JP2815764B2 - Metal catalyst carrier excellent in catalyst adhesion and method for producing the same - Google Patents
Metal catalyst carrier excellent in catalyst adhesion and method for producing the sameInfo
- Publication number
- JP2815764B2 JP2815764B2 JP4229701A JP22970192A JP2815764B2 JP 2815764 B2 JP2815764 B2 JP 2815764B2 JP 4229701 A JP4229701 A JP 4229701A JP 22970192 A JP22970192 A JP 22970192A JP 2815764 B2 JP2815764 B2 JP 2815764B2
- Authority
- JP
- Japan
- Prior art keywords
- nitrogen
- catalyst carrier
- metal catalyst
- metal
- ppm
- 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 - Fee Related
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 38
- 239000002184 metal Substances 0.000 title claims description 38
- 239000003054 catalyst Substances 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- 239000011888 foil Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- IWBUYGUPYWKAMK-UHFFFAOYSA-N [AlH3].[N] Chemical compound [AlH3].[N] IWBUYGUPYWKAMK-UHFFFAOYSA-N 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- -1 and wrapping them Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 241000264877 Hippospongia communis Species 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000112 cooling gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 241001663154 Electron Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
Landscapes
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は自動車排ガス浄化装置用
の触媒コンバーター等で用いられる金属触媒担体に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal catalyst carrier used in a catalytic converter for an automobile exhaust gas purifying apparatus.
【０００２】[0002]
【従来の技術】従来、この種の触媒コンバーターは、特
開昭５７−７１８９８号公報等によって開示されている
ように、アルミニウムを含むフェライト系ステンレス鋼
合金からなる素材表面に、耐スポーリング性を向上させ
るため、アルミニウム拡散によりアルミナウイスカ層を
形成させている。このアルミナウイスカ層はα−アルミ
ナである。さらにアルミナウイスカ層の上に白金やロジ
ウム等の金属触媒を含浸させたウォッシュコート層が形
成されており、このウォッシュコート層が触媒反応の媒
体となるものである。ここでウォッシュコート層には、
例えばγ−アルミナが用いられる。2. Description of the Related Art Conventionally, as disclosed in Japanese Patent Application Laid-Open No. 57-71898, this type of catalytic converter has a spalling resistance on the surface of a ferritic stainless steel alloy containing aluminum. For improvement, an alumina whisker layer is formed by aluminum diffusion. This alumina whisker layer is α-alumina. Further, a washcoat layer impregnated with a metal catalyst such as platinum or rhodium is formed on the alumina whisker layer, and this washcoat layer serves as a catalyst reaction medium. Here, the wash coat layer
For example, γ-alumina is used.
【０００３】上記のような金属触媒担体のアルミニウム
ウイスカ層はウォッシュコート層の付着性の向上を図る
ため、アンカー効果を表面に持たす狙いで針状酸化物の
形態をしている。しかしながら、このアルミナウイスカ
層はアンカー効果を持たせるのに十分な大きさに成長さ
せるためには長時間の酸化加熱処理を行う必要があり、
成長した酸化物は剥離し易いものであるため取扱いが非
常に難しいものである。[0003] The aluminum whisker layer of the metal catalyst carrier as described above is in the form of a needle-like oxide with the aim of having an anchor effect on the surface in order to improve the adhesion of the washcoat layer. However, in order to grow this alumina whisker layer to a size large enough to have an anchor effect, it is necessary to perform a long-time oxidation heat treatment,
The grown oxide is very difficult to handle because it is easily peeled.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、従来のアル
ミナウイスカ層形成処理によりウォッシュコート層の付
着性の向上を図る方法とは異なる方法により、ウォッシ
ュ層の密着性を向上させたメタル触媒担体およびその製
造方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention relates to a metal catalyst carrier in which the adhesion of a wash layer is improved by a method different from the conventional method of improving the adhesion of a wash coat layer by forming an alumina whisker layer. And a method for producing the same.
【０００５】[0005]
【課題を解決するための手段】本発明は、上記目的のた
めに成分および熱処理の条件を検討した結果構成された
もので、その要旨とするところは以下のとおりである。
すなわち、 （１）Ａｌ含有ステンレス鋼製の平らな箔と波付け加工
した箔を交互に重ね合わせ、これらを多重に巻いた金属
ハニカムとこれらを囲む金属外筒からなるメタル触媒担
体において、前記箔の両表面が窒素−アルミニウムの化
合物を含有する皮膜で被覆されていること。 （２）（１）記載の皮膜中の窒素濃度の最高値が１０原
子％以上であること。 （３）（１）記載のＡｌ含有ステンレス鋼製の箔が重量
％でＣｒ：１０〜４０wt％、Ａｌ：１〜１０wt％を含有
し、残部がＦｅと不可避不純物からなる組成であるこ
と。 （４）Ａｌ含有ステンレス鋼製の平らな箔と波付け加工
した箔を交互に巻き込んだ金属ハニカムを金属外筒内に
装填してメタル触媒担体を形成した後、続いて酸素濃度
が１００ppm 以下の窒素ガスの加熱雰囲気ガス中で８０
０℃〜１３００℃に加熱し、続いて冷却を行うこと。 （５）（４）記載の加熱雰囲気ガスが （Ａ）酸素濃度が１００ppm 以下の窒素と水素の混合ガ
ス （Ｂ）酸素濃度が１００ppm 以下の窒素とアルゴンの混
合ガスのいずれかであること。 （６）Ａｌ含有ステンレス鋼製の平らな箔と波付け加工
した箔を交互に重ね合わせ、これらを多重に巻いた金属
ハニカムとこれらを囲む金属外筒からなるメタル触媒担
体の製造において、０．１torr以下の減圧下で８００℃
〜１３００℃で加熱処理を行い、続いて （Ａ）酸素濃度が１００ppm 以下の窒素ガス （Ｂ）酸素濃度が１００ppm 以下の窒素と水素の混合ガ
ス （Ｃ）酸素濃度が１００ppm 以下の窒素とアルゴンの混
合ガスのいずれかの雰囲気ガス中で冷却すること。 （７）（４）あるいは（６）に記載のＡｌ含有ステンレ
ス鋼製の箔が重量％でＣｒ：１０〜４０wt％、Ａｌ：１
〜１０wt％を含有し、残部がＦｅと不可避不純物からな
る組成であること。SUMMARY OF THE INVENTION The present invention has been made as a result of studying the components and heat treatment conditions for the above purpose, and the gist thereof is as follows.
(1) A flat metal foil containing aluminum and a corrugated foil are alternately superimposed on each other, and the metal catalyst carrier is formed of a metal honeycomb formed by wrapping these foils and a metal outer cylinder surrounding them. Are coated with a film containing a compound of nitrogen-aluminum. (2) The maximum value of the nitrogen concentration in the film described in (1) is 10 atomic% or more. (3) The aluminum-containing stainless steel foil described in (1) contains, by weight, 10:10 to 40% by weight of Cr and 1 to 10% by weight of Al, with the balance being Fe and unavoidable impurities. (4) A metal honeycomb in which a flat foil made of Al-containing stainless steel and a corrugated foil are alternately wound is loaded into a metal outer cylinder to form a metal catalyst carrier, and subsequently, an oxygen concentration of 100 ppm or less. 80 in a heated atmosphere of nitrogen gas
Heating to 0 ° C to 1300 ° C followed by cooling. (5) The heating atmosphere gas described in (4) is any one of (A) a mixed gas of nitrogen and hydrogen having an oxygen concentration of 100 ppm or less, and (B) a mixed gas of nitrogen and argon having an oxygen concentration of 100 ppm or less. (6) In the production of a metal catalyst carrier comprising a metal honeycomb formed by alternately stacking flat foils made of Al-containing stainless steel and corrugated foils, and wrapping them, and a metal outer cylinder surrounding the honeycombs. 800 ° C under reduced pressure of 1 torr or less
A heat treatment is performed at １1300 ° C., followed by (A) a nitrogen gas having an oxygen concentration of 100 ppm or less (B) a mixed gas of nitrogen and hydrogen having an oxygen concentration of 100 ppm or less (C) a nitrogen gas having an oxygen concentration of 100 ppm or less Cooling in any atmosphere gas of the mixed gas. (7) The aluminum-containing stainless steel foil according to (4) or (6) is, in terms of% by weight, Cr: 10 to 40% by weight, Al: 1
10 to 10% by weight, with the balance being Fe and inevitable impurities.
【０００６】[0006]
【作用】本発明のメタル触媒担体およびその製造方法
は、特定量のアルミニウムを含有するステンレス鋼に対
し、熱処理により表面に窒素とアルミニウムの化合物を
含有する皮膜を形成させ、その化合物とウォッシュコー
ト層（γ−アルミナ）との親和性の良さを利用して、ウ
ォッシュコート層の付着性を向上させることを特徴とし
ている。According to the metal catalyst carrier and the method for producing the same of the present invention, a film containing a compound of nitrogen and aluminum is formed on a surface of a stainless steel containing a specific amount of aluminum by heat treatment, and the compound and a wash coat layer are formed. It is characterized by improving the adhesion of the washcoat layer by utilizing the good affinity with (γ-alumina).
【０００７】本発明の限定理由を以下に説明する。本発
明のメタル触媒担体の箔表面における皮膜とその成分に
ついて説明する。窒素−アルミニウムの化合物はα−ア
ルミナに比べ活性であり、γ−アルミナを付着させる際
に酸化物から窒化物に変化するため、メタル表面とウォ
ッシュコート層との間には強い親和力が生じると考えら
れる。このことから、メタル触媒担体の箔表面は窒素と
アルミニウムの化合物を含む皮膜でなければならない。
また、皮膜中の成分としては窒素、アルミニウム以外に
酸素があるが、酸素とアルミニウムの化合物は窒素−ア
ルミニウムの化合物のような親和性を持たない。そのた
め箔表面の皮膜が十分な親和性を発揮するためには一定
濃度以上の窒素が皮膜中に含有している必要があり、皮
膜中の窒素濃度の最高値を１０原子％以上と定めた。The reasons for limiting the present invention will be described below. The coating on the foil surface of the metal catalyst carrier of the present invention and its components will be described. It is believed that the nitrogen-aluminum compound is more active than α-alumina and changes from oxide to nitride when γ-alumina is deposited, resulting in a strong affinity between the metal surface and the washcoat layer. Can be For this reason, the foil surface of the metal catalyst carrier must be a film containing a compound of nitrogen and aluminum.
The components in the film include oxygen in addition to nitrogen and aluminum, but a compound of oxygen and aluminum does not have an affinity like a compound of nitrogen-aluminum. Therefore, in order for the film on the foil surface to exhibit sufficient affinity, it is necessary for the film to contain nitrogen at a certain concentration or more, and the maximum value of the nitrogen concentration in the film is determined to be 10 atomic% or more.
【０００８】本発明のメタル触媒担体は耐食性および耐
酸化性に優れたものでなければならず、Ｃｒは重量％で
１０％以上必要であり、４０％を超えるとその効果が飽
和するばかりでなく、板の靭性が低下し製造性が著しく
困難になる。またＡｌは耐酸化性向上に有効であり、触
媒担持性を向上させる窒素−アルミニウムの化合物を表
面皮膜として形成させるためのＡｌの供給源であるため
重量％として１％以上含有する必要がある。しかしなが
らステンレス鋼中に多くのＡｌを含有させることは、鋼
の靭性を低下させ冷間圧延等の塑性加工性に悪影響をお
よぼすため、上限として１０％と定めた。[0008] The metal catalyst carrier of the present invention must be excellent in corrosion resistance and oxidation resistance. Cr needs to be 10% or more by weight, and when it exceeds 40%, not only the effect is saturated, but also In addition, the toughness of the sheet decreases, and the productivity becomes extremely difficult. Further, Al is effective for improving the oxidation resistance, and is a source of Al for forming a nitrogen-aluminum compound for improving the catalyst supporting property as a surface film, so that it must be contained in 1% or more by weight. However, the inclusion of a large amount of Al in stainless steel lowers the toughness of the steel and adversely affects plastic workability such as cold rolling. Therefore, the upper limit is set to 10%.
【０００９】表面の皮膜が窒素−アルミニウムの化合物
からなるステンレス鋼箔の製造方法は過去において研究
されていない技術である。これはＡｌは酸化アルミニウ
ム（アルミナ）の状態が非常に安定であるため、大気
（窒素約７９vol.％、酸素約２１vol.％）中での加熱や
気密性の良くない容器による窒素ガス中での加熱で酸化
しただけでは酸化物のみが生成され窒化物は全く生成さ
れないことから工業的にはあまり注目されなかったため
である。本発明者らはこのようなステンレス鋼箔の製造
方法として、酸化を極力防止しながら窒化を促進させる
熱処理の観点から研究を行い最適な方法および条件を見
出した。The method for producing a stainless steel foil whose surface film is made of a nitrogen-aluminum compound is a technique which has not been studied in the past. This is because Al is very stable in the state of aluminum oxide (alumina), so it can be heated in the atmosphere (about 79 vol.% Of nitrogen, about 21 vol.% Of oxygen) or in nitrogen gas by a container with poor airtightness. This is because only oxides are generated only by oxidizing by heating, and no nitrides are generated at all. The present inventors have conducted research from the viewpoint of a heat treatment that promotes nitridation while preventing oxidation as much as possible, and have found an optimum method and conditions as a method for producing such a stainless steel foil.
【００１０】本発明の熱処理雰囲気としては窒素−アル
ミニウムの化合物を生成させるために窒素ガス中で行わ
れなければならない。更に酸化を抑制するため窒素ガス
の酸素成分は酸素濃度で１００ppm 以下でなければなら
ない。またこの時の雰囲気ガスとして窒素ガス以外に水
素と窒素の混合ガスを用いた場合水素がＣｒ，Ａｌの酸
化を著しく抑制することから、窒素−アルミニウムの化
合物生成に効果的であった。但しこの場合も酸素濃度は
１００ppm 以下でなければならない。不活性ガスと窒素
ガスの混合ガスを用いた場合でも酸素濃度を１００ppm
以下に制御しておけば同様の効果を持つ。不活性ガスと
してはヘリウム、ネオン、アルゴン等があるが、工業的
に用いる場合コスト的に有利なアルゴンを採用した。The heat treatment atmosphere of the present invention must be performed in a nitrogen gas in order to generate a nitrogen-aluminum compound. To further suppress oxidation, the oxygen component of the nitrogen gas must be 100 ppm or less in oxygen concentration. In addition, when a mixed gas of hydrogen and nitrogen was used as the atmosphere gas in addition to the nitrogen gas, the hydrogen significantly suppressed the oxidation of Cr and Al, which was effective for the formation of a nitrogen-aluminum compound. However, also in this case, the oxygen concentration must be 100 ppm or less. Even when a mixed gas of inert gas and nitrogen gas is used, the oxygen concentration is 100 ppm
The same effect can be obtained if the following control is performed. Helium, neon, argon and the like are used as the inert gas, but argon which is economically advantageous in industrial use is employed.
【００１１】また、減圧下で一定温度まで加熱を行い窒
素ガスで冷却を行う方法も有効である。これは、酸化を
抑制しながら加熱された状態から窒素冷却中に一挙に窒
素−アルミニウムの化合物を生成させるもので本発明の
皮膜生成方法としては効果的である。Further, a method of heating to a certain temperature under reduced pressure and cooling with nitrogen gas is also effective. This is a method for forming a nitrogen-aluminum compound at once from a heated state while cooling nitrogen while suppressing oxidation, and is effective as a film forming method of the present invention.
【００１２】この時加熱は０．１torr以下で行う必要が
あり、０．１torrを超えると残留酸素のために酸化が起
こり、冷却中に窒化が起こり難くなる。一方、減圧を行
う前に予め窒素、不活性ガス等で置換した後に減圧を行
えば多少高い圧力下でも酸化が起き難くなる。At this time, the heating must be performed at 0.1 torr or less, and if it exceeds 0.1 torr, oxidation occurs due to residual oxygen, and nitriding hardly occurs during cooling. On the other hand, if the pressure is reduced after substituting with nitrogen, an inert gas or the like before the pressure reduction is performed, oxidation hardly occurs even under a somewhat higher pressure.
【００１３】冷却ガスは窒素−アルミニウムの化合物を
生成させる目的から、窒素を含むガスであり、酸素濃度
が低いものでなければならず、従って、雰囲気ガスとし
ては窒素ガス、窒素と水素の混合ガス、窒素とアルゴン
の混合ガスのいずれかであり、酸素濃度としては１００
ppm 以下でなければならない。The cooling gas is a gas containing nitrogen and has a low oxygen concentration for the purpose of producing a nitrogen-aluminum compound. Therefore, the atmosphere gas is a nitrogen gas or a mixed gas of nitrogen and hydrogen. , Or a mixed gas of nitrogen and argon, with an oxygen concentration of 100
Must be less than ppm.
【００１４】熱処理温度は化合物の生成に大きく寄与し
ており、低過ぎると反応が遅く本発明の窒素−アルミニ
ウムの化合物を含む皮膜が生成されない。即ち、反応が
十分進行する温度としては８００℃以上必要である。ま
た温度が余り高いと材料強度が極端に低下し成形した金
属ハニカムの形が崩れてしまうため上限は１３００℃で
ある。The heat treatment temperature greatly contributes to the formation of the compound. If the temperature is too low, the reaction is slow, and the film containing the nitrogen-aluminum compound of the present invention is not formed. That is, the temperature at which the reaction sufficiently proceeds must be 800 ° C. or higher. On the other hand, if the temperature is too high, the material strength is extremely reduced and the shape of the formed metal honeycomb collapses, so the upper limit is 1300 ° C.
【００１５】[0015]
【実施例】表１に本発明例および表２に比較例を示す。
合金系としてＣｒ，Ａｌの成分を記載しており残部はＦ
ｅと不可避不純物からなっている。加熱処理条件として
は雰囲気ガスの主成分と酸素濃度および加熱温度を記し
ており、減圧下の熱処理の場合（本発明例No．１１〜１
５、比較例No．２３〜２５）は真空度を記載している。
減圧下加熱では冷却条件として冷却ガスの成分、酸素濃
度を示しており、他は加熱雰囲気ガスで冷却を行ってい
る。皮膜中の窒素濃度はＡＥＳ（Auger ele-ctron spec
troscopy) 装置を用いて測定しており、例えば本発明例
No．４とNo．１１の材料についてＡＥＳの深さ方向分析
結果を図１，図２に示しているが、この結果からNo．４
の皮膜中の窒素濃度は２５原子％、No．１１は３８原子
％と読み取れる。また比較例No．１９は図３に示すよう
に窒素濃度が７原子％と低い値となっている。ウォッシ
ュコート付着性は付着量および外観を総合的に判断して
決定し、その結果、本発明例No．１〜１８はウォッシュ
コート付着性が良好であり、比較例No．１９〜２６は付
着性が悪い。EXAMPLES Table 1 shows examples of the present invention and Table 2 shows comparative examples.
The composition of Cr and Al is described as the alloy system, and the rest is F
e and inevitable impurities. As the heat treatment conditions, the main components of the atmospheric gas, the oxygen concentration, and the heating temperature are described.
5, Comparative Example No. 23 to 25) describe the degree of vacuum.
In the heating under reduced pressure, the components of the cooling gas and the oxygen concentration are shown as the cooling conditions, and the others are cooled by the heating atmosphere gas. The nitrogen concentration in the film is measured by AES (Auger ele-ctron spec.
troscopy) is measured using an apparatus, for example,
No. 4 and No. 1 and 2 show the results of the AES depth direction analysis for the material No. 11; 4
The nitrogen concentration in the film of No. 25 11 can be read as 38 atomic%. In Comparative Example No. No. 19 has a low nitrogen concentration of 7 atomic% as shown in FIG. The washcoat adhesion was determined by comprehensively judging the amount and appearance of the washcoat. Comparative Examples Nos. 1 to 18 have good washcoat adhesion. 19 to 26 have poor adhesion.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【表２】 [Table 2]
【００１８】[0018]
【発明の効果】以上のことから明らかな如く、本発明に
よれば、アルミナウイスカ層を形成させることなく、ウ
ォッシュコート層の付着性を向上させることが可能とな
る。As is apparent from the above, according to the present invention, it is possible to improve the adhesion of the washcoat layer without forming an alumina whisker layer.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明例No．４の熱処理後の表面の皮膜組成を
ＡＥＳによって分析した図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. FIG. 4 is a diagram in which the film composition of the surface after heat treatment of No. 4 is analyzed by AES.
【図２】本発明例No．１１の熱処理後の表面の皮膜組成
をＡＥＳによって分析した図である。FIG. 11 is a diagram in which the film composition of the surface after the heat treatment of No. 11 is analyzed by AES.
【図３】本発明例No．１９の熱処理後の表面の皮膜組成
をＡＥＳによって分析した図である。FIG. 3 shows the present invention sample No. 19 is a diagram in which the film composition of the surface after the heat treatment of No. 19 is analyzed by AES.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 伊藤 功 東京都千代田区大手町２−６−３ 新日 本製鐵株式会社内 (58)調査した分野(Int.Cl.6，ＤＢ名) B01J 21/00 - 38/74──────────────────────────────────────────────────続 き Continuing the front page (72) Inventor Isao Ito 2-6-3 Otemachi, Chiyoda-ku, Tokyo Nippon Steel Corporation (58) Field surveyed (Int. Cl. 6 , DB name) B01J 21/00-38/74
Claims (7)
付け加工した箔を交互に重ね合わせ、これらを多重に巻
いた金属ハニカムとこれらを囲む金属外筒からなるメタ
ル触媒担体において、前記箔の両表面が窒素−アルミニ
ウムの化合物を含有する皮膜で被覆されていることを特
徴とする触媒付着性に優れたメタル触媒担体。An aluminum-containing stainless steel flat foil and a corrugated foil are alternately superimposed on each other, and the metal catalyst carrier is composed of a metal honeycomb wound in multiple layers and a metal outer cylinder surrounding the honeycomb. Characterized in that both surfaces are coated with a film containing a compound of nitrogen-aluminum.
以上であることを特徴とする請求項１記載の触媒付着性
に優れたメタル触媒担体。2. The maximum nitrogen concentration in a film is 10 atomic%.
2. The metal catalyst carrier according to claim 1, which is excellent in catalyst adhesion.
０〜４０wt％、Ａｌ：１〜１０wt％を含有し、残部がＦ
ｅと不可避不純物からなる組成であることを特徴とする
請求項１記載の触媒付着性に優れたメタル触媒担体。3. A stainless steel foil containing Cr: 1 by weight%.
0 to 40 wt%, Al: 1 to 10 wt%, the balance being F
2. The metal catalyst carrier according to claim 1, wherein the metal catalyst carrier has a composition comprising e and unavoidable impurities.
付け加工した箔を交互に巻き込んだ金属ハニカムを金属
外筒内に装填してメタル触媒担体を形成した後、続いて
酸素濃度が１００ppm 以下の窒素ガスの雰囲気ガス中で
８００℃〜１３００℃に加熱し、続いて冷却を行うこと
を特徴とする触媒付着性に優れたメタル触媒担体の製造
方法。4. A metal honeycomb in which flat foils made of Al-containing stainless steel and corrugated foils are alternately wound are loaded into a metal outer cylinder to form a metal catalyst carrier, and then an oxygen concentration of 100 ppm A method for producing a metal catalyst carrier having excellent catalyst adhesion, wherein the metal catalyst carrier is heated to 800 ° C. to 1300 ° C. in an atmosphere gas of the following nitrogen gas and then cooled.
ス （Ｂ）酸素濃度が１００ppm 以下の窒素とアルゴンの混
合ガスのいずれかであることを特徴とする請求項４記載
の触媒付着性に優れたメタル触媒担体の製造方法。5. The heating atmosphere gas is any one of (A) a mixed gas of nitrogen and hydrogen having an oxygen concentration of 100 ppm or less, and (B) a mixed gas of nitrogen and argon having an oxygen concentration of 100 ppm or less. Item 5. The method for producing a metal catalyst carrier having excellent catalyst adhesion according to Item 4.
付け加工した箔を交互に重ね合わせ、これらを多重に巻
いた金属ハニカムとこれらを囲む金属外筒からなるメタ
ル触媒担体の製造において、０．１torr以下の減圧下で
８００℃〜１３００℃で加熱処理を行い、続いて （Ａ）酸素濃度が１００ppm 以下の窒素ガス （Ｂ）酸素濃度が１００ppm 以下の窒素と水素の混合ガ
ス （Ｃ）酸素濃度が１００ppm 以下の窒素とアルゴンの混
合ガスのいずれかの雰囲気ガス中で冷却することを特徴
とする触媒付着性に優れたメタル触媒担体の製造方法。6. A method for producing a metal catalyst carrier comprising a metal honeycomb formed by alternately stacking flat foils made of Al-containing stainless steel and corrugated foils, and winding these in multiple layers and a metal outer cylinder surrounding them. A heat treatment is performed at 800 ° C. to 1300 ° C. under a reduced pressure of 0.1 torr or less, followed by (A) a nitrogen gas having an oxygen concentration of 100 ppm or less (B) a mixed gas of nitrogen and hydrogen having an oxygen concentration of 100 ppm or less (C) A method for producing a metal catalyst carrier having excellent catalyst adhesion, characterized by cooling in an atmosphere gas of a mixed gas of nitrogen and argon having an oxygen concentration of 100 ppm or less.
Ｃｒ：１０〜４０wt％、Ａｌ：１〜１０wt％を含有し、
残部がＦｅと不可避不純物からなる組成であることを特
徴とする請求項４あるいは５記載の触媒付着性に優れた
メタル触媒担体。7. An aluminum-containing stainless steel foil containing 10% to 40% by weight of Cr and 10% to 10% by weight of Al in weight%;
6. The metal catalyst carrier having excellent catalyst adhesion according to claim 4, wherein the balance is a composition comprising Fe and unavoidable impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4229701A JP2815764B2 (en) | 1992-08-28 | 1992-08-28 | Metal catalyst carrier excellent in catalyst adhesion and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4229701A JP2815764B2 (en) | 1992-08-28 | 1992-08-28 | Metal catalyst carrier excellent in catalyst adhesion and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0671185A JPH0671185A (en) | 1994-03-15 |
| JP2815764B2 true JP2815764B2 (en) | 1998-10-27 |
Family
ID=16896348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4229701A Expired - Fee Related JP2815764B2 (en) | 1992-08-28 | 1992-08-28 | Metal catalyst carrier excellent in catalyst adhesion and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2815764B2 (en) |
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|---|---|---|---|---|
| US8556999B2 (en) * | 2007-07-27 | 2013-10-15 | Swift Fuels, Llc | Renewable engine fuel and method of producing same |
| US9145566B2 (en) | 2007-07-27 | 2015-09-29 | Swift Fuels, Llc | Renewable engine fuel and method of producing same |
| JP5872179B2 (en) | 2011-03-10 | 2016-03-01 | 株式会社エフ・シー・シー | Method for producing catalyst carrier for exhaust gas purification |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH0671185A (en) | 1994-03-15 |
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