JP2831117B2 - Combustion catalyst - Google Patents
Combustion catalystInfo
- Publication number
- JP2831117B2 JP2831117B2 JP27938990A JP27938990A JP2831117B2 JP 2831117 B2 JP2831117 B2 JP 2831117B2 JP 27938990 A JP27938990 A JP 27938990A JP 27938990 A JP27938990 A JP 27938990A JP 2831117 B2 JP2831117 B2 JP 2831117B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- combustion
- combustion catalyst
- sic
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は燃焼触媒に関し、更に詳しくはガスタービン
燃焼コンバスター、ボイラの低NOx化燃焼用、自動車排
ガス浄化（ガソリン車,CO/HC浄化，ディーゼル車，カー
ボンスーツ等）用及び航空機及び飛昇体用エンジンの失
火防止用触媒に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a combustion catalyst, and more particularly, to a gas turbine combustion combustor, a boiler for lowering NOx combustion, an automobile exhaust gas purification (gasoline vehicle, CO / HC purification, The present invention relates to a catalyst for preventing misfiring of engines for diesel vehicles, carbon suits, etc.), aircraft and flying vehicles.
従来、燃焼触媒は金属やセラミックスを基材とした成
形体に白金（Pt）やパラジウム（Pd）を担持したものが
主流である。耐熱性金属としては、高アルミナ含有メタ
ル、セラミックスとしてはMgO,Al2O3,TiO2結晶性複合酸
化物ムライトやコージェライトが知られている。成形体
としてはハニカムや格子状の平行流担体や発泡体等が適
用され、特に微粒子状カーボン質には発泡体が有効であ
る。Conventionally, the mainstream of a combustion catalyst is one in which platinum (Pt) or palladium (Pd) is supported on a molded body made of a metal or ceramic as a base material. As a heat-resistant metal, a high-alumina-containing metal is known, and as a ceramic, MgO, Al 2 O 3 , and TiO 2 crystalline composite oxide mullite and cordierite are known. As the molded body, a honeycomb, a lattice-shaped parallel flow carrier, a foam, or the like is applied, and a foam is particularly effective for particulate carbonaceous material.
金属材料は機械的強度、特に靭性に富むが、タングス
テンを除いては融点が低く、燃焼の条件、空／燃比の制
御がはずれると溶解する場合がある。Metal materials have high mechanical strength, especially toughness, but have a low melting point except for tungsten, and may dissolve if combustion conditions and air / fuel ratio are not controlled.
その点、セラミックスは1800℃程度までの高融点を示
すも、耐衝撃性に乏しい。しかも1800℃では燃焼触媒の
基材として満足できる耐熱性ではない。そのため、燃焼
触媒の実用化のためには、耐熱性を示し、かつ熱衝撃性
に強い触媒担体用基材の開発が望まれている。In that respect, ceramics have a high melting point up to about 1800 ° C, but have poor impact resistance. Moreover, at 1800 ° C., the heat resistance is not satisfactory as a base material for a combustion catalyst. Therefore, for practical use of a combustion catalyst, development of a substrate for a catalyst carrier that exhibits heat resistance and has high thermal shock resistance is desired.
本発明は上記技術水準に鑑み、かつ上記要望に応じ、
耐熱性でかつ熱衝撃に強い燃焼触媒を提供しようとする
ものである。The present invention has been made in view of the above technical level, and in response to the above demands,
An object of the present invention is to provide a combustion catalyst that is heat-resistant and resistant to thermal shock.
本発明は （１） メソフェーズを含有する石油ピッチを成形し、
その後炭化した成形体に炭化珪素を生成させた基材に、
白金及び／又はパラジウムを担持してなることを特徴と
する燃焼触媒、 （２） 前記１の基材を焼成して、表面に二酸化珪素の
被膜を形成させた基材に、白金及び／又はパラジウムを
担持してなることを特徴とする燃焼触媒、 である。The present invention provides (1) forming a petroleum pitch containing a mesophase,
Then, on the base material that produced silicon carbide in the carbonized molded body,
Combustion catalyst characterized by carrying platinum and / or palladium; (2) platinum and / or palladium on a substrate having a surface coated with silicon dioxide by firing the first substrate. A combustion catalyst characterized by carrying.
耐熱性もあり、極めて引張り強度の高い黒鉛構造を示
す炭素質の触媒基材化が本発明の主体である。The main subject of the present invention is to use a carbonaceous catalyst base material which has heat resistance and exhibits a graphite structure with extremely high tensile strength.
黒鉛構造を示す炭素質はいわゆる炭素繊維質と同形体
であり、本発明の黒鉛構造を示す炭素質は石油ピッチの
他に工業化学的原料、石炭液化物からも合成可能である
が前者（工業化学的原料）からの炭素質は高価であり、
後者（石炭液化物）は不純物が混入するため、高強度の
炭素質を狙う場合、不純物除去が必要となり、かえって
高価となるため、石油ピッチが好ましい。The carbonaceous material having a graphite structure is isomorphous to the so-called carbon fiber material, and the carbonaceous material having a graphite structure of the present invention can be synthesized from industrial chemical raw materials and coal liquefied products in addition to petroleum pitch. Carbon material from chemical raw materials is expensive,
Since the latter (coal liquefied material) contains impurities, it is necessary to remove impurities when aiming for high-strength carbonaceous materials.
黒鉛構造をもつ炭素質は酸素のない条件下では2500℃
程度の耐熱性を示す。しかし、酸素存在下では炭素質の
表面状態にもよるが400℃程度から減量（酸化）が始ま
り、特にPt,Pd等触媒活性成分を担持すると極めて短時
間で燃焼し消耗する。Carbonaceous material with graphite structure is 2500 ℃ under oxygen-free condition
Shows a degree of heat resistance. However, in the presence of oxygen, weight loss (oxidation) starts at about 400 ° C., depending on the surface condition of the carbonaceous material. In particular, when a catalytically active component such as Pt or Pd is carried, it burns and is consumed in a very short time.
この耐熱性炭素質を表面保護のため、本発明では炭化
珪素（SiC）化し、触媒基材として供するものであり、
更に耐酸化性をも付与するためSiCの表面を酸化させてS
iO2を形成させたものを触媒基材とするものである。In order to protect the surface of the heat-resistant carbonaceous material, in the present invention, silicon carbide (SiC) is formed and used as a catalyst substrate.
In addition, to impart oxidation resistance, the surface of SiC is oxidized to
The catalyst substrate on which iO 2 is formed is used.
2500℃以上の耐熱材である黒鉛化炭素質の表面をSiC
化し、さらにこのSiCからSiO2の緻密なガラス質被膜の
生成により、耐酸化性の賦与を行ない、耐熱性ならび機
械的強度をもつ触媒担体を供し、結果的に所望される燃
焼触媒が提供される。The surface of graphitized carbonaceous material which is heat resistant at 2500 ℃ or more
The formation of a dense vitreous film of SiO 2 from SiC provides oxidation resistance, provides a catalyst carrier having heat resistance and mechanical strength, and consequently provides a desired combustion catalyst. You.
（比較例１） 厚さ50μの20Cr−5Al−残Feなる耐熱鋼箔を400目／
（インチ）２のハニカム形状にした基材に、塩化白金酸
をエタノールに溶解してPtとして1wt％担持した。これ
を550℃にて３時間、H2還元して触媒とした。(Comparative Example 1) A heat-resistant steel foil having a thickness of 50μ and a thickness of 20Cr-5Al-remaining Fe of 400 meshes /
(Inch) Platinum chloroplatinic acid was dissolved in ethanol and carried on Pt by 1 wt% on the honeycomb-shaped substrate of No. 2 . This was reduced with H 2 at 550 ° C. for 3 hours to obtain a catalyst.
市販のコージュライトの400目／（インチ）２のハニ
カムに金属基材と同様にPt1wt％を担持した触媒を調製
した。A catalyst was prepared in which 400 wt./(inch) 2 of commercially available cordierite was loaded with 1 wt% of Pt in the same manner as the metal substrate.
これらの触媒上に、空気／灯油の化学量論比1.1に混
合したガスを空搭速度（S.V.）106・h-1,450℃の反応条
件で接触させると燃焼熱のため金属基材もコージュライ
ト基材の触媒も溶融解体した。On these catalysts, the air / kerosene stoichiometric ratio 1.1 mixed gas air搭速degree (SV) 10 6 · h -1 , even 450 ° C. Metal substrates for combustion heat and are contacted at reaction conditions The cordierite-based catalyst was also melted down.
（実施例１） メソフェーズ（工学的異方性相）を50％含有する石油
ピッチをｎ−ヘキサンを少量加え高圧下で加温し、常
温、常圧下に暴露して発泡体を形成させた。これを徐々
に加熱し脱水素することにより黒鉛化した。(Example 1) A petroleum pitch containing 50% of a mesophase (engineered anisotropic phase) was heated under high pressure with a small amount of n-hexane added thereto, and exposed to normal temperature and normal pressure to form a foam. This was gradually heated and dehydrogenated to be graphitized.
この構造体（黒鉛化した発泡体）は空孔率が83％で通
気性のある連続気孔を有している。この炭素構造体に比
較例と同様にPtを1wt％担持し、全く同様の条件にて灯
油にて燃焼試験をした。このPtを担持しない炭素構造体
は窒素気流中では2500℃でも何ら変化のない耐熱性材料
であるが、Ptを担持して触媒化した後は、炭素質が酸化
され、担持したPtは剥離すると同時に炭素質も燃焼消失
した。This structure (graphitized foam) has a porosity of 83% and has air-permeable continuous pores. 1% by weight of Pt was carried on this carbon structure as in the comparative example, and a combustion test was performed with kerosene under exactly the same conditions. This carbon structure that does not carry Pt is a heat-resistant material that does not change at all even at 2500 ° C. in a nitrogen stream, but after carrying and catalyzing Pt, the carbonaceous material is oxidized, and the carried Pt peels off. At the same time, the carbonaceous material was burnt away.
この炭素構造体を1000℃で加熱しSiH4と少量の空気を
接触せしめてて炭素構造体表面にSiCを形成させた。こ
のSiCは1000℃にて焼成（使用時でも、触媒調製時を問
わず）すると緻密なSiO2被膜を形成する。このような特
性をもつSiC表面に比較例と同様にPt1wt％を担持し、10
00℃に焼成し触媒化した。This carbon structure was heated at 1000 ° C. to bring SiH 4 into contact with a small amount of air to form SiC on the surface of the carbon structure. This SiC forms a dense SiO 2 coating when fired at 1000 ° C. (regardless of use or preparation of the catalyst). 1 wt% of Pt was supported on the SiC surface having such characteristics as in the comparative example,
It was calcined at 00 ° C to catalyze.
これを比較例と同様の条件にて灯油の燃焼を実施した
が、10分間後でも触媒に燃焼溶融、気散の変化は認めら
れなかった。The kerosene was burned under the same conditions as in the comparative example. However, even after 10 minutes, no change was observed in the combustion melting and air diffusion of the catalyst.
（実施例２） 前記の方法でSiCを形成させた炭素構造体に、比較例
と同じ方法（但し、Pdの原料は塩化パラジウム）でPdを
1wt％を担持して焼成した触媒を試作し、燃焼テストを
実施した。Pdの場合は400％以上の反応温度で充分燃焼
し、Pdの場合と同様全く支障はなかった。(Example 2) Pd was added to the carbon structure on which SiC was formed by the above-described method by the same method as in the comparative example (however, the raw material of Pd was palladium chloride).
A catalyst was prepared as a trial which carried 1 wt% and calcined, and a combustion test was performed. In the case of Pd, it burned sufficiently at a reaction temperature of 400% or more, and there was no problem as in the case of Pd.
（実施例３） Pt（0.5wt％）＋Pd（0.5wt％）を、表面にSiCを形成
させた炭素構造体に担持して焼成した後、比較例と同様
な条件で触媒化し、燃焼テストした。この触媒も燃焼は
400℃で充分続行し、Pdの場合の同様全く支障はなかっ
た。Example 3 Pt (0.5 wt%) + Pd (0.5 wt%) was carried on a carbon structure having SiC formed on the surface and calcined, then catalyzed under the same conditions as in the comparative example, and subjected to a combustion test. . This catalyst also burns
The process was continued sufficiently at 400 ° C., and there was no problem as in the case of Pd.
本発明のメソフェーズを含有する石油ピッチを炭素構
造体とし、この構造体にSiCを形成させた基材、または
このSiCの表面をSiC2にした基材よりなる触媒は、耐熱
性、耐酸化性を賦与し、ガスタービンに適用すれば低NO
x燃焼を可能とする。また、ボイラーのバーナー部に適
用しても低NOx燃焼を可能とする。A petroleum pitch containing the mesophase of the present invention is used as a carbon structure, and a catalyst comprising a base material having SiC formed on the structure or a base material having the surface of SiC formed of SiC 2 has heat resistance, oxidation resistance. Low NO when applied to gas turbines
x Enables combustion. Also, low NOx combustion can be achieved even when applied to the boiler burner.
さらに、ディーゼルエンジンの排ガス中に本発明の発
泡体構造物を基材とする触媒を採用すれば未燃カーボン
の捕集や捕集した微粒子の再燃焼を可能にする。さらに
航空気のエンジンに採用しておけば、万一失火した場合
でも再着火に効果がある。Furthermore, if a catalyst based on the foamed structure of the present invention is used in the exhaust gas of a diesel engine, it is possible to collect unburned carbon and reburn the collected fine particles. Furthermore, if it is used in an aeronautical engine, it is effective in re-ignition even in the event of a misfire.
フロントページの続き (56)参考文献 特開 平３−159908（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) B01J 21/00 - 38/74(56) References JP-A-3-159908 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) B01J 21/00-38/74
Claims (2)
し、その後炭化した成形体に炭化珪素を生成させた基材
に、白金及び／又はパラジウムを担持してなることを特
徴とする燃焼触媒。1. A combustion catalyst comprising: forming a petroleum pitch containing a mesophase; and then supporting platinum and / or palladium on a substrate obtained by forming silicon carbide in a carbonized formed body.
珪素の被膜を形成させた基材に、白金及び／又はパラジ
ウムを担持してなることを特徴とする燃焼触媒。2. A combustion catalyst comprising the substrate according to claim 1, wherein platinum and / or palladium are carried on a substrate having a surface coated with silicon dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27938990A JP2831117B2 (en) | 1990-10-19 | 1990-10-19 | Combustion catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27938990A JP2831117B2 (en) | 1990-10-19 | 1990-10-19 | Combustion catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04156947A JPH04156947A (en) | 1992-05-29 |
| JP2831117B2 true JP2831117B2 (en) | 1998-12-02 |
Family
ID=17610450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27938990A Expired - Lifetime JP2831117B2 (en) | 1990-10-19 | 1990-10-19 | Combustion catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2831117B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012024745A (en) * | 2010-07-28 | 2012-02-09 | Hitachi Ltd | Catalyst material and method of manufacturing the same |
-
1990
- 1990-10-19 JP JP27938990A patent/JP2831117B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04156947A (en) | 1992-05-29 |
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