JPH08168680A - Metal carrier for purifying exhaust gas of low thermal capacity and low back pressure - Google Patents
Metal carrier for purifying exhaust gas of low thermal capacity and low back pressureInfo
- Publication number
- JPH08168680A JPH08168680A JP6316323A JP31632394A JPH08168680A JP H08168680 A JPH08168680 A JP H08168680A JP 6316323 A JP6316323 A JP 6316323A JP 31632394 A JP31632394 A JP 31632394A JP H08168680 A JPH08168680 A JP H08168680A
- Authority
- JP
- Japan
- Prior art keywords
- thickness
- foil
- exhaust gas
- content
- honeycomb body
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 29
- 239000002184 metal Substances 0.000 title claims description 29
- 239000011888 foil Substances 0.000 claims abstract description 72
- 239000010935 stainless steel Substances 0.000 claims abstract description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 16
- 230000003647 oxidation Effects 0.000 description 26
- 238000007254 oxidation reaction Methods 0.000 description 26
- 239000000463 material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 230000006378 damage Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 230000008646 thermal stress Effects 0.000 description 5
- 230000002159 abnormal effect Effects 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 1
- 206010019345 Heat stroke Diseases 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、自動車、ボイラー、発
電用等の内燃機関の排ガス浄化用に使用される触媒のメ
タル担体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal carrier for a catalyst used for purifying exhaust gas from internal combustion engines such as automobiles, boilers and power generators.
【０００２】[0002]
【従来の技術】自動車、ボイラー、発電用等の内燃機関
の排ガス浄化用触媒の担体には、耐熱ステンレス鋼製の
外筒に、同ステンレス鋼製のメタルハニカム体を嵌入し
たメタル担体、あるいはセラミック製のハニカム体を嵌
入したセラミック担体が使用されている。メタル担体
は、セラミック担体に比べて熱容量が小さく、触媒が作
用する温度に早く加熱されるので、エンジン始動初期の
排ガス浄化能力が優れている。また、ハニカム体の壁
が、薄い金属箔からなるので排気抵抗が小さく、エンジ
ン出力の損失が少ないという利点を有している。2. Description of the Related Art As a carrier for an exhaust gas purifying catalyst for an internal combustion engine for automobiles, boilers, power generators, etc., a metal carrier in which a heat-resistant stainless steel outer cylinder is fitted with a metal honeycomb body made of the same, or a ceramic A ceramic carrier in which a honeycomb body made of metal is inserted is used. Since the metal carrier has a smaller heat capacity than the ceramic carrier and is heated to a temperature at which the catalyst acts, it has an excellent exhaust gas purifying ability at the initial stage of engine start. Further, since the wall of the honeycomb body is made of a thin metal foil, it has advantages that exhaust resistance is small and engine output loss is small.
【０００３】従来のメタル担体において、ハニカム体
は、排ガスに対する耐熱性を維持するため、Ａｌを含有
する耐熱ステンレス鋼箔で製造されており、箔の厚さは
５０μｍ前後のものが多かった。上記のような各種内燃
機関の排ガス浄化に際し、エンジン始動初期、ハニカム
体の温度が低く、触媒が作用する温度に達するまでの期
間は、浄化が不十分となる。したがって、より厳しい排
ガス規制に対応するには、排ガスによる触媒の昇温時間
をより短縮することのできるメタル担体が必要となる。In the conventional metal carrier, the honeycomb body is manufactured from a heat-resistant stainless steel foil containing Al in order to maintain heat resistance against exhaust gas, and the thickness of the foil is often around 50 μm. In the exhaust gas purification of various internal combustion engines as described above, the purification is insufficient in the period until the temperature at which the honeycomb body reaches the temperature at which the catalyst acts at the initial stage of engine startup. Therefore, in order to comply with stricter exhaust gas regulations, a metal carrier capable of further shortening the temperature rising time of the catalyst due to exhaust gas is required.
【０００４】この場合、ハニカム体の箔厚をより一層薄
くすることが有効であることが、特開平６−９９０７６
号公報の開示で公知であるが、箔厚を薄くすると耐酸化
性が低下することも知られている。これに対処するため
に、特開平１−１５９３８４号公報では、２５〜４５μ
ｍ厚のＦｅ−Ｃｒ−Ａｌ系合金箔の両面に、０．２〜
２．５μｍのＡｌ層を設ける技術を提案している。しか
しながら、本発明者らの実験では、薄箔化することによ
り、耐酸化性もさることながら、ハニカム体が、使用中
に高温・高圧の排ガスによってちぎれ飛んだり、熱応力
によってつぶれたり、破断したりするトラブルが頻発
し、その対策がより重要であることを認識した。In this case, it is effective to make the foil thickness of the honeycomb body even thinner, as disclosed in JP-A-6-99076.
As is known from the disclosure of Japanese Patent Laid-Open Publication No. JP-A No. 2003-163, it is also known that the oxidation resistance is reduced when the foil thickness is reduced. In order to deal with this, in Japanese Patent Application Laid-Open No. 1-159384, 25-45 μm is used.
On both sides of the Fe-Cr-Al alloy foil of m thickness, 0.2 to
A technique for providing a 2.5 μm Al layer is proposed. However, in the experiments conducted by the present inventors, by thinning the foil, the honeycomb body has a high oxidation resistance while being torn off by high-temperature and high-pressure exhaust gas during use, or crushed by thermal stress, and broken. We recognized that such troubles frequently occurred and that countermeasures were more important.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、自動車、ボ
イラー、発電用等の各種内燃機関の排ガス浄化用に使用
される触媒のメタル担体であって、ハニカム体の壁厚を
薄くすることにより、触媒が作用する温度に達するまで
の昇温時間を短縮して、エンジン始動初期の浄化能力を
向上するとともに、排気抵抗を下げてエンジン出力の損
失を低減することができ、かつ箔厚の薄手化によるハニ
カム体の機械的な破壊を防止し、併せて耐酸化性の低下
にも対処したメタル担体を提供することを目的とする。The present invention is a metal carrier for a catalyst used for exhaust gas purification of various internal combustion engines such as automobiles, boilers, power generators, and the like, by reducing the wall thickness of a honeycomb body. , It is possible to shorten the temperature rising time to reach the temperature at which the catalyst acts, improve the purification capacity in the initial stage of engine startup, reduce exhaust resistance to reduce engine output loss, and reduce the foil thickness. It is an object of the present invention to provide a metal carrier which prevents mechanical destruction of the honeycomb body due to the formation of the honeycomb structure and at the same time copes with the deterioration of the oxidation resistance.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
の本発明は、Ａｌを含有する耐熱ステンレス鋼箔からな
るハニカム体で構成され、該箔の厚さｔ（μｍ）が１７
μｍ以上４０μｍ未満、７００℃における耐力が３５０
／ｔ（ｋｇｆ／ｍｍ2 ）以上であり、かつ、Ａｌ含有量
ＸＡ（重量％）と厚さｔの関係が（１）式を満足し、Ｃ
ｒ含有量ＸＣ（重量％）と厚さｔの関係が（２）式を満
足していることを特徴とする低熱容量・低背圧の排ガス
浄化用メタル担体である。 １００／ｔ≦ＸＡ≦６ （１） １０＋２００／ｔ≦ＸＣ≦３０ （２）The present invention for achieving the above object comprises a honeycomb body made of a heat-resistant stainless steel foil containing Al, and the thickness t (μm) of the foil is 17
μm or more and less than 40 μm, proof stress at 700 ° C is 350
/ T (kgf / mm 2 ) or more, and the relationship between the Al content X A (% by weight) and the thickness t satisfies the expression (1), and C
The exhaust gas purifying metal carrier has a low heat capacity and a low back pressure, characterized in that the relationship between the r content X C (wt%) and the thickness t satisfies the expression (2). 100 / t ≦ X A ≦ 6 (1) 10 + 200 / t ≦ X C ≦ 30 (2)
【０００７】そして、耐熱ステンレス鋼箔が、Ｎｂ，Ｍ
ｏ，Ｔａ，Ｗの少なくとも１種を含有しており、該各元
素の含有量（重量％）と厚さｔ（μｍ）の関係が（３）
式を満足し、かつ、該各元素の含有量（重量％）が、Ｎ
ｂは１％以下、Ｍｏは４％以下、Ｔａは３％以下、Ｗは
４％以下であることが好ましく、さらに、重量％にて
０．０３％以上０．１５％以下の希土類元素（Ｙを含
む）を含有していることが好ましい。 ３５０／ｔ≦７＋１６．５Ｎｂ1/2 ＋１０．５Ｔａ1/2 ＋１．９Ｍｏ＋１．２Ｗ （３）The heat-resistant stainless steel foil is made of Nb, M
It contains at least one of O, Ta and W, and the relationship between the content (wt%) of each element and the thickness t (μm) is (3)
Satisfying the formula, and the content (% by weight) of each element is N
It is preferable that b is 1% or less, Mo is 4% or less, Ta is 3% or less, W is 4% or less, and further, 0.03% or more and 0.15% or less by weight% of the rare earth element (Y Is included). 350 / t ≦ 7 + 16.5Nb 1/2 + 10.5Ta 1/2 1.9Mo + 1.2W (3)
【０００８】[0008]
【作用】メタル担体の低熱容量化および低背圧化を達成
するためには、ハニカム体を構成する金属箔の薄手化を
図る必要がある。本発明者らは、薄手化した箔が、メタ
ル担体の使用環境に応じて、十分な耐熱性を有するよ
う、箔の適正な成分設計を行った。ここで、十分な耐熱
性を有するとは、高温・高速の排ガスで高サイクル疲労
を起こさず、エンジン始動および停止時の温度変化に伴
う熱応力や、冷熱サイクルによる熱疲労に抗することの
できる高温強度と、耐高温酸化性を有することである。In order to reduce the heat capacity and the back pressure of the metal carrier, it is necessary to thin the metal foil forming the honeycomb body. The present inventors have designed the foil appropriately so that the thinned foil has sufficient heat resistance depending on the environment in which the metal carrier is used. Here, having sufficient heat resistance does not cause high cycle fatigue with high temperature and high speed exhaust gas, and can withstand thermal stress due to temperature change at engine start and stop and thermal fatigue due to cold heat cycle. It has high-temperature strength and high-temperature oxidation resistance.
【０００９】高温強度と耐酸化性が重要であることは、
箔厚が５０μｍ前後の従来のメタル担体でも同じである
が、特に薄箔で構成されたメタル担体では、排ガスによ
る箔のちぎれや、熱応力によるハニカム体のつぶれや座
屈が生じ易く、また箔の酸化によって箔中のＡｌが枯渇
して異常酸化に至るまでの時間も短くなるため、高温強
度と耐酸化性には特別に配慮する必要がある。以下に、
本発明で箔厚や箔材成分組成を規定した理由を説明す
る。The importance of high temperature strength and oxidation resistance is
The same applies to the conventional metal carrier having a foil thickness of about 50 μm, but especially in the case of a metal carrier composed of thin foil, the foil is likely to be torn or the honeycomb body is likely to be crushed or buckled due to thermal stress. Since the time until the Al in the foil is depleted and abnormal oxidation is shortened due to the oxidation of Al, it is necessary to give special consideration to high temperature strength and oxidation resistance. less than,
The reason for defining the foil thickness and the composition of the foil material in the present invention will be described.
【００１０】まず、耐熱ステンレス鋼箔の厚さについて
検討した結果、１７μｍ未満では、如何に合金設計上で
配慮しても、座屈やハニカム体のつぶれが生じ易いう
え、高温排ガスによる高サイクル疲労を生じて、ハニカ
ム体が損傷を受けあるいは破壊された。そして、４０μ
ｍ以上では、ハニカム体の背圧が高くなり、排気抵抗を
下げてエンジン出力の損失を低減する上で、従来のメタ
ルハニカム体に対する優位性を発揮できない。また４０
μｍ以上では、触媒が作用する３００℃以上の温度に加
熱されるまでの時間が、従来のメタルハニカム体のもの
に近くなる。したがって、耐熱性を有するハニカム体用
として、箔の厚さを１７μｍ以上４０μｍ未満とした。First, as a result of studying the thickness of the heat-resistant stainless steel foil, if the thickness is less than 17 μm, buckling and crushing of the honeycomb body are likely to occur even if the alloy design is taken into consideration and high cycle fatigue due to high temperature exhaust gas. And the honeycomb body was damaged or destroyed. And 40μ
If it is m or more, the back pressure of the honeycomb body becomes high, and in order to reduce the exhaust resistance and reduce the loss of engine output, the advantage over the conventional metal honeycomb body cannot be exhibited. Again 40
When the thickness is more than μm, the time until the catalyst is heated to a temperature of 300 ° C. or more becomes close to that of the conventional metal honeycomb body. Therefore, the thickness of the foil is set to 17 μm or more and less than 40 μm for the honeycomb body having heat resistance.
【００１１】本発明においては、ハニカム体を構成する
箔の厚さを薄くするほど、箔の高温強度を高める必要が
ある。この場合、メタル担体の昇温過程で、箔の温度が
６００〜７５０℃のとき、外筒からハニカム体にかけて
の温度勾配が最も大きくなり、このとき最大の熱歪が生
じる。そして、６００℃から７５０℃における材料強度
が低いと、温度勾配が最大となる部位の近傍部に熱歪が
集中し、薄箔担体では特に箔の座屈やハニカム体のつぶ
れを生じ易く、箔の熱疲労破壊を早める。本発明者ら
は、これらの破壊を防止するには図１の斜線部に示すよ
うに、箔材の７００℃における耐力を、箔厚ｔ（μｍ）
との関係で３５０／ｔ（ｋｇｆ／ｍｍ2 ）以上にすべき
であることを知見した。ここにおいて、６００〜７５０
℃の材料強度を７００℃で代表させたのは、７００℃の
材料強度を高くすれば、６００〜７５０℃の強度もほぼ
比例して高くなるからである。In the present invention, it is necessary to increase the high temperature strength of the foil as the thickness of the foil forming the honeycomb body is reduced. In this case, in the process of raising the temperature of the metal carrier, when the temperature of the foil is 600 to 750 ° C., the temperature gradient from the outer cylinder to the honeycomb body becomes the largest, and the maximum thermal strain occurs at this time. When the material strength at 600 ° C. to 750 ° C. is low, the thermal strain is concentrated in the vicinity of the portion where the temperature gradient is maximum, and in the thin foil carrier, the buckling of the foil and the collapse of the honeycomb body are likely to occur. Accelerates thermal fatigue destruction. In order to prevent these destructions, the present inventors have determined the yield strength of the foil material at 700 ° C. as shown by the hatched portion in FIG.
It has been found that it should be 350 / t (kgf / mm 2 ) or more in relation to Here, 600 to 750
The reason why the material strength at 700C is represented by 700 ° C is that if the material strength at 700 ° C is increased, the strength at 600 to 750 ° C also increases substantially in proportion.
【００１２】つぎに、本発明におけるハニカム体の成分
組成について説明する。排ガスによる通常の酸化雰囲気
において、Ａｌ含有ステンレス鋼箔の表面には、Ａｌ2
Ｏ3の強固な皮膜が生成し、これが障壁となって、箔の
酸化が防止される。このため、Ａｌ2 Ｏ3 の生成に伴
い、箔に含有されるＡｌ量が消費されることになる。こ
こで、ハニカム体の表面積を一定とすれば、Ａｌ2 Ｏ3
生成のために消費されるＡｌ量は、箔の厚さに関係なく
一定であるから、箔を薄くした場合には、所要のＡｌ濃
度を高くする必要がある。Next, the component composition of the honeycomb body of the present invention will be described. In a normal oxidizing atmosphere due to exhaust gas, Al 2
A strong film of O 3 is formed, which serves as a barrier and prevents the foil from oxidizing. Therefore, the amount of Al contained in the foil is consumed as the Al 2 O 3 is produced. Here, if the surface area of the honeycomb body is constant, Al 2 O 3
Since the amount of Al consumed for generation is constant regardless of the thickness of the foil, it is necessary to increase the required Al concentration when the foil is thin.
【００１３】本発明者は、厚さ１７〜４０μｍのステン
レス鋼箔について、排ガスによる通常の酸化雰囲気での
耐酸化性を実験により評価した結果、箔の厚さｔ（μ
ｍ）に応じて、Ａｌ含有量ＸＡ（重量％）が、図２の曲
線ＡＢの上側（曲線ＡＢを含む）であれば問題ないこと
が判明した。曲線ＡＢを式に表すと、ＸＡ＝１００／ｔ
となる。そして、Ａｌ含有量が６％を超えると、通常の
圧延で箔まで製造するのが困難である。したがって、排
ガスによる通常の酸化雰囲気で耐酸化性を有するハニカ
ム体用として、箔の厚さｔが１７μｍ以上４０μｍ未満
で、かつＡｌ含有量ＸＡ（重量％）と箔の厚さｔ（μ
ｍ）の関係が、 １００／ｔ≦ＸＡ≦６ （１） を満足する範囲のＡｌを含有させることとした。The inventor of the present invention experimentally evaluated the oxidation resistance of a stainless steel foil having a thickness of 17 to 40 μm in a normal oxidizing atmosphere due to exhaust gas, and as a result, the foil thickness t (μ
It was found that there is no problem if the Al content X A (% by weight) is above the curve AB in FIG. 2 (including the curve AB) according to m). Expressing the curve AB in the formula, X A = 100 / t
Becomes When the Al content exceeds 6%, it is difficult to manufacture a foil by ordinary rolling. Therefore, for a honeycomb body having oxidation resistance in a normal oxidizing atmosphere due to exhaust gas, the foil thickness t is 17 μm or more and less than 40 μm, and the Al content X A (wt%) and the foil thickness t (μ
In the relationship of m), Al is included in the range of 100 / t ≦ X A ≦ 6 (1).
【００１４】また、Ａｌ含有ステンレス鋼箔において、
上記のように、箔表面に形成される酸化皮膜は主として
Ａｌ2 Ｏ3 であり、酸化の進行により主としてＡｌが消
費されるが、Ｃｒも若干ながら皮膜中に存在して酸化の
進行と共に消費される。特に、Ａｌ2 Ｏ3 皮膜を健全な
状態に保持しておくためには、母材中に一定量以上のＣ
ｒが存在する必要がある。したがって、Ｃｒ含有量も箔
厚の薄いものほど多くする必要があり、本発明者らの実
験によれば、Ｃｒ含有量ＸＣ（重量％）は、 １０＋２００／ｔ≦ＸＣ≦３０ （２） とすればよいことが判明した。上限の３０は、３０％を
超えてＣｒを添加すると材質が劣化するので設けた。In the Al-containing stainless steel foil,
As described above, the oxide film formed on the foil surface is mainly Al 2 O 3 , and Al is mainly consumed by the progress of oxidation, but Cr is also present in the film to some extent but is consumed as the oxidation progresses. It In particular, in order to keep the Al 2 O 3 coating in a sound state, a certain amount of C or more in the base metal
r must be present. Therefore, it is necessary to increase the Cr content as the foil thickness becomes thinner, and according to the experiments by the present inventors, the Cr content X C (% by weight) is 10 + 200 / t ≦ X C ≦ 30 (2) It turned out that The upper limit of 30 is provided because the material deteriorates when Cr is added in excess of 30%.
【００１５】ここで、本発明において、箔の高温強度
を、前記のように７００℃での耐力が３５０／ｔ（ｋｇ
ｆ／ｍｍ2 ）以上となるように高めるには、鉄と原子半
径のやゝ異なる元素を固溶させたり、あるいは、高温で
安定な析出物が分散して析出するような析出物形成元素
等を添加するのが有効である。特に、Ｎｂ，Ｍｏ，Ｔ
ａ，Ｗの少なくとも１種を重量％で（３）式を満足する
ように添加することが好ましい。ただし、これらの元素
は、過剰に添加すると、多量の析出物を生じるなど、材
質の劣化をきたすので、添加量の上限を、Ｎｂは１％、
Ｍｏは４％、Ｔａは３％、Ｗは４％とする。 ３５０／ｔ≦７＋１６．５Ｎｂ1/2 ＋１０．５Ｔａ1/2 ＋１．９Ｍｏ＋１．２Ｗ （３）Here, in the present invention, the high temperature strength of the foil is such that the yield strength at 700 ° C. is 350 / t (kg) as described above.
f / mm 2 ) or more, in order to increase it to a value higher than f / mm 2 ), an element having an atomic radius slightly different from that of iron is solid-dissolved, or a precipitate-forming element such that a stable precipitate is dispersed at high temperature Is effective. Especially, Nb, Mo, T
It is preferable to add at least one of a and W so as to satisfy the formula (3) in weight%. However, if these elements are added excessively, a large amount of precipitates are generated, which causes deterioration of the material, so the upper limit of the addition amount is 1% for Nb,
Mo is 4%, Ta is 3%, and W is 4%. 350 / t ≦ 7 + 16.5Nb 1/2 + 10.5Ta 1/2 1.9Mo + 1.2W (3)
【００１６】また本発明において、排ガスによる箔の耐
酸化性に関し、通常は、排気ガスの温度が９００℃以下
であるが、特に排気ガスの温度が９００℃を超える場合
は、箔の耐高温酸化性をより高める必要がある。そのた
め、本発明では、重量％にて０．０３％以上０．１５％
以下の希土類元素（Ｙを含む）を添加することが好まし
い。ここで、希土類元素はＹを含み、原子番号５７のＬ
ａから７１のＬｕまでをいい、また、個々の元素に分離
精製されてない、Ｌａ、Ｃｅ等の軽希土類元素の集合体
（ミッシュメタル）を添加する場合もある。本明細書で
はこの集合体をランタノイド（Ｌｎ）と記す。これら希
土類元素の合計が０．０３％未満では、９００℃を超え
る過酷な酸化雰囲気での耐高温酸化性の改善効果が不足
し、０．１５％を超えて添加すると耐酸化性が低下する
うえ、熱間加工性も悪化して熱間圧延が困難になる。In the present invention, regarding the oxidation resistance of the foil due to the exhaust gas, the temperature of the exhaust gas is usually 900 ° C. or lower, but especially when the temperature of the exhaust gas exceeds 900 ° C., the high temperature oxidation resistance of the foil is high. We need to be more sexual. Therefore, in the present invention, the weight% is 0.03% or more and 0.15% or more.
The following rare earth elements (including Y) are preferably added. Here, the rare earth element includes Y, and L of atomic number 57
In some cases, an aggregate (Misch metal) of light rare earth elements such as La and Ce which is not separated and refined into individual elements is added. In this specification, this aggregate is referred to as a lanthanoid (Ln). If the total content of these rare earth elements is less than 0.03%, the effect of improving the high temperature oxidation resistance in a severe oxidizing atmosphere exceeding 900 ° C is insufficient, and if it is added in excess of 0.15%, the oxidation resistance decreases. However, the hot workability also deteriorates and hot rolling becomes difficult.
【００１７】本発明の排ガス浄化用メタル担体は、ハニ
カム体が厚さ１７μｍ以上４０μｍ未満の薄手の耐熱ス
テンレス鋼箔で形成され、熱容量が小さいので、エンジ
ン始動初期、触媒が作用する３００℃以上の温度に達す
るまでの時間が短縮され、排ガス浄化能力が向上する。
さらに、ハニカム体の排気抵抗が低下し、エンジン出力
の損失を低減することができる。In the exhaust gas purifying metal carrier of the present invention, the honeycomb body is formed of a thin heat-resistant stainless steel foil having a thickness of 17 μm or more and less than 40 μm, and has a small heat capacity. The time to reach the temperature is shortened and the exhaust gas purification capacity is improved.
Furthermore, the exhaust resistance of the honeycomb body is reduced, and the loss of engine output can be reduced.
【００１８】そして、このように薄手化したハニカム体
であっても、構成材料のステンレス鋼成分が、目的に応
じ適正に設計されているので、特別に厳しいエンジンの
運転状態を除いて、使用時に座屈するようなことはな
く、エンジン始動時および停止時の温度変化による熱応
力、およびエンジン稼働時の高温高サイクル疲労による
破壊を生じることもない。さらに、必要な耐酸化性も確
保されていて問題ない。Even in such a thinned honeycomb body, the stainless steel components of the constituent materials are properly designed in accordance with the purpose, so that it can be used at the time of use except for particularly severe engine operating conditions. It will not buckle, and will not cause thermal stress due to temperature changes at the time of engine start and engine stop, or destruction due to high temperature and high cycle fatigue during engine operation. Furthermore, there is no problem because the required oxidation resistance is secured.
【００１９】[0019]
実施例１： 表１に示す各化学組成の１５〜３８μｍ厚
のステンレス鋼箔を試作し、このうち３０μｍ厚さの箔
で、波付け加工したものと、波付けしない平箔とを重ね
て巻回し、直径７８ｍｍ長さ１０５ｍｍのハニカム体を
製作した。これを厚さ１ｍｍのステンレス鋼製外筒に嵌
入し、ハニカム内およびハニカムと外筒の間を部分的に
ろう付けし、直径８０ｍｍのメタル担体を試作した。箔
製造の過程で厚さ２ｍｍの板から高温引張試験片を採取
し、７００℃での耐力を測定した結果を、合金組成から
計算によって算出したものと比較して表１に示す。さら
に、各箔の１５〜３８μｍの４種類の厚さの平箔につい
て、耐酸化性の試験を行った結果を併せて表１に示す。
なお、表１において高温耐力の計算値は、（３）式の右
辺の値である。Example 1 A 15 to 38 μm thick stainless steel foil of each chemical composition shown in Table 1 was prototyped, and a 30 μm thick foil was corrugated, and a flat foil that was not corrugated was overlapped and wound. By turning, a honeycomb body having a diameter of 78 mm and a length of 105 mm was manufactured. This was fitted into a stainless steel outer cylinder having a thickness of 1 mm and partially brazed inside the honeycomb and between the honeycomb and the outer cylinder, and a metal carrier having a diameter of 80 mm was experimentally manufactured. Table 1 shows the results of measuring the proof stress at 700 ° C. of a high temperature tensile test piece taken from a plate having a thickness of 2 mm in the process of foil production, in comparison with those calculated from the alloy composition. Further, Table 1 also shows the results of the oxidation resistance test performed on the flat foils of four thicknesses of 15 to 38 μm of each foil.
In Table 1, the calculated high-temperature yield strength is the value on the right side of equation (3).
【００２０】耐酸化性の試験は、使用される排気ガスの
最高温度より１００℃だけ高い温度で大気中２００時間
の連続加熱試験を行えばよいことが経験的に判ってい
る。すなわち、希土類元素を含まない１〜７の合金箔に
ついては、８５０℃で使用されることを想定し、９５０
℃×２００時間の試験を、また希土類元素を含有する８
〜１３の合金については、９５０℃で使用されることを
想定して、１０５０℃×２００時間の試験を行った。表
１において、耐酸化性評価の○は試験後も健全酸化状態
でＡｌ2 Ｏ3 皮膜が全面をカバーした状態を示す。△は
一部にＦｅ系の黒い異常酸化スポットが生じたことを示
す。また×は箔の多くの部分に異常酸化が発生したこと
を示す。さらに、試作した各メタル担体に触媒を担持さ
せ、排気量２０００ｃｃのガソリンエンジンのエキゾー
ストマニホールド直下に装着して耐久強度試験を行っ
た。各メタル担体について、ハニカム体の損傷状況の評
価結果を表１に示す。It has been empirically known that the oxidation resistance test may be performed by a continuous heating test for 200 hours in the atmosphere at a temperature higher by 100 ° C. than the maximum temperature of the exhaust gas used. That is, for the alloy foils 1 to 7 containing no rare earth element, it is assumed that they are used at 850 ° C.
℃ × 200 hours test, also containing rare earth elements 8
The alloys of Nos. 13 to 13 were tested at 1050 ° C. for 200 hours, assuming that they will be used at 950 ° C. In Table 1, ◯ of the oxidation resistance evaluation shows a state where the Al 2 O 3 coating covers the entire surface in a sound oxidation state even after the test. Δ indicates that a black Fe-based abnormal oxidation spot was partially generated. Moreover, x shows that abnormal oxidation occurred in many parts of the foil. Further, a catalyst was carried on each of the trial-produced metal carriers, and the catalyst was mounted directly below the exhaust manifold of a gasoline engine with a displacement of 2000 cc, and a durability strength test was conducted. Table 1 shows the evaluation results of the damage state of the honeycomb body for each metal carrier.
【００２１】エンジン試験は、５０００ｒｐｍフルスロ
ットル５分、エンジン停止・冷却１０分の冷熱行程を１
２００回繰返すエンジンベンチ試験を行って、５０〜１
００回毎に点検して評価したものである。表１に示すと
おり、（１），（２），（３）式にｔ＝３０を代入して
これらを満足する合金組成のものは、３０μｍ箔担体と
して７００℃耐力の合格レベルである１１．７ｋｇｆ／
ｍｍ2 以上の耐力を示し、また耐酸化性の試験にも合
格、エンジンベンチによる１２００回の冷熱耐久試験に
も耐え、ハニカムの局部的な破壊も生じなかったが、上
記各式のいずれかを満足しない箔組成のものでは、熱疲
労破壊によるハニカムのずれ、または異常酸化を生じ
た。In the engine test, 5000 rpm full throttle 5 minutes, engine stopping / cooling 10 minutes cold heat stroke 1
Performed an engine bench test repeated 200 times to obtain 50-1
It is inspected and evaluated every 00 times. As shown in Table 1, alloy compositions having t = 30 substituted into the formulas (1), (2), and (3) and satisfying these conditions have a pass level of 700 ° C proof stress as a 30 µm foil carrier. 7 kgf /
It exhibited a proof stress of mm 2 or more, passed the oxidation resistance test, and survived the 1200 heat / cold endurance test on the engine bench, and did not cause local destruction of the honeycomb. With the unsatisfactory foil composition, displacement of the honeycomb due to thermal fatigue fracture or abnormal oxidation occurred.
【００２２】[0022]
【表１】 [Table 1]
【００２３】実施例２： 表１のＮｏ．１０の合金箔に
ついて、厚さ１５、２０、３０、３８、４０、５０μｍ
の箔を試作し、実施例１と同様の担体を製造して、エン
ジンに装着し、回転数を５０００ｒｐｍにしたときの圧
損をマノメーターにより測定した。５０μｍ箔担体の圧
損を１．００としたときの各担体の圧損比を表２に示
す。これらの結果が示すように、箔厚が薄くなるにした
がい、確実に圧損は低くなることが判る。Example 2 No. 1 in Table 1 Thickness of 10, 20, 30, 38, 40, 50 μm for 10 alloy foils
The foil was manufactured as a prototype, a carrier similar to that of Example 1 was manufactured, mounted on an engine, and the pressure loss when the rotation speed was set to 5000 rpm was measured by a manometer. Table 2 shows the pressure loss ratio of each carrier when the pressure loss of the 50 μm foil carrier was 1.00. As shown by these results, it can be seen that the pressure loss surely decreases as the foil thickness decreases.
【００２４】[0024]
【表２】 [Table 2]
【００２５】実施例３： 実施例２の各厚さの箔を使用
した担体に触媒を担持させ、排気量２０００ｃｃのガソ
リンエンジンのエキゾーストマニホールド直下に装着
し、エンジンを始動させ、回転数１６００ｒｐｍ，吸入
空気圧−５０ｋＰａのやゝ負荷をかけた状態で運転し
て、担体中心部の温度が３００℃に達するまでの時間を
測定した。３００℃は、触媒が作用する最低温度であ
る。その結果、表３に示すように、３００℃までの到達
時間は箔厚の増加とともに長くなるが、その傾向は、箔
圧の大きい方で飽和気味となる。すなわち、箔厚が４０
μｍのものは、５０μｍのものに近い時間を示し、薄手
化の効果は、実施例２の背圧の場合と同様、厚さ４０μ
ｍ未満で顕著になることがわかる。Example 3: A catalyst was supported on a carrier using the foil of each thickness of Example 2, and the catalyst was mounted directly below the exhaust manifold of a gasoline engine with a displacement of 2000 cc, the engine was started, and the rotation speed was 1600 rpm and suction was performed. The operation was performed under a slight load of air pressure of −50 kPa, and the time until the temperature of the center of the carrier reached 300 ° C. was measured. 300 ° C. is the lowest temperature at which the catalyst works. As a result, as shown in Table 3, the arrival time up to 300 ° C. becomes longer as the foil thickness increases, but this tendency tends to be saturated at the higher foil pressure. That is, the foil thickness is 40
The thickness of μm shows a time close to that of 50 μm, and the effect of thinning is 40 μm in thickness as in the case of the back pressure of Example 2.
It can be seen that when it is less than m, it becomes remarkable.
【００２６】[0026]
【表３】 [Table 3]
【００２７】[0027]
【発明の効果】本発明は、自動車、ボイラー、発電用等
の内燃機関の排ガス浄化用に使用される触媒のメタル担
体であって、ハニカム体が厚さ１７μｍ以上４０μｍ未
満の薄手の耐熱ステンレス鋼箔で形成されているので、
熱容量が小さく、エンジン始動初期、触媒が作用する３
００℃以上の温度に達する時間が短縮され、排ガスの初
期浄化能力が向上する。さらに、ハニカム体の排気抵抗
が低下し、エンジン出力の損失を低減することができ
る。INDUSTRIAL APPLICABILITY The present invention is a metal carrier of a catalyst used for purifying exhaust gas of an internal combustion engine for automobiles, boilers, power generators, etc., and a thin honeycomb body having a thickness of 17 μm or more and less than 40 μm. Because it is made of foil,
The heat capacity is small, and the catalyst acts at the initial stage of engine start 3
The time to reach a temperature of 00 ° C. or higher is shortened, and the initial purification capability of exhaust gas is improved. Furthermore, the exhaust resistance of the honeycomb body is reduced, and the loss of engine output can be reduced.
【００２８】そして、このように薄手化したハニカム体
であっても、構成材料のステンレス鋼成分が、目的に応
じ適正に設計されているので、使用時に座屈するような
ことがなく、エンジン始動時および停止時の温度変化に
よる熱応力、およびエンジン稼働時の高温高サイクル疲
労による破壊を生じることもない。さらに、耐酸化性も
問題ない。したがって、本発明は、環境対策および省エ
ネ対策に大きく貢献するものである。Even in such a thin honeycomb body, since the stainless steel components of the constituent materials are properly designed according to the purpose, there is no buckling at the time of use and at the time of engine starting. Also, the thermal stress due to the temperature change at the time of stop and the fracture due to the high temperature and high cycle fatigue during the operation of the engine do not occur. Further, there is no problem with oxidation resistance. Therefore, the present invention greatly contributes to environmental measures and energy saving measures.
【図１】本発明における箔の厚さと７００℃における材
料強度の関係を示すグラフである。FIG. 1 is a graph showing the relationship between the foil thickness and the material strength at 700 ° C. in the present invention.
【図２】本発明における箔の厚さとＡｌ含有量の範囲を
示す図である。FIG. 2 is a diagram showing the range of foil thickness and Al content in the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｂ２１Ｄ 47/00 Ａ (72)発明者 太田 仁史 愛知県東海市東海町５−３ 新日本製鐵株 式会社名古屋製鐵所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI technical display location // B21D 47/00 A (72) Inventor Hitoshi Ota 5-3 Tokai-cho, Tokai-shi, Aichi Japan Steelmaking stock company Nagoya Steel Works
Claims (3)
なるハニカム体で構成され、該箔の厚さｔ（μｍ）が１
７μｍ以上４０μｍ未満、７００℃における耐力が３５
０／ｔ（ｋｇｆ／ｍｍ2 ）以上であり、かつ、Ａｌ含有
量ＸＡ（重量％）と厚さｔの関係が（１）式を満足し、
Ｃｒ含有量ＸＣ（重量％）と厚さｔの関係が（２）式を
満足していることを特徴とする低熱容量・低背圧の排ガ
ス浄化用メタル担体。 １００／ｔ≦ＸＡ≦６ （１） １０＋２００／ｔ≦ＸＣ≦３０ （２）1. A honeycomb body made of a heat-resistant stainless steel foil containing Al, having a thickness t (μm) of 1
7μm or more and less than 40μm, the proof stress at 700 ℃ is 35
0 / t (kgf / mm 2 ) or more, and the relationship between the Al content X A (% by weight) and the thickness t satisfies the expression (1),
A metal carrier for exhaust gas purification having a low heat capacity and a low back pressure, characterized in that the relationship between the Cr content X C (% by weight) and the thickness t satisfies the expression (2). 100 / t ≦ X A ≦ 6 (1) 10 + 200 / t ≦ X C ≦ 30 (2)
ａ，Ｗの少なくとも１種を含有しており、該各元素の含
有量（重量％）と厚さｔ（μｍ）の関係が（３）式を満
足し、かつ、該各元素の含有量（重量％）が、Ｎｂは１
％以下、Ｍｏは４％以下、Ｔａは３％以下、Ｗは４％以
下であることを特徴とする請求項１記載の低熱容量・低
背圧の排ガス浄化用メタル担体。 ３５０／ｔ≦７＋１６．５Ｎｂ1/2 ＋１０．５Ｔａ1/2 ＋１．９Ｍｏ＋１．２Ｗ （３）2. The heat-resistant stainless steel foil is Nb, Mo, T
at least one of a and W is contained, the relationship between the content (% by weight) of each element and the thickness t (μm) satisfies the expression (3), and the content of each element ( Wt%), but Nb is 1
% Or less, Mo is 4% or less, Ta is 3% or less, and W is 4% or less. The metal carrier for exhaust gas purification with low heat capacity and low back pressure according to claim 1. 350 / t ≦ 7 + 16.5Nb 1/2 + 10.5Ta 1/2 1.9Mo + 1.2W (3)
０３％以上０．１５％以下の希土類元素（Ｙを含む）を
含有していることを特徴とする請求項２記載の低熱容量
・低背圧の排ガス浄化用メタル担体。3. The heat-resistant stainless steel foil, when contained in a weight percentage of 0.
The metal carrier for exhaust gas purification having a low heat capacity and a low back pressure according to claim 2, wherein the metal carrier contains a rare earth element (including Y) in an amount of 03% or more and 0.15% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31632394A JP3210535B2 (en) | 1994-12-20 | 1994-12-20 | Metal carrier for purifying exhaust gas with low heat capacity and low back pressure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31632394A JP3210535B2 (en) | 1994-12-20 | 1994-12-20 | Metal carrier for purifying exhaust gas with low heat capacity and low back pressure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08168680A true JPH08168680A (en) | 1996-07-02 |
| JP3210535B2 JP3210535B2 (en) | 2001-09-17 |
Family
ID=18075856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31632394A Expired - Lifetime JP3210535B2 (en) | 1994-12-20 | 1994-12-20 | Metal carrier for purifying exhaust gas with low heat capacity and low back pressure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3210535B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002105606A (en) * | 2000-07-27 | 2002-04-10 | Nippon Steel Corp | Fe-Cr-Al BASED ALLOY |
| US6656435B1 (en) | 1998-03-30 | 2003-12-02 | Emitec Gesellschaft Fuer Emissionstechnologie Mbh | Honeycomb body with adsorber material, in particular, for a hydrocarbon trap |
| JP2007524001A (en) * | 2004-02-23 | 2007-08-23 | サンドビック インテレクチュアル プロパティー アクティエボラーグ | Cr-Al steel for high temperature applications |
| EP2048258A1 (en) | 2002-11-20 | 2009-04-15 | Nippon Steel Corporation | Honeycomb bodies employing high Al stainless steel sheet and process for production thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5760525B2 (en) | 2010-03-30 | 2015-08-12 | Ｊｆｅスチール株式会社 | Stainless steel foil and catalyst carrier for exhaust gas purification apparatus using the foil |
| JP5126437B1 (en) | 2011-04-01 | 2013-01-23 | Ｊｆｅスチール株式会社 | Stainless steel foil and catalyst carrier for exhaust gas purification apparatus using the foil |
-
1994
- 1994-12-20 JP JP31632394A patent/JP3210535B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6656435B1 (en) | 1998-03-30 | 2003-12-02 | Emitec Gesellschaft Fuer Emissionstechnologie Mbh | Honeycomb body with adsorber material, in particular, for a hydrocarbon trap |
| JP2002105606A (en) * | 2000-07-27 | 2002-04-10 | Nippon Steel Corp | Fe-Cr-Al BASED ALLOY |
| EP2048258A1 (en) | 2002-11-20 | 2009-04-15 | Nippon Steel Corporation | Honeycomb bodies employing high Al stainless steel sheet and process for production thereof |
| US7601672B2 (en) | 2002-11-20 | 2009-10-13 | Nippon Steel Corporation | High Al stainless steel sheet and honeycomb bodies employing them |
| JP2007524001A (en) * | 2004-02-23 | 2007-08-23 | サンドビック インテレクチュアル プロパティー アクティエボラーグ | Cr-Al steel for high temperature applications |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3210535B2 (en) | 2001-09-17 |
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