyst of the present invention, the carrier b is mainly composed of YSZ, and the mass ratio of the catalyst A to the total mass of the catalyst A and the catalyst B (A / (A + B) × 100) is 5. It is preferable that it is -50 mass%. This mass ratio is more preferably 5 to 30% by mass.
When the exhaust gas-purifying catalyst of the present invention contains the catalyst A and the catalyst B at such a mass ratio, the present inventor shows that the catalytic ability is unpredictably superior compared to the case of the catalyst A or the catalyst B alone. I found it.
As described above, the reason why the catalyst performance is so excellent when the exhaust gas purifying catalyst of the present invention includes the catalyst A and the catalyst B including the carrier b mainly composed of YSZ in a specific ratio is not clear at this stage. It is presumed to be due to the interaction between the elution component, catalyst A and catalyst B.
本発明の排ガス浄化用触媒は、触媒Ａを含み、さらに触媒Ｂを含んでもよいが、その他に含んでもよいものとして、Ｚｒおよびセリウム以外の希土類元素や遷移金属（例えばＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃａ、Ｓｒ、Ｌａ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｎｂ、Ｍｏ、Ｓｉ）の酸化物および複合酸化物が挙げられる。 The exhaust gas purifying catalyst of the present invention includes catalyst A and may further include catalyst B, but may include other rare earth elements and transition metals other than Zr and cerium (for example, Li, Na, K, Rb). Cs, Mg, Ca, Sr, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo , Si) oxides and composite oxides.
＜本発明の排ガス浄化用触媒の製造方法＞
次に、本発明の排ガス浄化用触媒の製造方法について説明する。
本発明の排ガス浄化用触媒の製造方法は特に限定されないが、前記担体の表面に前記活性金属を担持させる担持工程［α］と、前記溶出成分を含む材料および前記活性金属を担持させた前記担体を、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程［α］と、前記溶出成分および／またはこれに由来する成分を前記担体の表面で固化して触媒を得る固化工程［α］とを備える製造方法であることが好ましい。
このような製造方法を、以下では「本発明の触媒の製造方法［α］」ともいう。
<Method for producing exhaust gas purifying catalyst of the present invention>
Next, the manufacturing method of the exhaust gas purifying catalyst of the present invention will be described.
The production method of the exhaust gas purifying catalyst of the present invention is not particularly limited, but the carrying step [α] for carrying the active metal on the surface of the carrier, the material containing the elution component, and the carrier carrying the active metal Is contacted with a solvent that dissolves the eluted component to elute at least a part of the eluted component into the solvent, and the eluted component and / or a component derived therefrom is applied to the surface of the carrier. And a solidification step [α] to obtain a catalyst by solidification with a production method.
Hereinafter, such a production method is also referred to as “a production method of the catalyst of the present invention [α]”.
また、本発明の触媒の製造方法［α］は、前記溶出成分を含む前記担体ａの表面に前記活性金属を担持させる担持工程［β］と、前記活性金属を担持させた前記担体ａを、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程［β］と、前記溶出成分および／またはこれに由来する成分を前記担体ａの表面で固化して触媒Ａを得る固化工程［β］とを備える製造方法であることがより好ましい。
このような製造方法を、以下では「本発明の触媒の製造方法［β］」ともいう。
本発明の触媒の製造方法［β］は本発明の触媒の製造方法［α］の下位概念であるが、本発明の触媒の製造方法［β］が本発明の触媒の製造方法［α］と異なる点は、溶出工程である。具体的には、本発明の触媒の製造方法［α］における溶出工程［α］では、前記溶出成分を含む材料および前記活性金属を担持させた前記担体を用いるが、本発明の触媒の製造方法［β］では、前記溶出成分を含む担体ａを用いる。本発明の触媒の製造方法［β］における溶出工程［β］では、担体ａを用いるので、本発明の触媒の製造方法［α］の溶出工程［α］で用いる「前記溶出成分を含む材料」を用いる必要がない。別の言い方をすれば、本発明の触媒の製造方法［β］の溶出工程［β］で用いる担体ａは、本発明の触媒の製造方法［α］の溶出工程［α］で用いる「前記溶出成分を含む材料」としても機能する。
これ以外の点では、本発明の触媒の製造方法［β］と本発明の触媒の製造方法［α］とは同様であってよい。つまり、本発明の触媒の製造方法［α］における担持工程［α］および固化工程［α］は、本発明の触媒の製造方法［β］における担持工程［β］および固化工程［β］と同様であってよい。
Further, the catalyst production method [α] of the present invention comprises a supporting step [β] for supporting the active metal on the surface of the support a containing the eluting component, and the support a supporting the active metal. An elution step [β] in which the eluted component is brought into contact with a solvent to dissolve the eluted component into the solvent, and the eluted component and / or a component derived from the eluted component on the surface of the carrier a More preferably, the production method comprises a solidification step [β] that solidifies to obtain catalyst A.
Hereinafter, such a production method is also referred to as “a production method of the catalyst of the present invention [β]”.
Although the catalyst production method [β] of the present invention is a subordinate concept of the catalyst production method [α] of the present invention, the catalyst production method [β] of the present invention is different from the catalyst production method [α] of the present invention. The difference is the elution process. Specifically, in the elution step [α] in the catalyst production method [α] of the present invention, the material containing the elution component and the carrier carrying the active metal are used, but the catalyst production method of the present invention is used. In [β], the carrier a containing the elution component is used. Since the carrier a is used in the elution step [β] in the catalyst production method [β] of the present invention, the “material containing the elution component” used in the elution step [α] of the catalyst production method [α] of the present invention. Need not be used. In other words, the carrier a used in the elution step [β] of the production method [β] of the catalyst of the present invention is the same as that used in the elution step [α] of the production method [α] of the catalyst of the present invention. It also functions as a “material containing components”.
In other respects, the catalyst production method [β] of the present invention and the catalyst production method [α] of the present invention may be the same. That is, the supporting step [α] and the solidifying step [α] in the catalyst production method [α] of the present invention are the same as the supporting step [β] and the solidifying step [β] in the catalyst manufacturing method [β] of the present invention. It may be.
また、本発明の触媒の製造方法［α］は、前記溶出成分を含む前記担体ａおよび前記溶出成分を含まない前記担体ｂの各々の表面に前記活性金属を担持させる担持工程［γ］と、前記活性金属を担持させた前記担体ａおよび前記活性金属を担持させた前記担体ｂを、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程［γ］と、前記溶出成分および／またはこれに由来する成分を前記担体ａおよび前記担体ｂの表面で固化して触媒Ａおよび触媒Ｂを得る固化工程［γ］とを備える製造方法であることがより好ましい。
このような製造方法を、以下では「本発明の触媒の製造方法［γ］」ともいう。
本発明の触媒の製造方法［γ］は本発明の触媒の製造方法［α］および本発明の触媒の製造方法［β］の下位概念であるが、本発明の触媒の製造方法［γ］が本発明の触媒の製造方法［α］と異なる点は、担体ａおよび担体ｂを用いる点である。本発明の触媒の製造方法［γ］では、本発明の触媒の製造方法［β］と同様に担体ａを用いるので、本発明の触媒の製造方法［β］の場合と同様に、本発明の触媒の製造方法［α］の溶出工程［α］で用いる「前記溶出成分を含む材料」を用いる必要がない。
これら以外の点では、本発明の触媒の製造方法［γ］と本発明の触媒の製造方法［α］とは同様であってよい。つまり、本発明の触媒の製造方法［α］における担持工程［α］および固化工程［α］は、本発明の触媒の製造方法［γ］における担持工程［γ］および固化工程［γ］と同様であってよい。
Further, the catalyst production method [α] of the present invention comprises a supporting step [γ] for supporting the active metal on the surfaces of the carrier a containing the eluting component and the carrier b not containing the eluting component, An elution step of bringing the carrier a carrying the active metal and the carrier b carrying the active metal into contact with a solvent that dissolves the elution component to elute at least a part of the elution component into the solvent [Γ] and a solidification step [γ] in which the elution component and / or the component derived therefrom is solidified on the surface of the carrier a and the carrier b to obtain the catalyst A and the catalyst B. Is more preferable.
Hereinafter, such a production method is also referred to as “a production method of the catalyst of the present invention [γ]”.
The catalyst production method [γ] of the present invention is a subordinate concept of the catalyst production method [α] of the present invention and the catalyst production method [β] of the present invention. The difference from the production method [α] of the catalyst of the present invention is that the carrier a and the carrier b are used. In the catalyst production method [γ] of the present invention, the carrier a is used in the same manner as in the catalyst production method [β] of the present invention. Therefore, as in the case of the catalyst production method [β] of the present invention, It is not necessary to use the “material containing the elution component” used in the elution step [α] of the catalyst production method [α].
Except for these points, the production method [γ] of the catalyst of the present invention and the production method [α] of the catalyst of the present invention may be the same. That is, the supporting step [α] and the solidifying step [α] in the catalyst production method [α] of the present invention are the same as the supporting step [γ] and the solidifying step [γ] in the catalyst manufacturing method [γ] of the present invention. It may be.
以下では、主として本発明の触媒の製造方法［α］について説明するが、特に断りがない限り、本発明の触媒の製造方法［α］についての説明は、本発明の触媒の製造方法［β］および本発明の触媒の製造方法［γ］についても適用される。
また、特に断りがない限り、担持工程［α］についての説明は、担持工程［β］および担持工程［γ］についても適用される。
また、特に断りがない限り、溶出工程［α］についての説明は、溶出工程［β］および溶出工程［γ］についても適用される。
また、特に断りがない限り、固化工程［α］についての説明は、固化工程［β］および固化工程［γ］についても適用される。
Hereinafter, the production method [α] of the catalyst of the present invention will be mainly described, but unless otherwise specified, the production method [α] of the catalyst of the present invention will be described. The present invention also applies to the catalyst production method [γ] of the present invention.
Unless otherwise specified, the description of the supporting step [α] also applies to the supporting step [β] and the supporting step [γ].
Unless otherwise specified, the description of the elution step [α] also applies to the elution step [β] and the elution step [γ].
Unless otherwise specified, the description of the solidification step [α] is also applied to the solidification step [β] and the solidification step [γ].
＜担持工程［α］＞
本発明の触媒の製造方法［α］における担持工程［α］について説明する。
担持工程［α］は、前記担体の表面に前記活性金属を担持させる工程である。
ここで担持工程［β］では、前記担体ａの表面に前記活性金属を担持させる。
また、担持工程［γ］では、前記担体ａおよび前記担体ｂの表面に前記活性金属を担持させる。
担体の表面に活性金属を担持させる方法は、担体の種類によらず同じであってよい。
<Supporting process [α]>
The supporting step [α] in the catalyst production method [α] of the present invention will be described.
The supporting step [α] is a step of supporting the active metal on the surface of the carrier.
Here, in the supporting step [β], the active metal is supported on the surface of the carrier a.
In the supporting step [γ], the active metal is supported on the surfaces of the carrier a and the carrier b.
The method for supporting the active metal on the surface of the support may be the same regardless of the type of support.
担持工程［α］において用いる担体の製造方法は特に限定されない。 The method for producing the carrier used in the supporting step [α] is not particularly limited.
担体ａの場合、例えば、Ｂａ、ＡｌおよびＺｒからなる群から選ばれる少なくとも１つを含む、粉末状、液状またはそれらを分散もしくは溶解して溶液とした酸化物、水酸化物、硝酸塩、塩化物、酢酸塩、炭酸塩または錯塩の１種類以上を原料として、従来公知の方法（固相混合法、含浸法など）によって、Ｂａ、ＡｌおよびＺｒを含む混合物を得た後、必要に応じて乾燥させ、その後、焼成することで得ることができる。
また、例えば、硝酸塩などの可溶性または液状の原料を用い、これを含む溶液をスプレーノズル等で高温領域に噴霧することで直接、担体aを得ることもできる。これは、例えばホソカワミクロン社製のナノクリエータを用いて行うことができる。
In the case of the carrier a, for example, an oxide, hydroxide, nitrate or chloride containing at least one selected from the group consisting of Ba, Al and Zr, in the form of powder, liquid, or a solution obtained by dispersing or dissolving them. Then, a mixture containing Ba, Al and Zr is obtained by a conventionally known method (solid phase mixing method, impregnation method, etc.) using at least one of acetate, carbonate or complex salt as a raw material, and then dried as necessary. And then calcined.
Further, for example, the carrier a can be obtained directly by using a soluble or liquid raw material such as nitrate and spraying a solution containing the raw material onto a high temperature region with a spray nozzle or the like. This can be performed, for example, using a nano creator manufactured by Hosokawa Micron.
また、担体ａは、Ｂａ、ＡｌおよびＺｒからなる群から選ばれる少なくとも１つを含む１種類以上の前記原料を湿式粉砕してスラリー状の前記原料とした後、必要に応じて乾燥させ、その後、焼成することで得ることが好ましい。湿式粉砕とは、前記原料を水や有機溶媒に浸した状態で分散、粉砕、解砕または混合する方法である。例えば前記原料と水とをボールミルに入れて粉砕等する方法である。
また、湿式粉砕して得た前記スラリー状の原料を噴霧乾燥した後、焼成して担体ａを得ることが好ましい。噴霧乾燥とは、前記スラリー状の原料を噴霧し、霧状とした後または霧状としながら乾燥する方法である。具体的には、前記スラリー状の原料と気体とを流し込むことでノズル先端から乾燥雰囲気内へスラリー状の原料の液滴を吐出させて、粉状の乾燥物を得る方法である。また、乾燥搭の上部から下部へ向かいダウンフローの乾燥ガスを用いて乾燥することが好ましい。また、噴霧乾燥はスプレードライヤーを用いて行うことが好ましい。スプレードライヤーの乾燥用熱風の入口温度は１５０〜３００℃であることが好ましく、１８０〜２２０℃であることがより好ましい。また、出口温度は９０〜１３０℃であることが好ましく、１００〜１２０℃であることがより好ましい。また、噴霧盤の周速は２６〜９２ｍ／ｓｅｃであることが好ましく、７３〜８４ｍ／ｓｅｃであることがより好ましい。
In addition, the carrier a is wet pulverized into at least one kind of the raw material containing at least one selected from the group consisting of Ba, Al, and Zr to obtain the slurry-like raw material, and then dried as necessary. It is preferable to obtain by firing. The wet pulverization is a method of dispersing, pulverizing, pulverizing or mixing the raw materials in a state of being immersed in water or an organic solvent. For example, the raw material and water are put in a ball mill and pulverized.
Further, it is preferable that the slurry-like raw material obtained by wet pulverization is spray-dried and then fired to obtain the carrier a. Spray drying is a method in which the slurry-like raw material is sprayed and made into a mist or dried while being mist. Specifically, the slurry-like raw material and gas are poured to discharge a slurry-like raw material droplet from the nozzle tip into the dry atmosphere, thereby obtaining a powdery dried product. Moreover, it is preferable to dry using the drying gas of a down flow toward the lower part from the upper part of a drying tower. The spray drying is preferably performed using a spray dryer. It is preferable that the inlet temperature of the hot air for drying of a spray dryer is 150-300 degreeC, and it is more preferable that it is 180-220 degreeC. Moreover, it is preferable that outlet temperature is 90-130 degreeC, and it is more preferable that it is 100-120 degreeC. Moreover, it is preferable that the peripheral speed of a spraying board is 26-92 m / sec, and it is more preferable that it is 73-84 m / sec.
また、前記原料またはこれが乾燥した前記乾燥物の焼成は、例えば従来公知の方法で行うことができる。例えば従来公知の焼成炉（トンネル炉、マッフル炉、ロータリーキルン等）を用いて９００〜１６００℃程度の温度で、１〜５０ｈ程度、焼成して、担体ａを得ることができる。 Moreover, the firing of the raw material or the dried product from which the raw material has been dried can be performed by, for example, a conventionally known method. For example, the carrier a can be obtained by firing at a temperature of about 900 to 1600 ° C. for about 1 to 50 hours using a conventionally known firing furnace (a tunnel furnace, a muffle furnace, a rotary kiln or the like).
担体ｂの場合、例えば、Ｃｅを含む、粉末状、液状またはそれらを分散もしくは溶解して溶液とした酸化物、水酸化物、硝酸塩、塩化物、酢酸塩、炭酸塩または錯塩の１種類以上を原料として、従来公知の方法（固相混合法、含浸法など）によって処理した後、必要に応じて乾燥させ、その後、焼成することで得ることができる。焼成は、例えば従来公知の焼成炉を用いて行うことができる。
ここで担体ｂが酸化セリウムを主成分とするものである場合、担体ｂは９００℃以上の雰囲気に曝さないで製造することが好ましい。担体ｂを高温雰囲気に曝すと、本発明の排ガス浄化用触媒の触媒能が高くなり難い傾向があることを本発明者は見出した。
したがって、担体ｂが酸化セリウムを主成分とするものである場合、担体ｂを得る際は、Ｃｅを含む原料を好ましくは９００℃未満の温度、より好ましくは３００〜５００℃の温度、さらに好ましくは４００℃程度の温度で焼成する。
In the case of the carrier b, for example, one or more kinds of oxides, hydroxides, nitrates, chlorides, acetates, carbonates or complex salts containing Ce, powdered, liquid or dispersed or dissolved in solution are used. As a raw material, after processing by a conventionally well-known method (a solid phase mixing method, an impregnation method, etc.), it can be obtained by drying as needed and then firing. Firing can be performed, for example, using a conventionally known firing furnace.
Here, when the carrier b is mainly composed of cerium oxide, the carrier b is preferably produced without being exposed to an atmosphere of 900 ° C. or higher. The present inventor has found that when the carrier b is exposed to a high temperature atmosphere, the catalytic performance of the exhaust gas purifying catalyst of the present invention tends not to be high.
Therefore, when the carrier b is mainly composed of cerium oxide, when obtaining the carrier b, the raw material containing Ce is preferably at a temperature of less than 900 ° C., more preferably at a temperature of 300 to 500 ° C., more preferably Baking at a temperature of about 400 ° C.
担体ｂがＹＳＺまたはＢａＡｌ12Ｏ19の場合も、従来公知の方法で製造することができる。具体的には、担体ｂがＹＳＺの場合は例えば従来公知の固相法によって製造することができる。また、担体ｂがＢａＡｌ12Ｏ19の場合は例えば従来公知のアルコキシド法によって製造することができる。 Even when the carrier b is YSZ or BaAl 12 O 19 , it can be produced by a conventionally known method. Specifically, when the carrier b is YSZ, for example, it can be produced by a conventionally known solid phase method. Further, when the carrier b is BaAl 12 O 19 , it can be produced, for example, by a conventionally known alkoxide method.
担持工程［α］では、上記のようにして得ることができる担体（担体ａおよび／または担体ｂ）の表面に活性金属を担持させる。
前記担体の表面に活性金属を担持させる方法は特に限定されない。例えば従来公知の担持法を用いて活性金属を付けることができる。従来公知の担持法としては、固相混合法、含浸法が挙げられる。具体的には、例えば活性金属を構成する元素の塩を含む溶液（例えばジニトロジアンミン白金溶液）を、粉末状の担体にごくわずかずつ加え、担体表面が均一に濡れはじめた状態で含浸を終了し、その後、乾燥し、焼成することで得ることができる。例えば、従来公知の乾燥機を用いて８０〜２００℃の温度で０．５〜５０ｈ乾燥させた後、従来公知の焼成炉を用いて、空気中にて、３００〜５００℃の温度で０．５〜１０ｈ焼成して得ることができる。活性金属を構成する元素の塩を含む溶液として硝酸根を含むもの（例えばジニトロジアンミン白金溶液）を用いた場合、上記のように乾燥させた後、空気中にて３００〜５００℃の温度で焼成すると、硝酸根の少なくとも一部が除去されるので好ましい。
In the supporting step [α], an active metal is supported on the surface of the carrier (carrier a and / or carrier b) obtained as described above.
The method for supporting the active metal on the surface of the carrier is not particularly limited. For example, the active metal can be applied using a conventionally known supporting method. Conventionally known loading methods include a solid phase mixing method and an impregnation method. Specifically, for example, a solution containing a salt of an element constituting an active metal (for example, dinitrodiammine platinum solution) is added little by little to a powdery carrier, and the impregnation is completed in a state where the surface of the carrier begins to get wet uniformly. Then, it can be obtained by drying and firing. For example, after drying for 0.5 to 50 hours at a temperature of 80 to 200 ° C. using a conventionally known drier, using a conventionally known baking furnace, the temperature is set to 0.00 at a temperature of 300 to 500 ° C. It can be obtained by baking for 5 to 10 hours. When a solution containing a nitrate salt (for example, dinitrodiammine platinum solution) is used as the solution containing the salt of the element constituting the active metal, it is dried as described above and then fired at a temperature of 300 to 500 ° C. in the air. Then, since at least one part of a nitrate radical is removed, it is preferable.
＜溶出工程［α］＞
本発明の触媒の製造方法［α］における溶出工程［α］について説明する。
溶出工程［α］は、前記溶出成分を含む材料および前記活性金属を担持させた前記担体を、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる工程である。
ただし、溶出工程［β］または溶出工程［γ］では、用いる溶出成分を含む担体ａが「前記溶出成分を含む材料」としての役割をも果たすため、「前記溶出成分を含む材料」を用いなくてもよい。
<Elution process [α]>
The elution step [α] in the catalyst production method [α] of the present invention will be described.
In the elution step [α], the material containing the elution component and the carrier carrying the active metal are brought into contact with a solvent that dissolves the elution component to elute at least a part of the elution component into the solvent. It is a process.
However, in the elution step [β] or the elution step [γ], since the carrier a containing the elution component used also serves as “the material containing the elution component”, the “material containing the elution component” is not used. May be.
ここで「前記溶出成分を含む材料」とは、前述の担体ａを構成し得る成分を含む材料であってよい。また、「前記溶出成分を含む材料」は、例えば活性金属を担持していない担体ａそのものであってもよい。 Here, the “material containing the elution component” may be a material containing a component that can constitute the carrier a. In addition, the “material including the elution component” may be, for example, the carrier a that does not carry an active metal.
溶出工程［α］における溶出方法としては、例えば、前記溶出成分を含む材料と前記活性金属を担持させた前記担体とを溶媒に浸す方法が挙げられる。
また、溶出工程［β］の場合であれば、例えば活性金属を表面に付けた担体ａを溶媒に浸す方法が挙げられる。
また、溶出工程［γ］の場合であれば、活性金属を表面に担持させた担体ａと活性金属βを表面に担持させた担体ｂとを、所定の割合（担体ｂが酸化セリウムの場合であれば、本発明の排ガス浄化用触媒の含まれる触媒Ａおよび触媒Ｂの合計質量に対する触媒Ａの質量の比（Ａ／（Ａ＋Ｂ）×１００）が１０質量％超８０質量％未満となる割合）で混合した後、これらを溶媒に浸す方法が挙げられる。
ここで、前記溶出成分を含む材料、担体ａおよび担体ｂの少なくとも１つを、水等の溶媒に浸漬した後、溶媒を十分に攪拌する方法が好ましい。ここで、攪拌は１ｍｉｎ〜１００ｈ行うことが好ましく、５〜１００ｈ行うことがより好ましく、１０〜６０ｈ行うことがより好ましく、２０〜５０ｈ行うことがさらに好ましい。
また、前記溶出成分を含む材料、担体ａおよび担体ｂの少なくとも１つを、水等の溶媒に浸漬した後、水等の溶媒に浸漬した後、ホモジナイザーやビーズミルを用いて粉砕、解砕または混合を行う方法であってもよい。この場合、処理時間は１〜５４０ｍｉｎであることが好ましい。
溶媒としては水や有機溶媒を用いることができ、水を用いることが好ましい。担体ａがＢａＡｌ2Ｏ4を含む場合、溶媒として水を用いることが好ましい。
Examples of the elution method in the elution step [α] include a method of immersing a material containing the elution component and the carrier carrying the active metal in a solvent.
In the case of the elution step [β], for example, a method of immersing the carrier a having an active metal attached to the surface in a solvent can be mentioned.
In the case of the elution step [γ], the carrier a carrying the active metal on the surface and the carrier b carrying the active metal β on the surface are mixed at a predetermined ratio (in the case where the carrier b is cerium oxide). If present, the ratio of the mass of the catalyst A to the total mass of the catalyst A and the catalyst B included in the exhaust gas purifying catalyst of the present invention (a ratio in which A / (A + B) × 100) is more than 10 mass% and less than 80 mass%) And mixing them in a solvent and then immersing them in a solvent.
Here, it is preferable to immerse at least one of the material containing the elution component, the carrier a and the carrier b in a solvent such as water and then sufficiently stir the solvent. Here, stirring is preferably performed for 1 min to 100 h, more preferably 5 to 100 h, more preferably 10 to 60 h, and further preferably 20 to 50 h.
Moreover, after immersing at least one of the material containing the elution component, the carrier a and the carrier b in a solvent such as water, and then immersing in a solvent such as water, the mixture is pulverized, crushed or mixed using a homogenizer or a bead mill. It may be a method of performing. In this case, the processing time is preferably 1 to 540 min.
As the solvent, water or an organic solvent can be used, and water is preferably used. When the support a contains BaAl 2 O 4 , it is preferable to use water as the solvent.
このような溶出工程［α］によって、前記溶出成分を含む材料および／または前記担体ａから前記溶出成分の少なくとも一部を溶媒へ溶出させることができる。 By such an elution step [α], at least a part of the elution component can be eluted from the material containing the elution component and / or the carrier a into the solvent.
＜固化工程［α］＞
本発明の触媒の製造方法［α］における固化工程［α］について説明する。
固化工程［α］は、前記溶出成分および／またはこれに由来する成分を担体の表面で固化して前記触媒を得る工程である。
固化工程［β］の場合であれば、前記溶出成分および／またはこれに由来する成分を前記担体ａの表面で固化して触媒Ａを得る。
固化工程［γ］の場合であれば、前記溶出成分および／またはこれに由来する成分を前記担体ａおよび前記担体ｂの表面で固化して触媒Ａおよび触媒Ｂを得る。
<Solidification process [α]>
The solidification step [α] in the catalyst production method [α] of the present invention will be described.
The solidification step [α] is a step of obtaining the catalyst by solidifying the eluted component and / or a component derived therefrom on the surface of the carrier.
In the case of the solidification step [β], the elution component and / or the component derived therefrom is solidified on the surface of the carrier a to obtain the catalyst A.
In the case of the solidification step [γ], the elution component and / or the component derived therefrom are solidified on the surfaces of the carrier a and the carrier b to obtain catalyst A and catalyst B.
固化工程［α］では、前記溶出工程［α］によって得られたものを、必要に応じて乾燥させた後、焼成することで溶出由来成分を前記担体（担体ａおよび／または担体ｂ）の表面で固化して、前記活性金属を前記担体の表面に固定した触媒を得ることができる。例えば、従来公知の乾燥機を用いて８０〜２００℃の温度で０．５〜５０ｈ乾燥させた後、従来公知の焼成炉を用いて、空気中にて、３００〜５００℃の温度で０．５〜１０ｈ焼成して得ることができる。 In the solidification step [α], the material obtained in the elution step [α] is dried as necessary, and then baked to remove the elution-derived component from the surface of the carrier (carrier a and / or carrier b). By solidifying the catalyst, a catalyst in which the active metal is fixed on the surface of the support can be obtained. For example, after drying for 0.5 to 50 hours at a temperature of 80 to 200 ° C. using a conventionally known drier, using a conventionally known baking furnace, the temperature is set to 0.00 at a temperature of 300 to 500 ° C. It can be obtained by baking for 5 to 10 hours.
＜触媒担持構造体＞
次に、本発明の排ガス浄化用触媒を表面に有する触媒担持構造体について説明する。
この触媒担持構造体は、本発明の排ガス浄化用触媒を構造体の表面に付けてなるものである。ここで構造体としては、セラミックや金属からなるハニカム型、コルゲートタイプ、プレートタイプの構造体が挙げられる。
本発明の排ガス浄化用触媒を表面に有する触媒担持構造体を、以下では「本発明の構造体」ともいう。
<Catalyst carrying structure>
Next, a catalyst carrying structure having the exhaust gas purifying catalyst of the present invention on the surface will be described.
This catalyst supporting structure is formed by attaching the exhaust gas purifying catalyst of the present invention to the surface of the structure. Here, examples of the structure include honeycomb-type, corrugated-type, and plate-type structures made of ceramic or metal.
Hereinafter, the catalyst-supporting structure having the exhaust gas purifying catalyst of the present invention on the surface is also referred to as “the structure of the present invention”.
＜本発明の構造体の製造方法＞
本発明の構造体を製造する方法は特に限定されないが、ウォッシュコート法を好ましく適用することができる。ウォッシュコート法は、本発明の排ガス浄化用触媒を分散媒へ分散させ、必要に応じて粘度を調整して得たスラリー中へ前記構造体を浸漬し、引き上げた後、乾燥し、必要に応じて焼成する方法である。
<The manufacturing method of the structure of this invention>
The method for producing the structure of the present invention is not particularly limited, but a wash coat method can be preferably applied. The wash coat method involves dispersing the exhaust gas purifying catalyst of the present invention in a dispersion medium, immersing the structure in a slurry obtained by adjusting the viscosity as necessary, lifting, drying, and if necessary And firing.
本発明の構造体の製造方法は、前記担体の表面に前記活性金属を担持させる担持工程［α］と、前記溶出成分を含む材料および前記活性金属を担持させた前記担体を、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程［α］と、前記活性金属を担持した前記担体を、前記溶出工程によって得られる前記溶媒とともに構造体と接触させ、その後、前記溶媒を除去することで、前記溶出成分および／またはこれに由来する成分を前記担体の表面で固化し、あわせて前記活性金属を担持した前記担体を前記構造体の表面に付ける付着工程［α］とを備え、本発明の構造体が得られる製造方法であることが好ましい。
このような製造方法を、以下では「本発明の構造体の製造方法［α］」ともいう。
The structure production method of the present invention includes a supporting step [α] for supporting the active metal on the surface of the carrier, a material containing the eluting component, and the carrier supporting the active metal, An elution step [α] in which at least a part of the elution component is eluted into the solvent by contacting with a solvent to be dissolved; and the carrier carrying the active metal, together with the solvent obtained by the elution step, Contacting and then removing the solvent solidifies the elution component and / or a component derived therefrom on the surface of the carrier, and the carrier carrying the active metal on the surface of the structure. It is preferable that it is a manufacturing method provided with the adhesion | attachment process [(alpha)] to attach and the structure of this invention is obtained.
Hereinafter, such a production method is also referred to as “the production method of the structure of the present invention [α]”.
また、本発明の構造体の製造方法［α］は、前記溶出成分を含む前記担体ａの表面に前記活性金属を担持させる担持工程［β］と前記活性金属を担持させた前記担体ａを、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程［β］と、前記活性金属を担持した前記担体ａを、前記溶出工程によって得られる前記溶媒とともに構造体と接触させ、その後、前記溶媒を除去することで、前記溶出成分および／またはこれに由来する成分を前記担体ａの表面で固化し、あわせて前記活性金属を担持した前記担体ａを前記構造体の表面に付ける付着工程［β］とを備え、本発明の構造体が得られる製造方法であることが好ましい。
このような製造方法を、以下では「本発明の構造体の製造方法［β］」ともいう。
本発明の構造体の製造方法［β］は本発明の構造体の製造方法［α］の下位概念であるが、本発明の構造体の製造方法［β］が本発明の構造体の製造方法［α］と異なる点は、溶出工程である。具体的には、本発明の構造体の製造方法［α］における溶出工程［α］では、前記溶出成分を含む材料および前記活性金属を担持させた前記担体を用いるが、本発明の構造体の製造方法［β］では、前記溶出成分を含む担体ａを用いる。本発明の構造体の製造方法［β］における溶出工程［β］では、担体ａを用いるので、本発明の構造体の製造方法［α］の溶出工程［α］で用いる「前記溶出成分を含む材料」を用いる必要がない。別の言い方をすれば、本発明の構造体の製造方法［β］の溶出工程［β］で用いる担体ａは、本発明の構造体の製造方法［α］の溶出工程［α］で用いる「前記溶出成分を含む材料」としても機能する。
これ以外の点では、本発明の構造体の製造方法［β］と本発明の構造体の製造方法［α］とは同様であってよい。つまり、本発明の構造体の製造方法［α］における担持工程［α］および付着工程［α］は、本発明の構造体の製造方法［β］における担持工程［β］および付着工程［β］と同様であってよい。
The structure production method [α] of the present invention includes a supporting step [β] for supporting the active metal on the surface of the support a containing the eluting component and the support a supporting the active metal. The elution step [β] for bringing at least a part of the elution component into the solvent by contacting with the solvent for dissolving the elution component, and the carrier a carrying the active metal is obtained by the elution step. By contacting the structure together with a solvent and then removing the solvent, the eluted component and / or component derived therefrom is solidified on the surface of the carrier a, and the carrier a carrying the active metal together Is preferably attached to the surface of the structure, and the production method can obtain the structure of the present invention.
Hereinafter, such a production method is also referred to as “a method for producing a structure of the present invention [β]”.
The structure manufacturing method [β] of the present invention is a subordinate concept of the structure manufacturing method [α] of the present invention, but the structure manufacturing method [β] of the present invention is a method of manufacturing the structure of the present invention. The difference from [α] is the elution step. Specifically, in the elution step [α] in the production method [α] of the structure of the present invention, the material containing the elution component and the support carrying the active metal are used. In the production method [β], the carrier a containing the elution component is used. In the elution step [β] in the structure production method [β] of the present invention, since the carrier a is used, the “including the elution component” used in the elution step [α] of the structure production method [α] of the present invention is used. There is no need to use "material". In other words, the carrier a used in the elution step [β] of the structure production method [β] of the present invention is used in the elution step [α] of the structure production method [α] of the present invention. It also functions as a “material containing the elution component”.
In other respects, the structure manufacturing method [β] of the present invention and the structure manufacturing method [α] of the present invention may be the same. That is, the supporting step [α] and the attaching step [α] in the structure manufacturing method [α] of the present invention are the same as the supporting step [β] and the attaching step [β] in the structure manufacturing method [β] of the present invention. It may be the same.
また、本発明の構造体の製造方法［α］は、前記溶出成分を含む前記担体ａおよび前記溶出成分を含まない前記担体ｂの各々の表面に前記活性金属を担持させる担持工程［γ］と、前記活性金属を担持させた前記担体ａおよび前記活性金属を担持させた前記担体ｂを、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程［γ］と、前記活性金属を担持した前記担体ａおよび前記担体ｂを、前記溶出工程によって得られる前記溶媒とともに構造体と接触させ、その後、前記溶媒を除去することで、前記溶出成分および／またはこれに由来する成分を前記担体の表面で固化し、あわせて前記活性金属を担持した前記担体ａおよび前記担体ｂを前記構造体の表面に付ける付着工程［γ］とを備え、本発明の構造体が得られる製造方法であることが好ましい。
このような製造方法を、以下では「本発明の構造体の製造方法［γ］」ともいう。
本発明の構造体の製造方法［γ］は本発明の構造体の製造方法［α］および本発明の構造体の製造方法［β］の下位概念であるが、本発明の構造体の製造方法［γ］が本発明の構造体の製造方法［α］と異なる点は、担体ａおよび担体ｂを用いる点である。本発明の構造体の製造方法［γ］では、本発明の構造体の製造方法［β］と同様に担体ａを用いるので、本発明の構造体の製造方法［β］の場合と同様に、本発明の構造体の製造方法［α］の溶出工程［α］で用いる「前記溶出成分を含む材料」を用いる必要がない。
これら以外の点では、本発明の構造体の製造方法［γ］と本発明の構造体の製造方法［α］とは同様であってよい。つまり、本発明の構造体の製造方法［α］における担持工程［α］および付着工程［α］は、本発明の構造体の製造方法［γ］における担持工程［γ］および付着工程［γ］と同様であってよい。
The structure production method [α] of the present invention includes a supporting step [γ] for supporting the active metal on the surfaces of the carrier a containing the eluting component and the carrier b not containing the eluting component. Elution in which the carrier a carrying the active metal and the carrier b carrying the active metal are brought into contact with a solvent that dissolves the elution component to elute at least a part of the elution component into the solvent. The step [γ], the carrier a and the carrier b carrying the active metal, are brought into contact with the structure together with the solvent obtained by the elution step, and then the solvent is removed to remove the elution component and And / or an attaching step [γ] for solidifying a component derived therefrom on the surface of the carrier and attaching the carrier a and the carrier b carrying the active metal to the surface of the structure. It is preferred structure of the present invention is a manufacturing method obtained.
Hereinafter, such a production method is also referred to as “a method for producing a structure of the present invention [γ]”.
The manufacturing method [γ] of the structure of the present invention is a subordinate concept of the manufacturing method [α] of the structure of the present invention and the manufacturing method [β] of the structure of the present invention. [Γ] is different from the manufacturing method [α] of the structure of the present invention in that the carrier a and the carrier b are used. In the structure manufacturing method [γ] of the present invention, since the carrier a is used in the same manner as the structure manufacturing method [β] of the present invention, as in the case of the structure manufacturing method [β] of the present invention, It is not necessary to use the “material containing the elution component” used in the elution step [α] of the structure production method [α] of the present invention.
Except for these points, the structure manufacturing method [γ] of the present invention and the structure manufacturing method [α] of the present invention may be the same. That is, the supporting step [α] and the attaching step [α] in the structure manufacturing method [α] of the present invention are the same as the supporting step [γ] and the attaching step [γ] in the structure manufacturing method [γ] of the present invention. It may be the same.
以下では、主として本発明の構造体の製造方法［α］について説明するが、特に断りがない限り、本発明の構造体の製造方法［α］についての説明は、本発明の構造体の製造方法［β］および本発明の構造体の製造方法［γ］についても適用される。
また、特に断りがない限り、担持工程［α］についての説明は、担持工程［β］および担持工程［γ］についても適用される。
また、特に断りがない限り、溶出工程［α］についての説明は、溶出工程［β］および溶出工程［γ］についても適用される。
また、特に断りがない限り、付着工程［α］についての説明は、付着工程［β］および付着工程［γ］についても適用される。
Hereinafter, the structure manufacturing method [α] of the present invention will be mainly described. Unless otherwise specified, the structure manufacturing method [α] of the present invention will be described in accordance with the structure manufacturing method of the present invention. This also applies to [β] and the manufacturing method [γ] of the structure of the present invention.
Unless otherwise specified, the description of the supporting step [α] also applies to the supporting step [β] and the supporting step [γ].
Unless otherwise specified, the description of the elution step [α] also applies to the elution step [β] and the elution step [γ].
Unless otherwise specified, the description of the attachment step [α] also applies to the attachment step [β] and the attachment step [γ].
本発明の構造体の製造方法［α］について説明する。
本発明の構造体の製造方法［α］における担持工程［α］および溶出工程［α］は、前述の本発明の触媒の製造方法［α］における担持工程［α］および溶出工程［α］と同じである。
本発明の構造体の製造方法［β］における担体工程［β］および溶出工程［β］は、前述の本発明の触媒の製造方法［β］における担持工程［β］および溶出工程［β］と同じである。
本発明の構造体の製造方法［γ］における担体工程［γ］および溶出工程［γ］は、前述の本発明の触媒の製造方法［γ］における担持工程［γ］および溶出工程［γ］と同じである。
The structure production method [α] of the present invention will be described.
The supporting step [α] and the elution step [α] in the structure production method [α] of the present invention are the same as the supporting step [α] and the elution step [α] in the catalyst production method [α] of the present invention described above. The same.
The carrier step [β] and the elution step [β] in the structure production method [β] of the present invention are the same as the supporting step [β] and the elution step [β] in the catalyst production method [β] of the present invention described above. The same.
The carrier step [γ] and the elution step [γ] in the structure production method [γ] of the present invention are the same as the loading step [γ] and the elution step [γ] in the catalyst production method [γ] of the present invention described above. The same.
本発明の構造体の製造方法［α］における付着工程［α］について説明する。
本発明の構造体の製造方法［α］において付着工程［α］は、前記活性金属を担持した前記担体を、前記溶出工程によって得られる前記溶媒とともに構造体と接触させ、その後、前記溶媒を除去することで、前記溶出成分および／またはこれに由来する成分を前記担体の表面で固化し、あわせて前記活性金属を担持した前記担体を前記構造体の表面に付ける工程である。
The adhesion step [α] in the structure production method [α] of the present invention will be described.
In the structure production method [α] of the present invention, the attachment step [α] is performed by bringing the carrier carrying the active metal into contact with the structure together with the solvent obtained by the elution step, and then removing the solvent. Then, the eluting component and / or the component derived therefrom is solidified on the surface of the carrier, and the carrier carrying the active metal is attached to the surface of the structure.
前述のように、溶出工程では、溶出成分を含む材料または活性金属αを表面に付けた担体ａを溶媒に浸すことで、前記溶出成分の少なくとも一部を溶媒へ溶出させることができるが、付着工程では、活性金属を表面に付けた担体を浸した溶媒へ、さらにハニカム型等の構造体を浸し、この構造体を溶媒中から取り出した後、乾燥させ、必要に応じて焼成することで前記溶媒を除去することができる。このようにすることで、前記溶出成分および／またはこれに由来する成分を前記担体の表面で固化し、あわせて前記活性金属を担持した前記担体を前記構造体の表面に付けて触媒担持構造体を製造することができる。 As described above, in the elution step, at least a part of the elution component can be eluted in the solvent by immersing the carrier a having the surface containing the material containing the elution component or the active metal α in the solvent. In the process, a structure such as a honeycomb type is further immersed in a solvent dipped in a support with an active metal attached to the surface, the structure is taken out from the solvent, dried, and fired as necessary. The solvent can be removed. In this way, the elution component and / or the component derived therefrom is solidified on the surface of the support, and the support supporting the active metal is attached to the surface of the structure so as to attach the catalyst support structure. Can be manufactured.
本発明の構造体の製造方法［γ］のように触媒Ａと触媒Ｂとの混合物を表面に付けた触媒担持構造体を製造する場合は、溶出工程［γ］において、活性金属を表面に付けた担体ａとともに、活性金属を表面に付けた担体ｂを溶媒に浸し、そこへさらにハニカム型等の構造体を浸し、この構造体を溶媒中から取り出した後、乾燥させ、必要に応じて焼成することで前記溶媒を除去することができる。このようにすることで、前記溶出成分および／またはこれに由来する成分を前記担体ａおよび前記担体ｂの表面で固化し、あわせて前記活性金属を担持した前記担体ａおよび前記活性金属を担持した前記担体ｂを前記構造体の表面に付けて触媒担持構造体を製造することができる。 When producing a catalyst-supporting structure having a mixture of catalyst A and catalyst B on the surface as in the structure production method [γ] of the present invention, an active metal is attached to the surface in the elution step [γ]. In addition to the carrier a, the carrier b with the active metal on the surface is immersed in a solvent, and further a honeycomb type structure or the like is immersed in the solvent. The structure is taken out from the solvent, dried, and fired as necessary. By doing so, the solvent can be removed. By doing so, the elution component and / or the component derived therefrom are solidified on the surfaces of the carrier a and the carrier b, and the carrier a and the active metal carrying the active metal are also carried. A catalyst supporting structure can be manufactured by attaching the carrier b to the surface of the structure.
このようなハニカム型等の触媒担持構造体を、自動車のエンジンから距離があり比較的低温で使用される触媒またはエンジン近くの高温下で使用される触媒として用いると、例えばガソリン自動車の排ガス中の一酸化炭素（ＣＯ）、未燃炭化水素（ＨＣ）、窒素酸化物（ＮＯX）等を効率よく浄化することができる。 When such a honeycomb-type catalyst-supporting structure is used as a catalyst that is at a distance from an automobile engine and is used at a relatively low temperature or a catalyst that is used at a high temperature near the engine, for example, in the exhaust gas of a gasoline automobile Carbon monoxide (CO), unburned hydrocarbon (HC), nitrogen oxide (NO x ), etc. can be efficiently purified.
＜実験１＞
酸化アルミニウム粉末（和光純薬工業株式会社製、和光特級）２００ｇおよびイットリア安定化ジルコニア（ＹＳＺ）粉末（株式会社高純度化学研究所）７４ｇを、硝酸バリウム水溶液（８％）へ添加し、攪拌した。このような原料に含まれるＢａのすべてが担体においてＢａＡｌ2Ｏ4の態様になるとすると、担体に含まれるＢａＡｌ2Ｏ4の含有率は５４質量％と算出される。したがって、担体は実質的にＢａＡｌ2Ｏ4からなると考えられる。
次に、これを循環方式湿式粉砕機（ＬＡＢＳＴＡＲ、アシザワ・ファインテック社製）を用いて湿式粉砕し、スラリーを得た。ここで湿式粉砕の条件は、回転数：２４８０ｒｐｍ、循環量：１Ｌ／ｍｉｎ、粉砕時間：２０分とした。また、粉砕にはビーズ径１ｍｍのジルコニアビーズ４５５ｃｃを用いた。
次に、循環方式湿式粉砕機から得られたスラリーを回収し、スプレードライヤーの１つである噴霧造粒乾燥装置(大川原化工機株式会社製、商品名：ＬＢ−８型)を用いて乾燥し、乾燥粉体を得た。ここで、乾燥装置の入口温度を２００℃、出口温度を１１０℃、噴射盤の周速を７９ｍ／ｓｅｃとした。
次に、噴霧造粒乾燥装置で得られた乾燥粉体をマッフル炉で、大気雰囲気下、１５００℃で１０時間かけて焼成し、担体を得た。
<Experiment 1>
200 g of aluminum oxide powder (manufactured by Wako Pure Chemical Industries, Ltd., Wako Special Grade) and 74 g of yttria-stabilized zirconia (YSZ) powder (High Purity Chemical Laboratory Co., Ltd.) were added to an aqueous barium nitrate solution (8%) and stirred. . Assuming that all of Ba contained in such a raw material is in the form of BaAl 2 O 4 in the support, the content of BaAl 2 O 4 contained in the support is calculated to be 54% by mass. Therefore, it is considered that the carrier is substantially composed of BaAl 2 O 4 .
Next, this was wet pulverized using a circulation type wet pulverizer (LABSTAR, manufactured by Ashizawa Finetech) to obtain a slurry. Here, the conditions of the wet pulverization were as follows: rotation speed: 2480 rpm, circulation rate: 1 L / min, and pulverization time: 20 minutes. For pulverization, 455 cc of zirconia beads having a bead diameter of 1 mm was used.
Next, the slurry obtained from the circulation type wet pulverizer is recovered and dried using a spray granulation drying apparatus (trade name: LB-8, manufactured by Okawara Kako Co., Ltd.) which is one of spray dryers. A dry powder was obtained. Here, the inlet temperature of the drying apparatus was 200 ° C., the outlet temperature was 110 ° C., and the peripheral speed of the spray plate was 79 m / sec.
Next, the dried powder obtained by the spray granulation drying apparatus was baked in an air atmosphere at 1500 ° C. for 10 hours in a muffle furnace to obtain a carrier.
次に、得られた担体（１００ｇ）にジニトロジアンミン白金溶液（８．５％濃度、４．７ｇ）をごくわずかずつ添加し、その後、１５０℃、常圧下で一晩乾燥した後、４００℃、常圧下で３ｈ焼成し、活性金属が担持した担体を得た。 Next, dinitrodiammine platinum solution (8.5% concentration, 4.7 g) was added little by little to the obtained carrier (100 g), and then dried at 150 ° C. under normal pressure overnight, then at 400 ° C., Firing was carried out under normal pressure for 3 hours to obtain a carrier carrying an active metal.
そして、このうちの８０ｇをイオン交換水（常温）へ添加し、マグネティックスラーターで攪拌しながら４８時間保持した。
その後、溶液を１５０℃、常圧下で一晩乾燥した後、４００℃、常圧下で３ｈ焼成して触媒を得た。得られた触媒を、以下では触媒［１］ともいう。
And 80g of these was added to ion-exchange water (normal temperature), and it was hold | maintained for 48 hours, stirring with a magnetic slurter.
Thereafter, the solution was dried overnight at 150 ° C. under normal pressure and then calcined at 400 ° C. under normal pressure for 3 hours to obtain a catalyst. Hereinafter, the obtained catalyst is also referred to as catalyst [1].
そして、触媒［１］の比表面積を窒素吸着法（ＢＥＴ法）によって測定した。具体的な方法は前述の通りである。なお、表面積測定装置として、株式会社マウンテック Macsorb HM model 1220を用いた。
その結果、触媒の比表面積は５３ｍ2／ｇであった。
And the specific surface area of the catalyst [1] was measured by the nitrogen adsorption method (BET method). The specific method is as described above. As a surface area measuring apparatus, Mountec Macsorb HM model 1220 was used.
As a result, the specific surface area of the catalyst was 53 m 2 / g.
また、触媒［１］の粒度分布を測定した。具体的には、触媒［１］をヘキサメタリン酸ナトリウム水溶液へ添加し、超音波分散および攪拌によって分散させて、透過率が７０〜９０％となるように調節した後、レーザ散乱法（ＨＯＲＩＢＡ ＬＡ−９５０Ｖ２）を用いて粒度分布を測定した。その結果、平均粒子径（メジアン径）は１０μｍ以下であった。 Further, the particle size distribution of the catalyst [1] was measured. Specifically, the catalyst [1] is added to an aqueous solution of sodium hexametaphosphate, dispersed by ultrasonic dispersion and stirring, and adjusted to have a transmittance of 70 to 90%, and then laser scattering (HORIBA LA- 950V2) was used to measure the particle size distribution. As a result, the average particle diameter (median diameter) was 10 μm or less.
また、触媒［１］におけるＰｔの含有量をＩＣＰ発光分光分析装置を用いて測定したところ、担体の１００質量部に対して０．４質量部であった。なお、触媒［１］における担体の組成は、ジニトロジアンミン白金溶液へ添加する前と同一であった。 Moreover, when the content of Pt in the catalyst [1] was measured using an ICP emission spectroscopic analyzer, it was 0.4 parts by mass with respect to 100 parts by mass of the carrier. In addition, the composition of the carrier in the catalyst [1] was the same as before the addition to the dinitrodiammine platinum solution.
また、触媒［１］をＴＥＭ−ＥＤＸ分析に供し、ＴＥＭ写真を得た。図２に示す。なお、図２（ａ）は当該ＴＥＭ写真であり、図２（ｂ）は図２（ａ）のＴＥＭ写真を模写して図形化したものである。
図２より、活性金属であるＰｔ粒子（１２）の一部分（半分程度）が、ＢａＡｌ2Ｏ4またはＢａＡｌ2Ｏ4に由来する成分である溶出由来成分（１４）からなる層に埋もれており、ＢａＡｌ2Ｏ4がＰｔ粒子（１２）を担体（１６）の表面に固定していることを確認することができた。
Further, the catalyst [1] was subjected to TEM-EDX analysis to obtain a TEM photograph. As shown in FIG. 2A is the TEM photograph, and FIG. 2B is a copy of the TEM photograph shown in FIG. 2A.
From FIG. 2, a part (about half) of the Pt particles (12), which is an active metal, is buried in a layer composed of an elution-derived component (14) that is a component derived from BaAl 2 O 4 or BaAl 2 O 4 . It was confirmed that BaAl 2 O 4 fixed the Pt particles (12) to the surface of the carrier (16).
次に、ＹＳＺからなる担体を用意した。そして、担体（１００ｇ）にジニトロジアンミン白金溶液（８．５％濃度、４．７ｇ）をごくわずかずつ添加し、その後、１５０℃、常圧下で一晩乾燥した後、４００℃、常圧下で３ｈ焼成し、Ｐｔが担体に担持した触媒を得た。得られた触媒を、以下では触媒［２］ともいう。
そして、触媒［２］におけるＰｔの含有量をＩＣＰ発光分光分析装置を用いて測定したところ、担体の１００質量部に対して０．４質量部であった。なお、触媒［２］の組成は、ジニトロジアンミン白金溶液へ添加する前と同一であった。
また、触媒［２］の粒度分布を触媒［１］と同様の方法で測定したところ、平均粒子径（メジアン径）は０．０９μｍであった。
Next, a carrier made of YSZ was prepared. Then, a dinitrodiammine platinum solution (8.5% concentration, 4.7 g) was added little by little to the carrier (100 g), and then dried overnight at 150 ° C. under normal pressure, and then at 400 ° C. under normal pressure for 3 hours. Firing was performed to obtain a catalyst in which Pt was supported on a carrier. Hereinafter, the obtained catalyst is also referred to as catalyst [2].
And when content of Pt in catalyst [2] was measured using the ICP emission-spectral-analysis apparatus, it was 0.4 mass part with respect to 100 mass parts of a support | carrier. The composition of the catalyst [2] was the same as before the addition to the dinitrodiammine platinum solution.
Further, when the particle size distribution of the catalyst [2] was measured by the same method as that for the catalyst [1], the average particle size (median size) was 0.09 μm.
次に、触媒［１］および［２］について、各々４０ｇをイオン交換水（１１９ｇ）およびバインダーとともにバッチ式ボールミルを用いて湿式粉砕し、スラリーを得た。バインダーとしてはベーマイトを用い、ベーマイトの添加量は触媒１００質量部に対して１０質量部とした。また、湿式粉砕は回転数を１００ｒｐｍとし、粉砕時間は、スラリー中の固形分のメジアン径が２０μｍ程度以下となるように、５〜５４０分で調整した。また、ビーズ径５ｍｍのジルコニアビーズ２１０ｃｃを用いた。このような処理を施して固形分濃度が２７質量％のスラリーを２個得た。次に、各々のスラリーへコージェライト製のセラミックハニカム構造体（体積５．３ｃｍ3、４００ｃｅｌｌｓ／ｉｎｃｈ2）を浸漬し、３分放置した後、引き上げ、１５０℃で１ｈ乾燥した後、４００℃で３ｈ焼成する方法（ウォッシュコート法）によって、表面に触媒［１］または触媒［２］を備える触媒担持構造体を得た。触媒［１］を表面に備える触媒担持構造体を構造体［１］とし、同様に、触媒［２］を表面に備える触媒担持構造体を構造体［２］とした。
構造体［１］および［２］は、同じものを２個ずつ作製した。
Next, 40 g of each of the catalysts [1] and [2] was wet-ground using a batch type ball mill together with ion-exchanged water (119 g) and a binder to obtain a slurry. Boehmite was used as the binder, and the amount of boehmite added was 10 parts by mass with respect to 100 parts by mass of the catalyst. The wet pulverization was performed at a rotational speed of 100 rpm, and the pulverization time was adjusted in 5 to 540 minutes so that the median diameter of the solid content in the slurry was about 20 μm or less. Further, 210 cc of zirconia beads having a bead diameter of 5 mm was used. By performing such treatment, two slurries having a solid content concentration of 27% by mass were obtained. Next, a cordierite ceramic honeycomb structure (volume 5.3 cm 3 , 400 cells / inch 2 ) was immersed in each slurry, left for 3 minutes, pulled up, dried at 150 ° C. for 1 h, and then dried at 400 ° C. A catalyst-supporting structure having a catalyst [1] or a catalyst [2] on the surface was obtained by a method (wash coat method) of firing for 3 h. The catalyst supporting structure having the catalyst [1] on the surface was designated as the structure [1], and similarly, the catalyst supporting structure comprising the catalyst [2] on the surface was designated as the structure [2].
Two identical structures [1] and [2] were produced.
次に、２個の構造体［１］のうちの１個について、９００℃に調整したマッフル炉中（常圧下）に３０ｈ保持し、耐久処理（強制劣化加速処理）を施した。構造体［１］に耐久処理を施したものを、構造体［１０］とした。そして、同様に、構造体［２］についても耐久処理を施して、構造体［２０］を得た。 Next, one of the two structures [1] was held in a muffle furnace (under normal pressure) adjusted to 900 ° C. for 30 hours and subjected to durability treatment (forced deterioration acceleration treatment). The structure [10] was obtained by subjecting the structure [1] to durability treatment. Similarly, the structure [2] was subjected to durability treatment to obtain a structure [20].
このようにして構造体［１］および［２］ならびに構造体［１０］および［２０］の４個の構造体を得た。 In this way, four structures, ie, structures [1] and [2] and structures [10] and [20] were obtained.
次に、４個の構造体の各々について、常圧流通式の試験装置を用いてプロピレン転化率５０％の温度（Ｔ50）の測定を行った。具体的には、試験装置のホルダーに構造体を１つセットし、ここへモデルガスを空間速度５０，０００ｈ-1で通過させた。ホルダーにはヒータが設けられており、このヒータによって構造体の温度を１５０℃から６５０℃へ徐々に上昇させた。そして、モデルガス中のプロピレン浄化率が５０％となったときの温度を測定し、これを各構造体におけるＴ50とした。
ここで、モデルガスの組成は、Ｃ3Ｈ6：１６００ｐｐｍ、ＮＯ：１０００ｐｐｍ、ＣＯ：０．６％、Ｈ2：０．２％、Ｏ2：０．６％、Ｈ2Ｏ：１０．０％、Ｎ2：残部（すべて体積比率）であり、理論空気比は１４．７とした。
また、プロピレン浄化率は次の式により求めるものとし、この式によって算出されるプロピレン浄化率が５０％となる温度をＴ50とした。なお、この式におけるすべての濃度は体積濃度を意味する。
Next, the temperature (T 50 ) at a propylene conversion rate of 50% was measured for each of the four structures using a normal pressure flow type test apparatus. Specifically, one structure was set in the holder of the test apparatus, and the model gas was passed therethrough at a space velocity of 50,000 h −1 . The holder was provided with a heater, and the temperature of the structure was gradually increased from 150 ° C. to 650 ° C. by the heater. Then, the temperature at which the propylene purification rate of the model gas became 50% was determined, which was used as T 50 in each structure.
Here, the composition of the model gas is: C 3 H 6 : 1600 ppm, NO: 1000 ppm, CO: 0.6%, H 2 : 0.2%, O 2 : 0.6%, H 2 O: 10.0 %, N 2 : remainder (all volume ratios), and the theoretical air ratio was 14.7.
Further, the propylene purification rate shall be determined by the following equation, the temperature at which the propylene purification rate calculated by this equation becomes 50% was T 50. Note that all concentrations in this formula mean volume concentrations.
プロピレン浄化率＝（構造体入口のＣ3Ｈ6濃度−構造体出口のＣ3Ｈ6濃度）／構造体入口のＣ3Ｈ6濃度×１００ ・・・・式（Ｉ） Propylene purification ratio = (C 3 H 6 concentration of the structure inlet - structure outlet C 3 H 6 concentration) / structure inlet of C 3 H 6 concentration × 100 · · · · formula (I)
測定して求めた構造体［２］におけるＴ50を、構造体［１］のＴ50に対する相対値（構造体［１］のＴ50を１００とする相対値）として第１表に示す。同様に、測定して求めた構造体［２０］におけるＴ50を、構造体［１０］のＴ50に対する相対値（構造体［１０］のＴ50を１００とする相対値）として第１表に示す。 The T 50 in the structure [2] obtained by measurement is shown in Table 1 as a relative value to the T 50 of the structure [1] (relative value where the T 50 of the structure [1] is 100). Similarly, T 50 in structure [20] obtained by measurement is shown in Table 1 as a relative value to T 50 of structure [10] (relative value where T 50 of structure [10] is 100). Show.
第１表より、本発明の排ガス浄化用触媒に相当する触媒［１］を用いた本発明の構造体に相当する構造体［１］およびそれを耐久処理した構造体［１０］は、本発明の構造体に相当しない構造体［２］およびそれを耐久処理した構造体［２０］と比較して、Ｔ50が低く、触媒能に優れることが確認できた。 From Table 1, the structure [1] corresponding to the structure of the present invention using the catalyst [1] corresponding to the exhaust gas purifying catalyst of the present invention and the structure [10] obtained by subjecting it to the endurance treatment are shown in the present invention. Compared with the structure [2] not corresponding to the structure [2] and the structure [20] obtained by subjecting it to durability treatment, it was confirmed that T 50 was low and the catalytic ability was excellent.
＜実験２＞
酸化アルミニウム粉末（和光純薬工業株式会社製、和光特級）２００ｇおよびイットリア安定化ジルコニア（ＹＳＺ）粉末（株式会社高純度化学研究所）８５ｇを、硝酸バリウム水溶液（６％）へ添加し、攪拌した。なお、このような原料に含まれるＢａのすべてが担体ａ1においてＢａＡｌ2Ｏ4の態様になるとすると、担体に含まれるＢａＡｌ2Ｏ4の含有率は３０質量％と算出される。したがって、担体ａ1はＢａＡｌ2Ｏ4とＢａＡｌ12Ｏ19とが混在しているものと考えられる。
次に、これを循環方式湿式粉砕機（ＬＡＢＳＴＡＲ、アシザワ・ファインテック社製）を用いて湿式粉砕し、スラリーを得た。ここで湿式粉砕の条件は、回転数：２４８０ｒｐｍ、循環量：１Ｌ／ｍｉｎ、粉砕時間：２０分とした。また、粉砕にはビーズ径１ｍｍのジルコニアビーズ４５５ｃｃを用いた。
次に、循環方式湿式粉砕機から得られたスラリーを回収し、スプレードライヤーの１つである噴霧造粒乾燥装置(大川原化工機株式会社製、商品名：ＬＢ−８型)を用いて乾燥し、乾燥粉体を得た。ここで、乾燥装置の入口温度を２００℃、出口温度を１１０℃、噴射盤の周速を７９ｍ／ｓｅｃとした。
次に、噴霧造粒乾燥装置で得られた乾燥粉体をマッフル炉で、大気雰囲気下、１５００℃で１０時間かけて焼成し、担体ａ1を得た。
担体ａ1の組成を蛍光Ｘ線分析装置を用いて測定したところ、ＢａＯ：２０質量％、Ａｌ2Ｏ3：４３質量％、Ｙ２Ｏ３：４．８質量％、ＺｒＯ２：３１質量％であった。
<Experiment 2>
200 g of aluminum oxide powder (manufactured by Wako Pure Chemical Industries, Ltd., Wako Special Grade) and 85 g of yttria-stabilized zirconia (YSZ) powder (High Purity Chemical Laboratory Co., Ltd.) were added to an aqueous barium nitrate solution (6%) and stirred. . If all of Ba contained in such a raw material is in the form of BaAl 2 O 4 in the carrier a 1 , the content of BaAl 2 O 4 contained in the carrier is calculated to be 30% by mass. Therefore, it is considered that the carrier a 1 is a mixture of BaAl 2 O 4 and BaAl 12 O 19 .
Next, this was wet pulverized using a circulation type wet pulverizer (LABSTAR, manufactured by Ashizawa Finetech) to obtain a slurry. Here, the conditions of the wet pulverization were as follows: rotation speed: 2480 rpm, circulation rate: 1 L / min, and pulverization time: 20 minutes. For pulverization, 455 cc of zirconia beads having a bead diameter of 1 mm was used.
Next, the slurry obtained from the circulation type wet pulverizer is recovered and dried using a spray granulation drying apparatus (trade name: LB-8, manufactured by Okawara Kako Co., Ltd.) which is one of spray dryers. A dry powder was obtained. Here, the inlet temperature of the drying apparatus was 200 ° C., the outlet temperature was 110 ° C., and the peripheral speed of the spray plate was 79 m / sec.
Next, the dried powder obtained by the spray granulation dryer was baked in a muffle furnace at 1500 ° C. for 10 hours in an air atmosphere to obtain a carrier a 1 .
When the composition of the carrier a 1 was measured using a fluorescent X-ray analyzer, BaO: 20 mass%, Al 2 O 3 : 43 mass%, Y 2 O 3 : 4.8 mass%, ZrO 2 : 31 mass% Met.
次に、得られた担体ａ1（１００ｇ）にジニトロジアンミン白金溶液（８．５％濃度、４．７ｇ）をごくわずかずつ添加し、その後、１５０℃、常圧下で一晩乾燥した後、４００℃、常圧下で３ｈ焼成し、Ｐｔが担持した担体ａ1を得た。
そして、Ｐｔが担持した担体ａ1におけるＰｔの含有量をＩＣＰ発光分光分析装置を用いて測定したところ、担体ａ1の１００質量部に対して０．４質量部であった。なお、Ｐｔが担持した担体ａ1の組成は、ジニトロジアンミン白金溶液へ添加する前と同一であった。
Next, dinitrodiammine platinum solution (8.5% concentration, 4.7 g) was added little by little to the obtained carrier a 1 (100 g), and then dried overnight at 150 ° C. under normal pressure. The carrier a 1 carrying Pt was obtained by calcining at 0 ° C. under normal pressure for 3 hours.
And when the content of Pt in the carrier a 1 carrying Pt was measured using an ICP emission spectroscopic analyzer, it was 0.4 parts by mass with respect to 100 parts by mass of the carrier a 1 . The composition of the carrier a 1 carrying Pt was the same as that before the addition to the dinitrodiammine platinum solution.
また、Ｐｔが担持した担体ａ1の粒度分布を測定した。具体的には、Ｐｔが担持した担体ａ1をヘキサメタリン酸ナトリウム水溶液へ添加し、超音波分散および攪拌によって分散させて、透過率が７０〜９０％となるように調節した後、レーザ散乱法（ＨＯＲＩＢＡ ＬＡ−９５０Ｖ２）を用いて粒度分布を測定した。
その結果、平均粒子径（メジアン径）は１４μｍであった。
Further, the particle size distribution of the carrier a 1 carrying Pt was measured. Specifically, Pt-supported carrier a 1 is added to an aqueous sodium hexametaphosphate solution and dispersed by ultrasonic dispersion and stirring to adjust the transmittance to be 70 to 90%. The particle size distribution was measured using HORIBA LA-950V2).
As a result, the average particle diameter (median diameter) was 14 μm.
次に、酸化セリウムの粉末（株式会社高純度化学研究所、ＣｅＯ2：約８０質量％）を担体ｂ1とし、この１００ｇにジニトロジアンミン白金溶液（８．５％濃度、４．７ｇ）をごくわずかずつ添加し、その後、１５０℃、常圧下で一晩乾燥した後、４００℃、常圧下で３ｈ焼成し、Ｐｔが担持した担体ｂ1を得た。
そして、Ｐｔが担持した担体ｂ1におけるＰｔの含有量をＩＣＰ発光分光分析装置を用いて測定したところ、担体ｂ1の１００質量部に対して０．４質量部であった。なお、Ｐｔが担持した担体ｂ1の組成は、ジニトロジアンミン白金溶液へ添加する前と同一であった。
また、Ｐｔが担持した担体ｂ1の粒度分布をＰｔが担持した担体ａ1の場合と同様の方法で測定したところ、平均粒子径（メジアン径）は５．５μｍであった。
Next, cerium oxide powder (High Purity Chemical Laboratory Co., Ltd., CeO 2 : about 80% by mass) is used as the carrier b 1, and dinitrodiammine platinum solution (8.5% concentration, 4.7 g) is added to 100 g of this powder. After adding little by little, it was dried overnight at 150 ° C. under normal pressure and then calcined at 400 ° C. under normal pressure for 3 hours to obtain a carrier b 1 carrying Pt.
And when the content of Pt in the carrier b 1 carrying Pt was measured using an ICP emission spectroscopic analyzer, it was 0.4 parts by mass with respect to 100 parts by mass of the carrier b 1 . The composition of the carrier b 1 supported by Pt was the same as that before the addition to the dinitrodiammine platinum solution.
Further, when the particle size distribution of the carrier b 1 carrying Pt was measured by the same method as in the case of the carrier a 1 carrying Pt, the average particle diameter (median diameter) was 5.5 μm.
次に、Ｐｔが担持した担体ａ1とＰｔが担持した担体ｂ1とを混合して混合物を得た。ここで混合比は６通りとし、６個の混合物を得た。具体的には、Ｐｔが担持した担体ａ1とＰｔが担持した担体ｂ1との混合比（質量比）は、１００／０、８０／２０、５０／５０、２０／８０、１０／９０、０／１００とし、各々を混合物［１１］〜［１６］とした。 Next, the carrier a 1 carrying Pt and the carrier b 1 carrying Pt were mixed to obtain a mixture. Here, the mixing ratio was set to 6 to obtain 6 mixtures. Specifically, the mixing ratio (mass ratio) of the carrier a 1 carrying Pt and the carrier b 1 carrying Pt is 100/0, 80/20, 50/50, 20/80, 10/90, 0/100, each of which was a mixture [11] to [16].
次に、各々の混合物の８０ｇをイオン交換水（常温）へ添加し、マグネティックスラーターで一晩攪拌した。その後、溶液中から固形分を取り出し、その固形分を１５０℃、常圧下で一晩乾燥した後、４００℃、常圧下で３ｈ焼成し、本発明の排ガス浄化用触媒に相当する触媒［１１］〜［１６］を得た。 Next, 80 g of each mixture was added to ion-exchanged water (at room temperature) and stirred overnight with a magnetic slurter. Thereafter, the solid content is taken out from the solution, and the solid content is dried at 150 ° C. and normal pressure overnight, and then calcined at 400 ° C. and normal pressure for 3 hours, and the catalyst corresponding to the exhaust gas purifying catalyst of the present invention [11] To [16].
次に、触媒［１１］〜［１６］について、各々４０ｇをイオン交換水（１１９ｇ）およびバインダーとともにバッチ式ボールミルを用いて湿式粉砕し、スラリーを得た。バインダーとしてはベーマイトを用い、ベーマイトの添加量は触媒１００質量部に対して１０質量部とした。また、湿式粉砕は回転数を１００ｒｐｍとし、粉砕時間は、スラリー中の固形分のメジアン径が２０μｍ程度以下となるように、５〜４０分で調整した。また、ビーズ径５ｍｍのジルコニアビーズ２１０ｃｃを用いた。このような処理を施して固形分濃度が２７質量％のスラリーを６個得た。次に、各々のスラリーへコージェライト製のセラミックハニカム構造体（体積５．３ｃｍ3、４００ｃｅｌｌｓ／ｉｎｃｈ2）を浸漬し、３分放置した後、引き上げ、１５０℃で１ｈ乾燥した後、４００℃で３ｈ焼成する方法（ウォッシュコート法）によって、表面に本発明の排ガス浄化用触媒を備える触媒担持構造体を得た。触媒［１１］を表面に備える触媒担持構造体を構造体［１１］とし、同様に、触媒［１２］〜［１６］の各々を表面に備える触媒担持構造体を構造体［１２］〜［１６］とした。
構造体［１１］〜［１６］は、同じものを２個ずつ作製した。
Next, 40 g of each of the catalysts [11] to [16] was wet-ground using a batch type ball mill together with ion-exchanged water (119 g) and a binder to obtain a slurry. Boehmite was used as the binder, and the amount of boehmite added was 10 parts by mass with respect to 100 parts by mass of the catalyst. In addition, the wet pulverization was performed at a rotation speed of 100 rpm, and the pulverization time was adjusted in 5 to 40 minutes so that the median diameter of the solid content in the slurry was about 20 μm or less. Further, 210 cc of zirconia beads having a bead diameter of 5 mm was used. By performing such treatment, six slurries having a solid content concentration of 27% by mass were obtained. Next, a cordierite ceramic honeycomb structure (volume 5.3 cm 3 , 400 cells / inch 2 ) was immersed in each slurry, left for 3 minutes, pulled up, dried at 150 ° C. for 1 h, and then dried at 400 ° C. A catalyst-supporting structure having the exhaust gas purifying catalyst of the present invention on the surface was obtained by a method (wash coat method) of firing for 3 hours. The catalyst supporting structure including the catalyst [11] on the surface is referred to as the structure [11]. Similarly, the catalyst supporting structures including the catalysts [12] to [16] on the surface are the structures [12] to [16. ].
Two identical structures [11] to [16] were produced.
次に、２個の構造体［１１］のうちの１個について、９００℃に調整したマッフル炉中（常圧下）に３０ｈ保持し、耐久処理（強制劣化加速処理）を施した。構造体［１１］に耐久処理を施したものを、構造体［１１０］とした。そして、同様に、構造体［１２］〜［１６］についても耐久処理を施して、構造体［１２０］〜［１６０］を得た。 Next, one of the two structures [11] was held in a muffle furnace (under normal pressure) adjusted to 900 ° C. for 30 hours and subjected to durability treatment (forced deterioration acceleration treatment). The structure [11] was obtained by subjecting the structure [11] to durability treatment. In the same manner, the structures [12] to [16] were subjected to durability treatment to obtain structures [120] to [160].
このようにして構造体［１１］〜［１６］および構造体［１１０］〜［１６０］の１２個の構造体を得た。 In this way, twelve structures of [11] to [16] and [110] to [160] were obtained.
次に、１２個の構造体の各々について、実験１と同様にして、常圧流通式の試験装置を用いてプロピレン転化率５０％の温度（Ｔ50）の測定を行った。 Next, for each of the twelve structures, the temperature (T 50 ) at a propylene conversion rate of 50% was measured in the same manner as in Experiment 1 using a normal pressure flow type test apparatus.
測定して求めた構造体［１１］〜［１６］におけるＴ50を、構造体［１１］のＴ50に対する相対値（構造体［１１］のＴ50を１００とする相対値）として第２表に示す。同様に、測定して求めた構造体［１１０］〜［１６０］におけるＴ50を、構造体［１１０］のＴ50に対する相対値（構造体［１１０］のＴ50を１００とする相対値）として第２表に示す。また、構造体［１１０］〜［１６０］における、触媒Ａ（Ｐｔが担持した担体ａ1）と触媒Ｂ（Ｐｔが担持した担体ｂ1）との合計質量に対する触媒Ａの質量の比（Ａ／（Ａ＋Ｂ）×１００）とＴ50（相対値）との関係を図３に示す。 The measured and the structure [11] ~ T 50 in [16] obtained, Table 2 as (relative value to 100 the T 50 of the structure [11]) value relative to T 50 of the structure [11] Shown in Similarly, the measured and the structure [110] ~ T 50 in [160] found, as a relative value with respect to the T 50 of the structure [110] (relative value to 100 the T 50 of the structure [110]) Table 2 shows. Further, in the structures [110] to [160], the ratio of the mass of the catalyst A to the total mass of the catalyst A (the carrier a 1 carrying Pt) and the catalyst B (the carrier b 1 carrying Pt) (A / The relationship between (A + B) × 100) and T 50 (relative value) is shown in FIG.
第２表および図３より、特に耐久処理を行った構造体［１１０］〜［１６０］について、触媒Ａと触媒Ｂとの合計質量に対する触媒Ａの質量の比（Ａ／（Ａ＋Ｂ）×１００）が１０質量％超８０質量％未満の場合にＴ50が低くなり、触媒能が優れることがわかった。また、この比（Ａ／（Ａ＋Ｂ）×１００）が２０〜５０質量％の場合にＴ50が特に低くなり、触媒能がより優れることがわかった。 From Table 2 and FIG. 3, the ratio of the mass of the catalyst A to the total mass of the catalyst A and the catalyst B (A / (A + B) × 100) for the structures [110] to [160] subjected to the durability treatment in particular. There T 50 is lowered in the case of less than 10 wt percent 80 wt%, it was found that the catalytic activity is excellent. Further, the ratio (A / (A + B) × 100) is T 50 is particularly low in the case of 20 to 50 wt%, it was found that the catalytic ability is more excellent.
＜実験３＞
ＢａＡｌ2Ｏ4からなる担体ａ2を用意した。そして、担体ａ2（１００ｇ）にジニトロジアンミン白金溶液（８．５％濃度、４．７ｇ）をごくわずかずつ添加し、その後、１５０℃、常圧下で一晩乾燥した後、４００℃、常圧下で３ｈ焼成し、Ｐｔが担持した担体ａ2を得た。
そして、Ｐｔが担持した担体ａ2におけるＰｔの含有量をＩＣＰ発光分光分析装置を用いて測定したところ、担体ａ2の１００質量部に対して０．４質量部であった。なお、Ｐｔが担持した担体ａ2の組成は、ジニトロジアンミン白金溶液へ添加する前と同一であった。
<Experiment 3>
A carrier a 2 made of BaAl 2 O 4 was prepared. Then, a dinitrodiammine platinum solution (8.5% concentration, 4.7 g) was added to the carrier a 2 (100 g) little by little, followed by drying overnight at 150 ° C. under normal pressure, and then at 400 ° C. under normal pressure. And a carrier a 2 carrying Pt was obtained.
And when the content of Pt in the carrier a 2 carrying Pt was measured using an ICP emission spectroscopic analyzer, it was 0.4 parts by mass with respect to 100 parts by mass of the carrier a 2 . The composition of the carrier a 2 supported by Pt was the same as that before the addition to the dinitrodiammine platinum solution.
また、Ｐｔが担持した担体ａ2の粒度分布を測定した。具体的には、Ｐｔが担持した担体ａ2をヘキサメタリン酸ナトリウム水溶液へ添加し、超音波分散および攪拌によって分散させて、透過率が７０〜９０％となるように調節した後、レーザ散乱法（ＨＯＲＩＢＡ ＬＡ−９５０Ｖ２）を用いて粒度分布を測定した。
その結果、平均粒子径（メジアン径）は１７μｍであった。
Further, the particle size distribution of the carrier a 2 supported by Pt was measured. Specifically, Pt-supported carrier a 2 is added to an aqueous sodium hexametaphosphate solution, and dispersed by ultrasonic dispersion and stirring to adjust the transmittance to be 70 to 90%. The particle size distribution was measured using HORIBA LA-950V2).
As a result, the average particle diameter (median diameter) was 17 μm.
次に、ＢａＡｌ12Ｏ19からなる担体ｂ2を用意した。そして、担体ｂ2（１００ｇ）にジニトロジアンミン白金溶液（８．５％濃度、４．７ｇ）をごくわずかずつ添加し、その後、１５０℃、常圧下で一晩乾燥した後、４００℃、常圧下で３ｈ焼成し、Ｐｔが担持した担体ｂ2を得た。
そして、Ｐｔが担持した担体ｂ2におけるＰｔの含有量をＩＣＰ発光分光分析装置を用いて測定したところ、担体ｂ2の１００質量部に対して０．４質量部であった。なお、Ｐｔが担持した担体ｂ2の組成は、ジニトロジアンミン白金溶液へ添加する前と同一であった。
また、Ｐｔが担持した担体ｂ2の粒度分布をＰｔが担持した担体ｂ2の場合と同様の方法で測定したところ、平均粒子径（メジアン径）は３．２μｍであった。
Next, a carrier b 2 made of BaAl 12 O 19 was prepared. Then, a dinitrodiammine platinum solution (8.5% concentration, 4.7 g) was added to the carrier b 2 (100 g) little by little, followed by drying overnight at 150 ° C. under normal pressure, and then at 400 ° C. under normal pressure. To obtain carrier b 2 carrying Pt.
And when the content of Pt in the carrier b 2 carrying Pt was measured using an ICP emission spectroscopic analyzer, it was 0.4 parts by mass with respect to 100 parts by mass of the carrier b 2 . The composition of the carrier b 2 supported by Pt was the same as that before the addition to the dinitrodiammine platinum solution.
Further, when Pt was measured in the same manner as with the carrier b 2 of the particle size distribution of the carrier b 2 carrying Pt was supported, the average particle diameter (median diameter) was 3.2 .mu.m.
次に、Ｐｔが担持した担体ａ2とＰｔが担持した担体ｂ2とを混合して混合物を得た。ここで混合比は７通りとし、７個の混合物を得た。具体的には、Ｐｔが担持した担体ａ2とＰｔが担持した担体ｂ2との混合比（質量比）は、１００／０、９０／１０、７０／３０、５０／５０、３０／７０、１５／８５、０／１００とし、各々を混合物［２１］〜［２７］とした。 Next, the carrier a 2 carrying Pt and the carrier b 2 carrying Pt were mixed to obtain a mixture. Here, the mixing ratio was set to 7 to obtain 7 mixtures. Specifically, the mixing ratio (mass ratio) of the carrier a 2 carrying Pt and the carrier b 2 carrying Pt is 100/0, 90/10, 70/30, 50/50, 30/70, 15/85 and 0/100, and each of them was a mixture [21] to [27].
次に、各々の混合物の８０ｇをイオン交換水（常温）へ添加し、マグネティックスラーターで一晩攪拌した。その後、溶液中から固形分を取り出し、その固形分を１５０℃、常圧下で一晩乾燥した後、４００℃、常圧下で３ｈ焼成し、本発明の排ガス浄化用触媒に相当する触媒［２１］〜［２７］を得た。 Next, 80 g of each mixture was added to ion-exchanged water (at room temperature) and stirred overnight with a magnetic slurter. Thereafter, the solid content is taken out from the solution, and the solid content is dried at 150 ° C. under normal pressure overnight, and then calcined at 400 ° C. under normal pressure for 3 hours. The catalyst corresponding to the exhaust gas purifying catalyst of the present invention [21] To [27].
次に、触媒［２１］〜［２７］の各々について、４０ｇをイオン交換水（１１９ｇ）およびバインダーとともにバッチ式ボールミルを用いて湿式粉砕し、スラリーを得た。バインダーとしてはベーマイトを用い、ベーマイトの添加量は混合触媒１００質量部に対して１０質量部とした。また、湿式粉砕は回転数を１００ｒｐｍとし、粉砕時間は、スラリー中の固形分のメジアン径が２０μｍ程度以下となるように、５〜４０分で調整した。また、ビーズ径５ｍｍのジルコニアビーズ２１０ｃｃを用いた。このような処理を施して固形分濃度が２７質量％のスラリーを７個得た。次に、各々のスラリーへコージェライト製のセラミックハニカム構造体（体積５．３ｃｍ3、４００ｃｅｌｌｓ／ｉｎｃｈ2）を浸漬し、３分放置した後、引き上げ、１５０℃で１ｈ乾燥した後、４００℃で３ｈ焼成する方法（ウォッシュコート法）によって、表面に本発明の排ガス浄化用触媒を備える触媒担持構造体を得た。触媒［２１］を表面に備える触媒担持構造体を構造体［２１］とし、同様に、触媒［２２］〜［２７］の各々を表面に備える触媒担持構造体を構造体［２２］〜［２７］とした。
構造体［２１］〜［２７］は、同じものを２個ずつ作製した。
Next, 40 g of each of the catalysts [21] to [27] was wet-ground using a batch type ball mill together with ion-exchanged water (119 g) and a binder to obtain a slurry. Boehmite was used as the binder, and the amount of boehmite added was 10 parts by mass with respect to 100 parts by mass of the mixed catalyst. In addition, the wet pulverization was performed at a rotation speed of 100 rpm, and the pulverization time was adjusted in 5 to 40 minutes so that the median diameter of the solid content in the slurry was about 20 μm or less. Further, 210 cc of zirconia beads having a bead diameter of 5 mm was used. By performing such treatment, seven slurries having a solid content concentration of 27% by mass were obtained. Next, a cordierite ceramic honeycomb structure (volume 5.3 cm 3 , 400 cells / inch 2 ) was immersed in each slurry, left for 3 minutes, pulled up, dried at 150 ° C. for 1 h, and then dried at 400 ° C. A catalyst-supporting structure having the exhaust gas purifying catalyst of the present invention on the surface was obtained by a method (wash coat method) of firing for 3 hours. The catalyst supporting structure including the catalyst [21] on the surface is referred to as the structure [21]. Similarly, the catalyst supporting structures including the catalysts [22] to [27] on the surface are the structures [22] to [27. ].
Two identical structures [21] to [27] were produced.
次に、２個の構造体［２１］のうちの１個について、９００℃に調整したマッフル炉中（常圧下）に３０ｈ保持し、耐久処理（強制劣化加速処理）を施した。構造体［２１］に耐久処理を施したものを、構造体［２１０］とした。そして、同様に、構造体［２２］〜［２７］についても耐久処理を施して、構造体［２２０］〜［２７０］を得た。 Next, one of the two structures [21] was kept in a muffle furnace (under normal pressure) adjusted to 900 ° C. for 30 hours, and subjected to durability treatment (forced deterioration acceleration treatment). The structure [21] was obtained by subjecting the structure [21] to durability treatment. In the same manner, the structures [22] to [27] were subjected to durability treatment to obtain structures [220] to [270].
このようにして構造体［２１］〜［２７］および構造体［２１０］〜［２７０］の１４個の構造体を得た。 In this way, 14 structures of [21] to [27] and [210] to [270] were obtained.
このようにして得た１４個の構造体の各々について、実験１および２と同様にして、プロピレン転化率５０％の温度（Ｔ50）の測定を行った。 For each of the 14 structures thus obtained, the temperature (T 50 ) at a propylene conversion rate of 50% was measured in the same manner as in Experiments 1 and 2.
測定して求めた構造体［２１］〜［２７］におけるＴ50を、構造体［２１］のＴ50に対する相対値（構造体［２１］のＴ50を１００とする相対値）として第３表に示す。同様に、測定して求めた構造体［２１０］〜［２７０］におけるＴ50を、構造体［２１０］のＴ50に対する相対値（構造体［２１０］のＴ50を１００とする相対値）として第３表に示す。また、構造体［２１０］〜［２７０］における、触媒Ａ（Ｐｔが担持した担体ａ2）と触媒Ｂ（Ｐｔが担持した担体ｂ2）との合計質量に対する触媒Ａの質量の比（Ａ／（Ａ＋Ｂ）×１００）とＴ50（相対値）との関係を図４に示す。 Table 3 the measured and the structure [21] ~ T 50 in [27] found, as a relative value with respect to the T 50 of the structure [21] (relative value to 100 the T 50 of the structure [21]) Shown in Similarly, the T 50 in the measured and calculated structure [210] - [270], as a relative value with respect to the T 50 of the structure [210] (relative value to 100 the T 50 of the structure [210]) It is shown in Table 3. In the structures [210] to [270], the ratio of the mass of the catalyst A to the total mass of the catalyst A (the carrier a 2 carrying Pt) and the catalyst B (the carrier b 2 carrying Pt) (A / The relationship between (A + B) × 100) and T 50 (relative value) is shown in FIG.
第３表および図４より、特に耐久処理を行った構造体［２１０］〜［２７０］について、触媒Ａと触媒Ｂとの合計質量に対する触媒Ａの質量の比（Ａ／（Ａ＋Ｂ）×１００）が５〜５０質量％の場合にＴ50が低くなり、触媒能が優れることがわかった。また、この比（Ａ／（Ａ＋Ｂ）×１００）が５〜３０質量％の場合にＴ50が特に低くなり、触媒能がより優れることがわかった。 From Table 3 and FIG. 4, the ratio of the mass of the catalyst A to the total mass of the catalyst A and the catalyst B (A / (A + B) × 100) for the structures [210] to [270] subjected to the durability treatment in particular. There T 50 is lowered in the case of 5 to 50 mass%, it was found that the catalytic activity is excellent. Further, the ratio (A / (A + B) × 100) is T 50 is particularly low in the case of 5 to 30 mass%, it was found that the catalytic ability is more excellent.
＜実験４＞ <Experiment 4>
ＹＳＺからなる担体ｂ3を用意した。そして、担体ｂ3（１００ｇ）にジニトロジアンミン白金溶液（８．５％濃度、４．７ｇ）をごくわずかずつ添加し、その後、１５０℃、常圧下で一晩乾燥した後、４００℃、常圧下で３ｈ焼成し、Ｐｔが担持した担体ｂ3を得た。
そして、Ｐｔが担持した担体ｂ3におけるＰｔの含有量をＩＣＰ発光分光分析装置を用いて測定したところ、担体ｂ3の１００質量部に対して０．４質量部であった。なお、Ｐｔが担持した担体ｂ3の組成は、ジニトロジアンミン白金溶液へ添加する前と同一であった。
また、Ｐｔが担持した担体ｂ3の粒度分布をＰｔが担持した担体ｂ2の場合と同様の方法で測定したところ、平均粒子径（メジアン径）は０．０９μｍであった。
A carrier b 3 made of YSZ was prepared. Then, a dinitrodiammine platinum solution (8.5% concentration, 4.7 g) was added to the carrier b 3 (100 g) little by little, followed by drying overnight at 150 ° C. under normal pressure, and then at 400 ° C. under normal pressure. Was fired for 3 hours to obtain a carrier b 3 carrying Pt.
And when the content of Pt in the carrier b 3 carrying Pt was measured using an ICP emission spectroscopic analyzer, it was 0.4 parts by mass with respect to 100 parts by mass of the carrier b 3 . The composition of the carrier b 3 supported by Pt was the same as before the addition to the dinitrodiammine platinum solution.
Further, when the particle size distribution of the carrier b 3 carrying Pt was measured by the same method as that for the carrier b 2 carrying Pt, the average particle diameter (median diameter) was 0.09 μm.
次に、実験３で得たＰｔが担持した担体ａ2とＰｔが担持した担体ｂ3とを混合して混合物を得た。ここで混合比は５通りとし、５個の混合物を得た。具体的には、Ｐｔが担持した担体ａ2とＰｔが担持した担体ｂ3との混合比（質量比）は、１００／０、８０／２０、５０／５０、２０／８０、０／１００とし、各々を混合物［３１］〜［３５］とした。 Next, the carrier a 2 carrying Pt obtained in Experiment 3 and the carrier b 3 carrying Pt were mixed to obtain a mixture. Here, the mixing ratio was five, and five mixtures were obtained. Specifically, the mixing ratio (mass ratio) of the carrier a 2 carrying Pt and the carrier b 3 carrying Pt is 100/0, 80/20, 50/50, 20/80, 0/100. , Each was used as a mixture [31] to [35].
次に、各々の混合物の８０ｇをイオン交換水（常温）へ添加し、マグネティックスラーターで一晩攪拌した。その後、溶液中から固形分を取り出し、その固形分を１５０℃、常圧下で一晩乾燥した後、４００℃、常圧下で３ｈ焼成し、本発明の排ガス浄化用触媒に相当する触媒［３１］〜［３５］を得た。 Next, 80 g of each mixture was added to ion-exchanged water (at room temperature) and stirred overnight with a magnetic slurter. Thereafter, the solid content is taken out from the solution, and the solid content is dried at 150 ° C. under normal pressure overnight, and then calcined at 400 ° C. under normal pressure for 3 hours. The catalyst corresponding to the exhaust gas purifying catalyst of the present invention [31] To [35].
次に、触媒［３１］〜［３５］について、各々４０ｇをイオン交換水（１１９ｇ）およびバインダーとともにバッチ式ボールミルを用いて湿式粉砕し、スラリーを得た。バインダーとしてはベーマイトを用い、ベーマイトの添加量は触媒１００質量部に対して１０質量部とした。また、湿式粉砕は回転数を１００ｒｐｍとし、粉砕時間は、スラリー中の固形分のメジアン径が２０μｍ程度以下となるように、５〜４０分で調整した。また、ビーズ径５ｍｍのジルコニアビーズ２１０ｃｃを用いた。このような処理を施して固形分濃度が２７質量％のスラリーを５個得た。次に、各々のスラリーへコージェライト製のセラミックハニカム構造体（体積５．３ｃｍ3、４００ｃｅｌｌｓ／ｉｎｃｈ2）を浸漬し、３分放置した後、引き上げ、１５０℃で１ｈ乾燥した後、４００℃で３ｈ焼成する方法（ウォッシュコート法）によって、表面に本発明の排ガス浄化用触媒を備える触媒担持構造体を得た。触媒［３１］を表面に備える触媒担持構造体を構造体［３１］とし、同様に、触媒［３２］〜［３５］の各々を表面に備える触媒担持構造体を構造体［３２］〜［３５］とした。
構造体［３１］〜［３５］は、同じものを２個ずつ作製した。
Next, 40 g of each of the catalysts [31] to [35] was wet-ground using a batch type ball mill together with ion-exchanged water (119 g) and a binder to obtain a slurry. Boehmite was used as the binder, and the amount of boehmite added was 10 parts by mass with respect to 100 parts by mass of the catalyst. In addition, the wet pulverization was performed at a rotation speed of 100 rpm, and the pulverization time was adjusted in 5 to 40 minutes so that the median diameter of the solid content in the slurry was about 20 μm or less. Further, 210 cc of zirconia beads having a bead diameter of 5 mm was used. By performing such treatment, five slurries having a solid content concentration of 27% by mass were obtained. Next, a cordierite ceramic honeycomb structure (volume 5.3 cm 3 , 400 cells / inch 2 ) was immersed in each slurry, left for 3 minutes, pulled up, dried at 150 ° C. for 1 h, and then dried at 400 ° C. A catalyst-supporting structure having the exhaust gas purifying catalyst of the present invention on the surface was obtained by a method (wash coat method) of firing for 3 hours. The catalyst supporting structure including the catalyst [31] on the surface is referred to as the structure [31]. Similarly, the catalyst supporting structures including the catalysts [32] to [35] on the surface are the structures [32] to [35. ].
Two identical structures [31] to [35] were produced.
次に、２個の構造体［３１］のうちの１個について、９００℃に調整したマッフル炉中（常圧下）に３０ｈ保持し、耐久処理（強制劣化加速処理）を施した。構造体［３１］に耐久処理を施したものを、構造体［３１０］とした。そして、同様に、構造体［３２］〜［３５］についても耐久処理を施して、構造体［３２０］〜［３５０］を得た。 Next, one of the two structures [31] was held in a muffle furnace adjusted to 900 ° C. (under normal pressure) for 30 hours and subjected to durability treatment (forced deterioration acceleration treatment). The structure [31] was obtained by subjecting the structure [31] to durability treatment. In the same manner, the structures [32] to [35] were subjected to durability treatment to obtain structures [320] to [350].
このようにして構造体［３１］〜［３５］および構造体［３１０］〜［３５０］の１０個の構造体を得た。 In this way, ten structures [31] to [35] and ten structures [310] to [350] were obtained.
このようにして得た１０個の構造体の各々について、実験１〜３と同様にして、プロピレン転化率５０％の温度（Ｔ50）の測定を行った。 For each of the 10 structures thus obtained, the temperature (T 50 ) at a propylene conversion rate of 50% was measured in the same manner as in Experiments 1 to 3.
測定して求めた構造体［３１］〜［３５］におけるＴ50を、構造体［３１］のＴ50に対する相対値（構造体［３１］のＴ50を１００とする相対値）として第４表に示す。同様に、測定して求めた構造体［３１０］〜［３５０］におけるＴ50を、構造体［３１０］のＴ50に対する相対値（構造体［３１０］のＴ50を１００とする相対値）として第４表に示す。また、構造体［３１０］〜［３５０］における、触媒Ａ（Ｐｔが担持した担体ａ3）と触媒Ｂ（Ｐｔが担持した担体ｂ3）との合計質量に対する触媒Ａの質量の比（Ａ／（Ａ＋Ｂ）×１００）とＴ50（相対値）との関係を図５に示す。 Table 50 shows T 50 in the structures [31] to [35] obtained by measurement as relative values to the T 50 of the structure [31] (relative values where the T 50 of the structure [31] is 100). Shown in Similarly, T 50 in the structures [310] to [350] obtained by measurement is a relative value with respect to T 50 of the structure [310] (relative value where T 50 of the structure [310] is 100). Table 4 shows. In addition, in the structures [310] to [350], the ratio of the mass of the catalyst A to the total mass of the catalyst A (the carrier a 3 carrying Pt) and the catalyst B (the carrier b 3 carrying Pt) (A / The relationship between (A + B) × 100) and T 50 (relative value) is shown in FIG.
第４表および図５より、特に耐久処理を行った構造体［３１０］〜［３５０］について、触媒Ａと触媒Ｂとの合計質量に対する触媒Ａの質量の比（Ａ／（Ａ＋Ｂ）×１００）が５質量％超５０質量％以下の場合にＴ50が低くなり、触媒能が優れることがわかった。また、この比（Ａ／（Ａ＋Ｂ）×１００）が５〜３０質量％の場合にＴ50が特に低くなり、触媒能がより優れることがわかった。 From Table 4 and FIG. 5, the ratio of the mass of the catalyst A to the total mass of the catalyst A and the catalyst B (A / (A + B) × 100) for the structures [310] to [350] subjected to the durability treatment in particular. There T 50 is lowered in the case of less than 5 wt percent 50 wt%, it was found that the catalytic activity is excellent. Further, the ratio (A / (A + B) × 100) is T 50 is particularly low in the case of 5 to 30 mass%, it was found that the catalytic ability is more excellent.
１ 触媒
２ 担体
４ 活性金属
６ 溶出由来成分
１２ Ｐｔ粒子
１４ 溶出由来成分
１６ 担体
DESCRIPTION OF SYMBOLS 1 Catalyst 2 Carrier 4 Active metal 6 Elution origin component 12 Pt particle 14 Elution origin component 16 Support
Claims (11)
前記担体が、前記溶出成分を含む担体ａと前記溶出成分を含まない担体ｂとからなり、
前記溶出成分および／またはこれに由来する成分が、前記担体ａに担持した活性金属を前記担体ａの表面に固定している触媒Ａと、
前記溶出成分および／またはこれに由来する成分が、前記担体ｂに担持した活性金属を前記担体ｂの表面に固定している触媒Ｂと
を含み、
前記担体ａは前記溶出成分、または前記溶出成分とその他成分とからなり、
前記溶出成分はＢａＡｌ2Ｏ4、Ａｌ（ＯＨ）3およびＡｌＯＯＨからなる群から選ばれる少なくとも１つであり、これらの合計含有率は前記担体ａにおいて５〜１００質量％であり、
前記その他成分は、
Ｂａ、ＡｌおよびＺｒならびにこれらの酸化物、
Ｂａ、Ａｌ、Ｚｒおよびこれらの酸化物ならびにアルカリ、アルカリ土類、希土類および遷移金属の少なくとも１つ、
Ｂａ、Ａｌ、ＺｒおよびＹならびにこれらの酸化物、または、
Ｂａ、Ａｌ、Ｚｒ、Ｙおよびこれらの酸化物ならびにアルカリ、アルカリ土類、希土類および遷移金属の少なくとも１つであり、
前記担体ｂは酸化セリウムを主成分とし、
前記触媒Ａと前記触媒Ｂとの合計質量に対する前記触媒Ａの質量比（Ａ／（Ａ＋Ｂ）×１００）が２０〜５０質量％である、排ガス浄化用触媒。 An eluting component and / or a component derived therefrom is an exhaust gas purifying catalyst comprising a catalyst in which an active metal supported on a carrier is fixed to the surface of the carrier,
The carrier comprises a carrier a containing the eluting component and a carrier b not containing the eluting component,
And catalyst A prior Symbol eluting component and / or components derived from this, securing the active metal supported on the support a on the surface of the carrier a,
Before SL eluted component and / or components derived from this, and a catalyst B that secure the active metal supported on the carrier b on the surface of the carrier b,
The carrier a consists of the elution component, or the elution component and other components,
The eluting component is at least one selected from the group consisting of BaAl 2 O 4 , Al (OH) 3 and AlOOH, and the total content thereof is 5 to 100% by mass in the carrier a,
The other ingredients are
Ba, Al and Zr and their oxides,
Ba, Al, Zr and their oxides and at least one of alkali, alkaline earth, rare earth and transition metals,
Ba, Al, Zr and Y and their oxides, or
Ba, Al, Zr, Y and oxides thereof and at least one of alkali, alkaline earth, rare earth and transition metal,
The carrier b is mainly composed of cerium oxide,
A catalyst for exhaust gas purification, wherein a mass ratio of the catalyst A to a total mass of the catalyst A and the catalyst B (A / (A + B) × 100) is 20 to 50% by mass.
前記担体が、前記溶出成分を含む担体ａと前記溶出成分を含まない担体ｂとからなり、
前記溶出成分および／またはこれに由来する成分が、前記担体ａに担持した活性金属を前記担体ａの表面に固定している触媒Ａと、
前記溶出成分および／またはこれに由来する成分が、前記担体ｂに担持した活性金属を前記担体ｂの表面に固定している触媒Ｂと
を含み、
前記担体ａは前記溶出成分、または前記溶出成分とその他の成分とからなり、
前記溶出成分はＢａＡｌ2Ｏ4、Ａｌ（ＯＨ）3およびＡｌＯＯＨからなる群から選ばれる少なくとも１つであり、これらの合計含有率は前記担体ａにおいて５〜１００質量％であり、
前記その他成分は、
Ｂａ、ＡｌおよびＺｒならびにこれらの酸化物、
Ｂａ、Ａｌ、Ｚｒおよびこれらの酸化物、ならびにアルカリ、アルカリ土類、希土類および遷移金属の少なくとも１つ、
Ｂａ、Ａｌ、ＺｒおよびＹならびにこれらの酸化物、または、
Ｂａ、Ａｌ、Ｚｒ、Ｙおよびこれらの酸化物、ならびにアルカリ、アルカリ土類、希土類および遷移金属の少なくとも１つであり、
前記担体ｂがＢａ、ＡｌおよびＺｒならびにこれらの酸化物、またはＢａ、Ａｌ、ＺｒおよびＹならびにこれらの酸化物を主成分とし、
前記触媒Ａと前記触媒Ｂとの合計質量に対する前記触媒Ａの質量比（Ａ／（Ａ＋Ｂ）×１００）が１５〜５０質量％である、排ガス浄化用触媒。 An eluting component and / or a component derived therefrom is an exhaust gas purifying catalyst comprising a catalyst in which an active metal supported on a carrier is fixed to the surface of the carrier,
The carrier comprises a carrier a containing the eluting component and a carrier b not containing the eluting component,
And catalyst A prior Symbol eluting component and / or components derived from this, securing the active metal supported on the support a on the surface of the carrier a,
Before SL eluted component and / or components derived from this, and a catalyst B that secure the active metal supported on the carrier b on the surface of the carrier b,
The carrier a consists of the elution component, or the elution component and other components,
The eluting component is at least one selected from the group consisting of BaAl 2 O 4 , Al (OH) 3 and AlOOH, and the total content thereof is 5 to 100% by mass in the carrier a,
The other ingredients are
Ba, Al and Zr and their oxides,
Ba, Al, Zr and their oxides, and at least one of alkali, alkaline earth, rare earth and transition metals,
Ba, Al, Zr and Y and their oxides, or
Ba, Al, Zr, Y and their oxides, and at least one of alkali, alkaline earth, rare earth and transition metals,
The carrier b is mainly composed of Ba, Al and Zr and their oxides, or Ba, Al, Zr and Y and their oxides,
A catalyst for exhaust gas purification, wherein a mass ratio of the catalyst A to the total mass of the catalyst A and the catalyst B (A / (A + B) × 100) is 15 to 50% by mass.
前記担体ｂはＢａＡｌ12Ｏ19からなり、
前記触媒Ａと前記触媒Ｂとの合計質量に対する前記触媒Ａの質量比（Ａ／（Ａ＋Ｂ）×１００）が１５〜３０質量％である、請求項３に記載の排ガス浄化用触媒。 The carrier a is composed of BaAl 2 O 4 as the elution component,
The carrier b is made of BaAl 12 O 19 ,
The exhaust gas purifying catalyst according to claim 3, wherein a mass ratio (A / (A + B) x 100) of the catalyst A to a total mass of the catalyst A and the catalyst B is 15 to 30% by mass.
前記担体ｂはＹＳＺからなり、
前記触媒Ａと前記触媒Ｂとの合計質量に対する前記触媒Ａの質量比（Ａ／（Ａ＋Ｂ）×１００）が２０〜５０質量％である、請求項３に記載の排ガス浄化用触媒。 The carrier a is composed of BaAl 2 O 4 as the elution component,
The carrier b is made of YSZ,
The exhaust gas purifying catalyst according to claim 3, wherein a mass ratio (A / (A + B) x 100) of the catalyst A to a total mass of the catalyst A and the catalyst B is 20 to 50 mass%.
前記活性金属を担持させた前記担体ａおよび前記活性金属を担持させた前記担体ｂを、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程と、
前記溶出成分および／またはこれに由来する成分を前記担体ａおよび前記担体ｂの表面で固化して触媒Ａおよび触媒Ｂを得る固化工程と
を備え、請求項１〜７のいずれかに記載の排ガス浄化用触媒が得られる、排ガス浄化用触媒の製造方法。 And as supported Engineering of supporting the active metal on the support a and the surface of each of said carrier b not including the elution component containing the eluted components,
An elution process in which the carrier a carrying the active metal and the carrier b carrying the active metal are brought into contact with a solvent that dissolves the elution component to elute at least a part of the elution component into the solvent. About
As solidified Engineering to obtain a catalyst A and catalyst B the elution component and / or components derived therefrom solidified on the surface of the support a and the carrier b and comprises a <br/>, any of the preceding claims A method for producing an exhaust gas purification catalyst, wherein the exhaust gas purification catalyst according to claim 1 is obtained.
前記活性金属を担持させた前記担体ａおよび前記活性金属を担持させた前記担体ｂを、前記溶出成分を溶解する溶媒と接触させて、前記溶出成分の少なくとも一部を溶媒中へ溶出させる溶出工程と、
前記活性金属を担持した前記担体ａおよび前記担体ｂを、前記溶出工程によって得られる前記溶媒とともに構造体と接触させ、その後、前記溶媒を除去することで、前記溶出成分および／またはこれに由来する成分を前記担体の表面で固化し、あわせて前記活性金属を担持した前記担体ａおよび前記担体ｂを前記構造体の表面に付ける付着工程と
を備え、請求項１〜７のいずれかに記載の排ガス浄化用触媒を表面に有する触媒担持構造体が得られる、触媒担持構造体の製造方法。 And as supported Engineering of supporting the active metal on the support a and the surface of each of said carrier b not including the elution component containing the eluted components,
An elution process in which the carrier a carrying the active metal and the carrier b carrying the active metal are brought into contact with a solvent that dissolves the elution component to elute at least a part of the elution component into the solvent. About
The carrier a and the carrier b carrying the active metal are brought into contact with the structure together with the solvent obtained by the elution step, and then the solvent is removed to thereby derive the elution component and / or the same. the ingredients solidified on the surface of said carrier, said carrier a and the carrier b carrying the active metal together as deposited Engineering be attached to a surface of said structure and provided with <br/>, of claims 1-7 A method for producing a catalyst-carrying structure, wherein a catalyst-carrying structure having the exhaust gas-purifying catalyst according to any one of the surfaces is obtained.
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