JP2006205037A - Reforming catalyst and catalyst for cleaning exhaust gas using this - Google Patents
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- JP2006205037A JP2006205037A JP2005019528A JP2005019528A JP2006205037A JP 2006205037 A JP2006205037 A JP 2006205037A JP 2005019528 A JP2005019528 A JP 2005019528A JP 2005019528 A JP2005019528 A JP 2005019528A JP 2006205037 A JP2006205037 A JP 2006205037A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 145
- 238000002407 reforming Methods 0.000 title claims abstract description 63
- 238000004140 cleaning Methods 0.000 title abstract 3
- 239000000758 substrate Substances 0.000 claims abstract description 37
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 30
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
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- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 abstract description 10
- 239000011572 manganese Substances 0.000 abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
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- 238000000034 method Methods 0.000 description 12
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 11
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 239000002759 woven fabric Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
本発明は、改質触媒及びこれを用いた排気ガス浄化用触媒に係り、更に詳細には、触媒能を有し、著しく大きな表面積を有する酸化マンガンウィスカーを利用した改質触媒及びこれを用いた排気ガス浄化用触媒に関する。 The present invention relates to a reforming catalyst and an exhaust gas purifying catalyst using the same, and more specifically, a reforming catalyst using a manganese oxide whisker having catalytic ability and a remarkably large surface area, and the same. The present invention relates to an exhaust gas purification catalyst.
従来、ホーランダイト型の酸化マンガンを調製・貴金属を担持させた粉末とアルミナ等のセラミックス粉末とを混合してスラリーを作成し、アルミナ支持材等に塗布してＣＯシフト触媒として使用することが提案されている（特許文献１参照。）。
また、酸化マンガンとアルカリ土類金属酸化物と貴金属を組合せたＮＯｘ還元触媒が提案されている（特許文献２参照。）。
A NOx reduction catalyst in which manganese oxide, an alkaline earth metal oxide, and a noble metal are combined has been proposed (see Patent Document 2).
しかしながら、上記特許文献１に記載の従来技術においては、多孔質基材表面上への塗布を行わなければならず、装置全体の中での触媒実効面積には限界があるという問題点があった。また、支持する多孔質基材が別個に必要であった。 However, in the prior art described in Patent Document 1, there is a problem in that coating on the surface of the porous substrate has to be performed, and there is a limit to the effective catalyst area in the entire apparatus. . Moreover, the porous base material to support was needed separately.
更に、上記特許文献２に記載の従来技術においては、触媒の改質効率と排気ガスの圧力損失とがトレードオフの関係となっており、大きな粒径分布をもつ排気ガスなどに適用すると目詰まりを起こし易いという問題点があった。 Furthermore, in the prior art described in Patent Document 2, the catalyst reforming efficiency and the exhaust gas pressure loss are in a trade-off relationship, and are clogged when applied to exhaust gas having a large particle size distribution. There was a problem that it was easy to cause.
本発明は、このような従来技術の有する課題に鑑みてなされたものであり、その目的とするところは、反応効率の優れた改質触媒及びこれを用いた排気ガス浄化用触媒を提供することにある。 The present invention has been made in view of such problems of the prior art, and an object of the present invention is to provide a reforming catalyst having excellent reaction efficiency and an exhaust gas purifying catalyst using the same. It is in.
本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、触媒能を有し、著しく大きな表面積を有する酸化マンガンウィスカーを利用することなどにより、上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by utilizing a manganese oxide whisker having catalytic ability and a remarkably large surface area. It came to be completed.
即ち、本発明の改質触媒は、基体と該基体表面に形成されたウィスカーと該基体及びウィスカーの一方又は双方の表面に担持された触媒成分とを有する。
そして、かかる基体はマンガンを含む合金及びセラミックスの一方又は双方を含有し、ウィスカーはマンガン酸化物を含有する。
That is, the reforming catalyst of the present invention has a substrate, whiskers formed on the surface of the substrate, and a catalyst component supported on one or both surfaces of the substrate and the whiskers.
The base contains one or both of an alloy containing manganese and ceramics, and the whisker contains manganese oxide.
また、本発明の排気ガス浄化用触媒は、上記本発明の改質触媒を用いたものであって、かかる改質触媒が排気ガス流路に配設されている。 The exhaust gas purifying catalyst of the present invention uses the above-described reforming catalyst of the present invention, and the reforming catalyst is disposed in the exhaust gas passage.
本発明によれば、触媒能を有し、著しく大きな表面積を有する酸化マンガンウィスカーを利用することなどとしたため、反応効率の優れた改質触媒及びこれを用いた排気ガス浄化用触媒を提供することができる。 According to the present invention, since a manganese oxide whisker having catalytic ability and a remarkably large surface area is used, a reforming catalyst having excellent reaction efficiency and an exhaust gas purification catalyst using the same are provided. Can do.
以下、本発明の改質触媒について詳細に説明する。
上述の如く、本発明の改質触媒は、基体と該基体表面に形成されたウィスカーと該基体及びウィスカーの一方又は双方の表面に担持された触媒成分とを有し、該基体はマンガンを含む合金及びセラミックスの一方又は双方を含有し、該ウィスカーはマンガン酸化物を含有する。
ここで、本発明の改質触媒は、後述する排気ガスに対してだけでなく、硫化水素やアンモニア、ホルムアルデヒドに対しても改質触媒として用いることができ、ダイオキシンや油煙などの分解反応においても触媒作用を発揮するため利用することができる。また、これらを含んだ廃棄物の処理過程においても用いることができる。
なお、本発明の改質触媒は、改質対象が気体である場合に特に優れた触媒作用を発揮するが、これに限定されるものではなく、気体や液体などの流体や、固体に対しても適用することが可能である。
Hereinafter, the reforming catalyst of the present invention will be described in detail.
As described above, the reforming catalyst of the present invention has a substrate, whiskers formed on the surface of the substrate, and a catalyst component supported on one or both surfaces of the substrate and the whiskers, and the substrate contains manganese. One or both of an alloy and ceramics are contained, and the whisker contains a manganese oxide.
Here, the reforming catalyst of the present invention can be used as a reforming catalyst not only for exhaust gas, which will be described later, but also for hydrogen sulfide, ammonia, and formaldehyde, and in a decomposition reaction such as dioxin and oil smoke. It can be used to exert a catalytic action. Moreover, it can be used in the process of the waste containing these.
The reforming catalyst of the present invention exhibits a particularly excellent catalytic action when the reforming target is a gas, but is not limited thereto, and is not limited to a fluid such as a gas or a liquid, or a solid. Can also be applied.
このように、基体表面に形成されたウィスカーによって微細な凹凸が形成されことにより、基体やウィスカー自体の触媒能を高めることができる。
従来の手法では、基体としてアルミナなどの触媒能を殆ど有さないものに触媒成分を担持させている場合が多く、本発明の改質触媒のように、触媒成分を担持させる基体やウィスカー自体が触媒能を有するため、従来の触媒成分の担持量より少ない量で触媒能を高めることができる。
また、微細な凹凸が形成されることにより、触媒成分が細かく分散された状態となるだけでなく、ガスが吸着され易い触媒活性部位としての機能を持たせることもできる。
更に、従来の改質触媒に用いられている樹脂やゼオライトなどの担体と比較して、ウィスカーを用いているため、耐衝撃性や耐熱性が著しく優れており、高温での使用にも適している。
As described above, the fine irregularities are formed by the whiskers formed on the surface of the base, thereby enhancing the catalytic ability of the base and the whiskers themselves.
In the conventional technique, the catalyst component is often supported on a substrate having almost no catalytic ability such as alumina, and the substrate or whisker itself supporting the catalyst component is not provided as in the reforming catalyst of the present invention. Since it has catalytic ability, the catalytic ability can be enhanced with an amount smaller than the conventional supported amount of the catalyst component.
Further, by forming fine irregularities, not only the catalyst components are finely dispersed, but also a function as a catalytic active site where gas is easily adsorbed can be provided.
Furthermore, compared to conventional resins such as resins and zeolites used for reforming catalysts, whiskers are used, so the impact resistance and heat resistance are remarkably superior, making them suitable for use at high temperatures. Yes.
まず、本発明の改質触媒の形状について説明する。
本発明において、基体の形状は特に限定されるものではなく、例えば粉粒体であっても、多孔質体であってもよい。
粉粒体の具体例としては、例えば粉末、チップ、円柱又は短繊維状のものなどを挙げることができる。また、多孔質体の具体例としては、例えば焼結合金や発泡金属などの金属基板、金属メッシュ（織布、不織布など）、ハニカム、円柱、円筒、コルゲート及びドーナツ状のものなどを挙げることができる。
First, the shape of the reforming catalyst of the present invention will be described.
In the present invention, the shape of the substrate is not particularly limited, and may be, for example, a powder or a porous material.
Specific examples of the granular material include, for example, powder, chips, columns or short fibers. Specific examples of the porous body include metal substrates such as sintered alloys and foamed metals, metal meshes (woven fabric, nonwoven fabric, etc.), honeycombs, cylinders, cylinders, corrugates, and donuts. it can.
また、本発明において、ウィスカーの形状は上記基体の表面に微細な凹凸が形成され表面積が大きくなるよう形成されていることが望ましく、基体が開気孔を有する多孔質体の場合には、ウィスカーがその開気孔の内部に形成されていることが望ましく、具体的には、開気孔の孔径がウィスカー形成前より形成後の方が小さくなるように形成されていることが望ましい。このような形状とすることにより、改質触媒の表面積が大きくなり、反応効率が向上する。更に、ウィスカーの表面に微細な凹凸を有する場合もある。
ここで、代表的なウィスカーは、外径（太さ）が１０〜５０００ｎｍで長さが１〜５０μｍである。
In the present invention, it is desirable that the whisker is formed so that fine irregularities are formed on the surface of the substrate to increase the surface area. When the substrate is a porous body having open pores, It is desirable that the pores are formed inside the open pores. Specifically, it is desirable that the pore size of the open pores is smaller after formation than before whisker formation. By setting it as such a shape, the surface area of a reforming catalyst becomes large and reaction efficiency improves. Furthermore, the whisker surface may have fine irregularities.
Here, a typical whisker has an outer diameter (thickness) of 10 to 5000 nm and a length of 1 to 50 μm.
次に、本発明の改質触媒の成分について説明する。
本発明において、基体の成分は、マンガンを含む合金及びセラミックスの一方又は双方を含有すれば特に限定されるものではないが、基体表面が酸化マンガンを含有する又は酸化マンガンからなることが望ましい。
Next, the components of the reforming catalyst of the present invention will be described.
In the present invention, the component of the substrate is not particularly limited as long as it contains one or both of an alloy containing manganese and ceramics, but it is desirable that the substrate surface contains manganese oxide or consists of manganese oxide.
また、本発明において、ウィスカーの成分は、マンガン酸化物を含有すれば特に限定されるものではないが、酸化マンガンを含有する又は酸化マンガンからなることが望ましい。 In the present invention, the whisker component is not particularly limited as long as it contains manganese oxide, but it preferably contains manganese oxide or consists of manganese oxide.
更に、本発明において、基体やウィスカーの表面に担持された触媒成分は、触媒性能を向上させることができれば特に限定されるものではないが、例えば担持された基体やウィスカーと異なる組成又は元素を含有することが望ましい。
このような触媒成分としては、例えば白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）、イリジウム（Ｉｒ）、金（Ａｕ）、錫（Ｓｎ）、鉄（Ｆｅ）又は銅（Ｃｕ）、及びこれらの任意の組み合わせに係る元素を挙げることができ、組み合わせる場合には混合したり合金化してもよい。なお、このような触媒成分は、排気ガスに対して特に顕著な触媒性能を発揮する。
Furthermore, in the present invention, the catalyst component supported on the surface of the substrate or whisker is not particularly limited as long as the catalyst performance can be improved. For example, the catalyst component contains a composition or element different from that of the supported substrate or whisker. It is desirable to do.
Examples of such a catalyst component include platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), gold (Au), tin (Sn), iron (Fe) or copper (Cu), and The element which concerns on these arbitrary combinations can be mentioned, and when combining, you may mix or alloy. Such a catalyst component exhibits particularly remarkable catalytic performance with respect to exhaust gas.
本発明の改質触媒は、支持体を更に備えていてもよく、かかる支持体は多孔質体であることが望ましい。支持体により、改質触媒を所望の形態に成型することが容易となり、また、孔径などの制御も容易となる。なお、支持体はウィスカーが形成されていなくてもよい。 The reforming catalyst of the present invention may further include a support, and the support is preferably a porous body. By using the support, it becomes easy to mold the reforming catalyst into a desired form, and it is easy to control the pore diameter and the like. Note that whiskers need not be formed on the support.
上記のような改質触媒は、例えば以下に述べるような方法で作製することができる。
（１）マンガンを含む合金やセラミックスの粉粒体の原料基体を密閉可能な炉に入れて不活性ガス（アルゴンや窒素）を導入して９００〜１０００℃で３０〜１０００分間加熱処理してマンガン酸化物を含有するウィスカーを形成する。
そして、従来公知の含浸法や、ＰＶＤ法、ＣＶＤ法などの蒸着法などにより触媒成分を担持して、ウィスカー付き触媒粒を得ることができる。
The reforming catalyst as described above can be produced, for example, by the method described below.
(1) Putting a raw material substrate of an alloy or ceramic powder containing manganese into a sealable furnace, introducing an inert gas (argon or nitrogen), and heat-treating at 900 to 1000 ° C. for 30 to 1000 minutes, manganese A whisker containing an oxide is formed.
And a catalyst particle with a whisker can be obtained by carrying a catalyst component by a conventionally known impregnation method, a vapor deposition method such as a PVD method or a CVD method.
（２）また、マンガンを含む合金やセラミックスの多孔質体の原料基体を用いることにより、ウィスカー付きの一体構造型改質触媒を得ることができる。
（３）更に、ニッケル発泡金属や合金メッシュなどの多孔質体である支持体にマンガンを含む合金やセラミックスの粉粒体を担持した原料基体を用いることによっても、ウィスカー付きの一体構造型改質触媒を得ることができる。
ここで、基体中のマンガンの含有量を制御することにより、ウィスカーの大きさを制御することもでき、上記（２）や（３）のように多孔質体の原料基体や支持体を用いることにより、改質触媒の多孔度や構造を容易に制御することができる。
(2) Further, by using a raw material substrate of an alloy containing manganese or a ceramic porous body, a monolithic reforming catalyst with whiskers can be obtained.
(3) Further, by using a raw material substrate carrying a manganese-containing alloy or ceramic powder on a porous support such as a nickel foam metal or alloy mesh, a monolithic modification with whiskers is also possible. A catalyst can be obtained.
Here, by controlling the manganese content in the substrate, the size of the whisker can also be controlled, and the porous material substrate or support is used as in (2) or (3) above. Thus, the porosity and structure of the reforming catalyst can be easily controlled.
なお、触媒成分の担持は、ウィスカーの形成前であれば、触媒成分を原料基体に予め担持しておく手順などが採用できる。また、ウィスカー形成後であれば、該ウィスカーに触媒成分を担持させる手順などが採用できる。更に、ウィスカーの形成中に触媒成分を担持させる手順も採用できる。これらの手順はいずれか１つを採用してもよいし、適宜組み合わせて採用してもよい。
図１は、本発明の改質触媒の走査型電子顕微鏡（ＳＥＭ）写真である。
The catalyst component may be loaded before the whisker is formed by a procedure in which the catalyst component is loaded on the raw material substrate in advance. Further, if the whisker is formed, a procedure for supporting the catalyst component on the whisker can be adopted. Furthermore, a procedure for supporting the catalyst component during the formation of the whisker can be employed. Any one of these procedures may be adopted, or a combination thereof may be adopted as appropriate.
FIG. 1 is a scanning electron microscope (SEM) photograph of the reforming catalyst of the present invention.
次に、本発明の排気ガス浄化用触媒について詳細に説明する。
上述の如く、本発明の排気ガス浄化用触媒は、上記本発明の改質触媒を用いたものであって、該改質触媒が排気ガス流路に配設されているものである。
特に触媒成分として、上述したＰｔ、Ｐｄ、Ｒｈ、Ｉｒ、Ａｕ、Ｓｎ、Ｆｅ又はＣｕなどの元素を適宜組み合わせることによって、炭化水素（ＨＣ）や一酸化炭素（ＣＯ）、窒素酸化物（ＮＯｘ）などを含む排気ガスを浄化することができる。
本発明の排気ガス浄化用触媒をいくつかの代表例により具体的に説明する。
Next, the exhaust gas purifying catalyst of the present invention will be described in detail.
As described above, the exhaust gas purifying catalyst of the present invention uses the reforming catalyst of the present invention, and the reforming catalyst is disposed in the exhaust gas passage.
In particular, hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx) can be obtained by appropriately combining the above-described elements such as Pt, Pd, Rh, Ir, Au, Sn, Fe or Cu as catalyst components. It is possible to purify exhaust gas including the like.
The exhaust gas purifying catalyst of the present invention will be specifically described with reference to some representative examples.
図２は、本発明の排気ガス浄化用触媒の一例を示す概略図である。かかる排気ガス浄化用触媒は、上記本発明の改質触媒の基体がペレット状をなして触媒容器に充填されており、このウィスカー付き触媒粒同士の間隙が上記触媒容器の排ガス上流側よりも排ガス下流側で小さいものである（同図（ａ）参照）。
このように、排ガス上流側で間隙を大きく、排ガス下流側で間隙を小さくすることにより、低圧力損失なものとすることができる。また、排気ガス中にはパティキュレートマター（ＰＭ）が含まれることがあり、このような構成とすることにより、ウィスカーがフィルターとして機能し、ＰＭは上流側で除去・燃焼され易く、排気ガス浄化用触媒は目詰まりが起こり難くなる。その結果、触媒性能が効率よく発揮され、排気ガス浄化用触媒の寿命を長くすることができる。
FIG. 2 is a schematic view showing an example of the exhaust gas purifying catalyst of the present invention. In this exhaust gas purifying catalyst, the base of the reforming catalyst of the present invention is packed in a catalyst container in the form of pellets, and the gap between the catalyst particles with whiskers is larger than the exhaust gas upstream side of the catalyst container. It is a small one on the downstream side (see FIG. 1A).
In this way, by reducing the gap on the upstream side of the exhaust gas and reducing the gap on the downstream side of the exhaust gas, low pressure loss can be achieved. In addition, particulate matter (PM) may be included in the exhaust gas. With such a configuration, the whisker functions as a filter, and PM is easily removed and burned upstream, so that exhaust gas purification is possible. The catalyst for use is less likely to clog. As a result, the catalyst performance is efficiently exhibited, and the life of the exhaust gas purifying catalyst can be extended.
ここで、「触媒容器」とは、排気ガス流路内に改質触媒を配設する容器であり、その形状は特に限定されるものではなく、排気ガス流路の一部分であってもよく、別個に設けてもよい。
例えば従来公知の一端が閉塞した複数個のセルを有し、隣接するセル間では、ひとつのセルの閉塞端と他のセルの開放端とが交互に配置された端面を有するハニカム担体、いわゆるチェッカードハニカムなどと称されるものであり、その端面が、複数個の異なるセルの閉塞端と開放端とで市松模様又はチェッカー板のような模様をなしているものであり、一方の端面と他方の端面とで、かかる市松模様におけるセル端部の開閉関係が逆転している担体を用いることができる。
Here, the “catalyst container” is a container in which the reforming catalyst is disposed in the exhaust gas flow path, and the shape thereof is not particularly limited, and may be a part of the exhaust gas flow path. It may be provided separately.
For example, a conventionally known honeycomb carrier having a plurality of cells whose one ends are closed, and an end face in which closed ends of one cell and open ends of other cells are alternately arranged between adjacent cells, a so-called check. It is called a card honeycomb or the like, and its end face has a checkered pattern or a checkerboard pattern with closed and open ends of a plurality of different cells, one end face and the other end It is possible to use a carrier in which the open / close relationship of the cell edge in the checkered pattern is reversed with the end face of the checkerboard.
また、「触媒容器の排ガス上流側」とは、適用される内燃機関の仕様や流入する排気ガスの性状などによって適宜定められるものであり、排気ガス浄化用触媒を低圧力損失なものとすることができればその位置については特に限定されるものではないが、例えば流入する排気ガス中のＰＭが存在しなくなる辺りまでを間隙の大きな上流側とすることが望ましい。 In addition, “the exhaust gas upstream side of the catalyst container” is appropriately determined according to the specifications of the applied internal combustion engine, the properties of the inflowing exhaust gas, etc., and the exhaust gas purifying catalyst has a low pressure loss. If possible, the position is not particularly limited. For example, it is desirable that the position where the PM in the inflowing exhaust gas does not exist is the upstream side having a large gap.
上述したいわゆるチェッカードハニカムにウィスカー付き触媒粒を充填する場合（図２（ｂ）参照。）には、備える複数のセルの全てについて、ウィスカー付き触媒粒同士の間隙が排ガス上流側よりも排ガス下流側で小さいものが本発明の排気ガス浄化用触媒に含まれることは言うまでもないが、備える複数のセルのうち、排ガス上流側に開放端を有するセル内においてウィスカー付き触媒粒同士の間隙を大きくし、排ガス下流側に開放端を有するセル内においてウィスカー付き触媒粒同士の間隙を小さくしたものも本発明の排気ガス浄化用触媒に含まれる。 When filling the so-called checkered honeycomb with the catalyst particles with whiskers (see FIG. 2 (b)), the gap between the catalyst particles with whiskers is downstream of the exhaust gas upstream of the exhaust gas upstream side for all of the plurality of cells provided. Needless to say, the exhaust gas purification catalyst of the present invention includes a small one on the side, but among the plurality of cells provided, the gap between the catalyst particles with whiskers is increased in the cell having the open end on the exhaust gas upstream side. In addition, the exhaust gas purifying catalyst of the present invention includes a catalyst in which the gap between the catalyst particles with whiskers is reduced in a cell having an open end on the exhaust gas downstream side.
なお、排ガス上流側のウィスカー付き触媒粒の間隙を大きくする手法としては、例えば比較的長くて太いウィスカーが形成されている触媒粒を排ガス上流側に充填し、比較的短くて細いウィスカーが形成されている触媒粒を排ガス下流側に充填することなどが挙げられる。 In addition, as a method of increasing the gap between the catalyst particles with whiskers on the exhaust gas upstream side, for example, the catalyst particles in which relatively long and thick whiskers are formed are filled on the exhaust gas upstream side, and relatively short and thin whiskers are formed. For example, filling the catalyst particles on the downstream side of the exhaust gas.
図３は、本発明の排気ガス浄化用触媒の他の一例を示す概略図である。かかる排気ガス浄化用触媒は、上記本発明の改質触媒が一体構造の多孔質体を形成しているものである。
代表的には、焼結合金や発泡金属などの金属基板、金属メッシュ（織布、不織布など）、ハニカム、円柱、円盤、円筒、コルゲート及びドーナツ状に成型したウィスカー付きの一体構造型改質触媒を排気ガス流路に配設したものである（同図（ａ）及び（ｂ）参照。）。
具体例としては、例えば多孔質体である金属基板により上述したようなチェッカードハニカムを形成し、次いで、加熱処理してウィスカーを形成し、更に触媒成分を担持して、チェッカードハニカム型の改質触媒を得、これを排気ガス流路に設置したものが挙げられる。
FIG. 3 is a schematic view showing another example of the exhaust gas purifying catalyst of the present invention. Such an exhaust gas purifying catalyst is one in which the reforming catalyst of the present invention forms a porous body having an integral structure.
Typically, a monolithic reforming catalyst with whiskers formed into a metal substrate such as sintered alloy or foam metal, metal mesh (woven fabric, non-woven fabric, etc.), honeycomb, cylinder, disk, cylinder, corrugated and donut shape. Is disposed in the exhaust gas flow path (see FIGS. 1A and 1B).
As a specific example, for example, a checkered honeycomb as described above is formed by a metal substrate that is a porous body, and then a heat treatment is performed to form whiskers. A catalyst obtained by obtaining a quality catalyst and installing it in an exhaust gas flow path can be mentioned.
また、第２の排気ガス浄化用触媒の好適例としては、一体構造をなす改質触媒が複数個あり、排ガス下流側の改質触媒のガス透過性より排ガス上流側の改質触媒のガス透過性が高いものが望ましい。かかる構成とすることにより、ＰＭは上流側で除去・燃焼され易く、排気ガス浄化用触媒は目詰まりが起こり難くなる。その結果、触媒性能が効率よく発揮され、排気ガス浄化用触媒の寿命を長くすることができる。 Further, as a preferred example of the second exhaust gas purification catalyst, there are a plurality of reforming catalysts having an integral structure, and the gas permeation of the reforming catalyst upstream of the exhaust gas is higher than the gas permeability of the reforming catalyst downstream of the exhaust gas. Those with high properties are desirable. By adopting such a configuration, PM is easily removed and burned on the upstream side, and the exhaust gas purification catalyst is less likely to be clogged. As a result, the catalyst performance is efficiently exhibited, and the life of the exhaust gas purifying catalyst can be extended.
図４は、本発明の排気ガス浄化用触媒の他の一例を示す概略図である。
具体例としては、例えばガス透過性が高い円盤状に成型したウィスカー付きの一体構造型改質触媒を上流側に配設し、上流側と比較してガス透過性が低い円盤状に形成したウィスカー付きの一体構造型改質触媒を下流側に配設した排気ガス浄化用触媒（同図（ａ）参照。）や、ガス透過性が高い円柱状に成型したウィスカー付きの一体構造型改質触媒を上流側に配設し、上流側と比較してガス透過性が低い円柱状に形成したウィスカー付きの一体構造型改質触媒を下流側に配設した排気ガス浄化用触媒が挙げられる（同図（ｂ）参照。）。
更には、チェッカードハニカム型の改質触媒において、上述したチェッカードハニカムにウィスカー付き触媒粒を充填する場合と同様に、備える複数のセルの全てについて、上流側においてウィスカーを粗く形成し、下流側においてウィスカーを密に形成したものや、備える複数のセルのうち、排ガス上流側に開放端を有するセル内においてウィスカーを粗く形成し、排ガス下流側に開放端を有するセル内においてウィスカーを密に形成したものが挙げられる（図５参照。）。
FIG. 4 is a schematic view showing another example of the exhaust gas purifying catalyst of the present invention.
As a specific example, for example, a whisker formed in a disk shape with a gas permeability lower than that of an upstream side is provided with a monolithic reforming catalyst with a whisker molded in a disk shape with a high gas permeability. Exhaust gas purification catalyst (see Fig. 1 (a)) provided with an integral structure reforming catalyst with a downstream, and an integral structure reforming catalyst with a whisker molded in a cylindrical shape with high gas permeability And an exhaust gas purification catalyst in which a monolithic reforming catalyst with a whisker formed in a columnar shape having a lower gas permeability than the upstream side is disposed on the downstream side. (Refer figure (b).).
Furthermore, in the checkered honeycomb type reforming catalyst, as in the case where the checkered honeycomb is filled with the catalyst particles with whiskers, whiskers are roughly formed on the upstream side of all the plurality of cells provided, and the downstream side Whisker is densely formed in a cell having an open end on the exhaust gas upstream side, and whisker is formed densely in a cell having an open end on the exhaust gas downstream side, among the cells having densely formed whiskers in (See FIG. 5).
上記のチェッカードハニカムにおけるウィスカーの形成状態は、例えば用いる金属基板に含まれるウィスカー構成元素の含有量を、基板の組成や支持体に対するウィスカー原料の担持量などを制御して、具体的には基板の外側で多く内側で少なくすることなどにより制御することができる。
また、ウィスカー付きの一体構造型改質触媒中にウィスカー付き触媒粒を充填するなど組合せることも可能であり、このような場合も本発明の範囲に含まれる。
The whisker formation state in the above-described checkered honeycomb is specifically determined by controlling the content of whisker constituent elements contained in the metal substrate to be used, the composition of the substrate, the amount of the whisker material supported on the support, and the like. It can be controlled by increasing the number outside and decreasing the number inside.
In addition, it is possible to combine such that the whisker-attached monolithic reforming catalyst is filled with whisker-attached catalyst particles.
以下、本発明を実施例及び比較例により更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.
（実施例１）
平均粒径５μｍのＮｉ−１０％Ｍｎ合金粉末からなる多孔質ロッド（０．１Ｌ）を、下記に示す条件で加熱処理して、表面にウィスカーを形成した。
Example 1
A porous rod (0.1 L) made of Ni-10% Mn alloy powder having an average particle size of 5 μm was heat-treated under the conditions shown below to form whiskers on the surface.
（加熱処理条件）
・加熱処理雰囲気 ：Ａｒガスフロー中
・加熱処理温度 ：昇温速度１０００℃／ｈで昇温し、１０００℃で２時間保持
(Heat treatment conditions)
・ Heat treatment atmosphere: Ar gas flow ・ Heat treatment temperature: Heated at a heating rate of 1000 ° C./h and held at 1000 ° C. for 2 hours
ウィスカー形成後、含浸法により表面にＰｔを担持して、本例の改質触媒を得た。得られた改質触媒の表面に形成されたウィスカーを、ＥＤＸで評価したところ、ＭｎとＯが検出された。 After the whisker formation, Pt was supported on the surface by an impregnation method to obtain the reforming catalyst of this example. When whiskers formed on the surface of the obtained reforming catalyst were evaluated by EDX, Mn and O were detected.
（比較例１）
平均粒径１μｍのゼオライト粉末と、平均粒径０．５μｍの酸化マンガン粉末を混合し、次いでペレット化した。含浸法により得られたペレットの表面に実施例１と同量のＰｔを担持して、本例の改質触媒を得た。
(Comparative Example 1)
Zeolite powder having an average particle diameter of 1 μm and manganese oxide powder having an average particle diameter of 0.5 μm were mixed and then pelletized. The same amount of Pt as in Example 1 was supported on the surface of the pellet obtained by the impregnation method to obtain a reforming catalyst of this example.
［性能評価］
上記各例の改質触媒を排気ガス流路に配設して、下記の表１に示す排気ガス（排気ガス温度４００℃）を空間速度１００００／ｈで導入した際のＮＯｘ転化率及びＣＯ転化率を測定した。得られた結果を表２に示す。
[Performance evaluation]
NOx conversion rate and CO conversion when the reforming catalyst of each of the above examples is disposed in the exhaust gas flow path and the exhaust gas (exhaust gas temperature 400 ° C.) shown in Table 1 below is introduced at a space velocity of 10,000 / h The rate was measured. The obtained results are shown in Table 2.
表２より、本発明の範囲に属する実施例１は、本発明外の比較例１と比較してＮＯｘ転化率及びＣＯ転化率が優れていることが分かる。 From Table 2, it can be seen that Example 1 belonging to the scope of the present invention is superior in NOx conversion rate and CO conversion rate as compared with Comparative Example 1 outside the present invention.
Claims (9)
上記基体がマンガンを含む合金及び／又はセラミックスを含有し、上記ウィスカーがマンガン酸化物を含有することを特徴とする改質触媒。 A reforming catalyst comprising a substrate, whiskers formed on the surface of the substrate, and a catalyst component supported on the surface of the substrate and / or whiskers,
A reforming catalyst, wherein the substrate contains an alloy and / or ceramic containing manganese, and the whisker contains a manganese oxide.
9. The exhaust gas according to claim 8, wherein there are a plurality of reforming catalysts having an integral structure, and the gas permeability of the reforming catalyst upstream of the exhaust gas is higher than the gas permeability of the reforming catalyst downstream of the exhaust gas. Gas purification catalyst.
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| JP2017080678A (en) * | 2015-10-28 | 2017-05-18 | 新日鐵住金株式会社 | Removal method of unburned component in exhaust gas, and removal method of nitrogen oxide in exhaust gas |
| US10335776B2 (en) | 2013-12-16 | 2019-07-02 | Basf Corporation | Manganese-containing diesel oxidation catalyst |
| US10864502B2 (en) | 2013-12-16 | 2020-12-15 | Basf Corporation | Manganese-containing diesel oxidation catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037690A (en) * | 1973-08-07 | 1975-04-08 | ||
| JPS63232850A (en) * | 1986-11-28 | 1988-09-28 | Nisshin Steel Co Ltd | Base material for catalytic converter |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5037690A (en) * | 1973-08-07 | 1975-04-08 | ||
| JPS63232850A (en) * | 1986-11-28 | 1988-09-28 | Nisshin Steel Co Ltd | Base material for catalytic converter |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10335776B2 (en) | 2013-12-16 | 2019-07-02 | Basf Corporation | Manganese-containing diesel oxidation catalyst |
| US10864502B2 (en) | 2013-12-16 | 2020-12-15 | Basf Corporation | Manganese-containing diesel oxidation catalyst |
| US11311865B2 (en) | 2013-12-16 | 2022-04-26 | Basf Corporation | Manganese-containing diesel oxidation catalyst |
| US11896962B2 (en) | 2013-12-16 | 2024-02-13 | Basf Corporation | Manganese-containing diesel oxidation catalyst |
| JP2017080678A (en) * | 2015-10-28 | 2017-05-18 | 新日鐵住金株式会社 | Removal method of unburned component in exhaust gas, and removal method of nitrogen oxide in exhaust gas |
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