JP3211409B2 - Exhaust gas purification filter material - Google Patents
Exhaust gas purification filter materialInfo
- Publication number
- JP3211409B2 JP3211409B2 JP27113892A JP27113892A JP3211409B2 JP 3211409 B2 JP3211409 B2 JP 3211409B2 JP 27113892 A JP27113892 A JP 27113892A JP 27113892 A JP27113892 A JP 27113892A JP 3211409 B2 JP3211409 B2 JP 3211409B2
- Authority
- JP
- Japan
- Prior art keywords
- dimensional
- exhaust gas
- filter material
- weight
- catalyst
- 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
Links
- 239000000463 material Substances 0.000 title claims description 16
- 238000000746 purification Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910002061 Ni-Cr-Al alloy Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 5
- 229910018487 Ni—Cr Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005254 chromizing Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006902 nitrogenation reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Filtering Materials (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、自動車用排ガス浄化
装置、石油ファンヒータの浄化装置に使用する排気ガス
浄化用のフィルタ材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a filter material for purifying exhaust gas used in an exhaust gas purifying apparatus for an automobile and a purifying apparatus for an oil fan heater.
【０００２】[0002]
【従来の技術と課題】自動車用、或いは石油ファンヒー
タ用排ガス浄化装置には、排気ガスを化学的に反応させ
て浄化するため貴金属系（白金等）の触媒が用いられて
いる。2. Description of the Related Art Noble metal (platinum or the like) catalysts are used in exhaust gas purifying apparatuses for automobiles or petroleum fan heaters in order to purify exhaust gases by chemical reaction.
【０００３】その触媒は、コーデイエライト製のハニカ
ムなどを担持体としてその表面に設けているが、従来の
担持体は表面が比較的平滑で担持力があまり強くない。[0003] The catalyst is provided on its surface with a honeycomb made of cordierite or the like as a support, but the conventional support has a relatively smooth surface and a low supporting force.
【０００４】これに対し、自動車エンジンにおける燃料
の燃焼技術、バーナにおける石油の燃焼技術の進歩でガ
スの排気温度は一段と高まる傾向にあり、このため、従
来の担持体では加熱−冷却が繰り返されると使用中に触
媒が剥落し、触媒による浄化効果を長時間維持すること
が難しくなってきている。On the other hand, the gas exhaust temperature tends to be further increased due to the advancement of fuel combustion technology in automobile engines and petroleum combustion technology in burners. For this reason, in the conventional carrier, heating and cooling are repeated. During use, the catalyst comes off, making it difficult to maintain the purification effect of the catalyst for a long time.
【０００５】そこで、この発明は、高温下での加熱冷却
の繰り返しによる温度変化や振動を受けても担持させて
ある触媒が安定して保持される排気ガス浄化用フィルタ
材を提供しようとするものである。Accordingly, an object of the present invention is to provide a filter material for purifying exhaust gas in which a supported catalyst is stably held even when subjected to temperature changes or vibrations due to repeated heating and cooling at high temperatures. It is.
【０００６】[0006]
【課題を解決するための手段】上記の課題を解決するた
め、この発明は、耐熱性の有る材料、好ましくはＮｉ−
Ｃｒ−Ａｌ系の材料で作られた三次元網状金属多孔体の
三次元骨格表面にアルミナ繊維状結晶を具備させたもの
を担持体とし、その担持体の骨格表面の結晶に触媒を絡
ませて担持させてあるものを排気ガス浄化用フィルタ材
として使用するようにしたのである。In order to solve the above-mentioned problems, the present invention provides a heat-resistant material, preferably Ni-
A three-dimensional mesh porous metal body made of a Cr-Al-based material and having a three-dimensional skeleton surface provided with alumina fibrous crystals is used as a support, and a catalyst is entangled with the crystal on the skeleton surface of the support to support the support. What was made to be used was used as a filter material for exhaust gas purification.
【０００７】なお、三次元骨格表面のアルミナ繊維状結
晶は、三次元網状金属多孔体がＮｉ−Ｃｒ−Ａｌ系のも
のである場合には、この多孔体を、大気中、或いは酸化
雰囲気（例えばＡｒとＯ2 の混合ガス雰囲気）中で８２
０〜９７０℃に加熱することにより容易に生成できる。The alumina fibrous crystal on the surface of the three-dimensional skeleton may be formed in the air or in an oxidizing atmosphere (for example, when the three-dimensional reticulated metal porous body is of a Ni—Cr—Al type). 82 in a mixed gas atmosphere of Ar and O 2 )
It can be easily produced by heating to 0 to 970 ° C.
【０００８】Ｎｉ−Ｃｒ−Ａｌ系の三次元網状金属多孔
体は、例えば、Ｎｉの三次元網状金属多孔体に、Ｃｒ、
Ａｌを拡散浸透して合金化することにより得られる。こ
の多孔体は、組成がＣｒ：１５〜４０重量％、Ａｌ：１
〜８重量％、残部：Ｎｉ及び不可避成分となるように拡
散浸透処理条件（粉末組成、粉末量、温度、時間）を選
定する。また、この組成中に、更に、イットリウム、ネ
オジウム等の希土類元素の１種もしくは２種以上を０．
０５〜０．５重量％含有させると、耐熱性の面でより優
れたものになる。[0008] The Ni-Cr-Al-based three-dimensional reticulated metal porous body includes, for example, Cr,
It is obtained by diffusing and infiltrating Al to form an alloy. This porous body has a composition of Cr: 15 to 40% by weight, Al: 1
８8% by weight, balance: Nitrogen and infiltration treatment conditions (powder composition, powder amount, temperature, time) are selected so as to be unavoidable components. Further, in this composition, one or more rare earth elements such as yttrium and neodymium are added to the composition.
When the content is from 0.5 to 0.5% by weight, the composition becomes more excellent in heat resistance.
【０００９】[0009]
【作用】三次元骨格表面のアルミナ繊維状結晶は、耐熱
性を有するため、１０００℃以上の高温にも耐える。そ
して、三次元骨格表面のアルミナ繊維状結晶により、三
次元骨格表面の平滑性が改善されて触媒が三次元骨格表
面の繊維に絡む形で強力に担持され、これにより、高温
下での加熱冷却の繰り返しによる温度変化や振動による
触媒の剥離脱落が防止される。The alumina fibrous crystal on the surface of the three-dimensional skeleton has heat resistance and can withstand a high temperature of 1000 ° C. or more. The alumina fibrous crystals on the surface of the three-dimensional skeleton improve the smoothness of the surface of the three-dimensional skeleton, and the catalyst is strongly supported in a form entangled with the fibers on the surface of the three-dimensional skeleton. Of the catalyst due to the temperature change and the vibration due to the repetition of the above is prevented.
【００１０】また、ＡｌをＣｒとともに合金化した三次
元網状金属多孔体は、Ａｌが硫黄や硫酸成分に強い安定
酸化物を形成するため、自動車の排ガスに対する耐食性
も良好である。[0010] Further, the three-dimensional reticulated metal porous body in which Al is alloyed together with Cr has a good corrosion resistance against exhaust gas from automobiles because Al forms a stable oxide which is strong against sulfur and sulfuric acid components.
【００１１】さらに、骨格表面が複雑に入り込むことに
より、触媒の担持量が多くなり、さらに排ガス中の固体
成分等の物理的捕集能力も高まる。[0011] Further, since the skeleton surface is complicatedly penetrated, the amount of supported catalyst is increased, and the ability to physically collect solid components and the like in the exhaust gas is also enhanced.
【００１２】以下に、Ｎｉ−Ｃｒ−Ａｌ系の三次元網状
金属多孔体について成分の含有量等を限定した理由を記
す。The reasons for limiting the content of components and the like in the Ni-Cr-Al-based three-dimensional reticulated metal porous body are described below.
【００１３】Ｃｒは、耐熱性、耐酸化性を確保する基本
元素である。本発明にあっては、アルミナ（Ａｌ
2 Ｏ3 ）皮膜が耐酸化性確保の主体となるが、Ｃｒが欠
乏するとこの皮膜の密着性や保護性が低下して耐酸化性
の維持に問題が出る。一方、Ｃｒが過剰になると靱性が
低下し、従ってこれ等の問題を共になくし得る範囲とし
てＣｒ含有量を１５〜４０重量％に規定した。[0013] Cr is a basic element for ensuring heat resistance and oxidation resistance. In the present invention, alumina (Al
The 2 O 3 ) film is the main component for securing the oxidation resistance. However, when Cr is deficient, the adhesion and protection of the film are reduced, and there is a problem in maintaining the oxidation resistance. On the other hand, when the Cr content is excessive, the toughness is reduced. Therefore, the content of Cr is set to 15 to 40% by weight as a range that can eliminate both of these problems.
【００１４】また、耐熱性を維持するためには、Ａｌも
１重量％は含有している必要がある。このＡｌは、１重
量％未満では耐熱性の改善効果が薄い。また、加工性の
点で８重量％以上含有するのは好ましくなく、従って、
その含有量は１〜８重量％とし、加工性の要求度合を考
えてその中から適当な値を選ぶ。Further, in order to maintain heat resistance, it is necessary that Al also contains 1% by weight. If this Al is less than 1% by weight, the effect of improving heat resistance is small. In addition, it is not preferable to contain 8% by weight or more from the viewpoint of processability.
The content is set to 1 to 8% by weight, and an appropriate value is selected from the values in consideration of the required degree of workability.
【００１５】Ｎｉ−Ｃｒ−Ａｌ系の三次元網状金属多孔
体は、純Ｎｉの三次元網状金属多孔体にクロマイジング
処理と称される拡散浸透処理を施してＮｉ−Ｃｒ系三次
元網状金属多孔体となし、次いで、これをパイプ状に成
型した後、カロライジング処理する２段合金化処理や、
純Ｎｉの三次元網状金属多孔体を先ず初めにパイプ状に
成型し、その後、Ｃｒ、Ａｌを同時に拡散浸透する１段
合金化処理等によって作ることができる。処理の条件次
第では骨格表面付近のＡｌ合金量を多くし、表面の耐熱
性をより一層向上させることもできる。しかし、この場
合も全体の合金組成に占めるＡｌの割合は１重量％から
最大８重量％が限度であり、これ以上の添加では、成形
体の表面と言えども振動衝撃により欠ける等、靱性につ
いての保証ができない。The Ni-Cr-Al-based three-dimensional reticulated metal porous body is obtained by subjecting a pure Ni three-dimensional reticulated metal porous body to a diffusion-infiltration treatment called a chromizing treatment, to obtain a Ni-Cr-based three-dimensional reticulated metal porous material. A two-stage alloying process of calorizing after forming this into a pipe, and then molding it into a pipe shape,
A three-dimensional net porous metal body made of pure Ni can be first formed into a pipe shape, and then formed by a one-stage alloying process in which Cr and Al are simultaneously diffused and infiltrated. Depending on the processing conditions, the amount of Al alloy near the skeleton surface can be increased, and the heat resistance of the surface can be further improved. However, also in this case, the proportion of Al in the entire alloy composition is limited from 1% by weight to a maximum of 8% by weight. I cannot guarantee it.
【００１６】アルミナ繊維状結晶は、骨格内にＡｌを拡
散させておいて熱処理するとできる。Ａｌはカロライン
ジング処理中の拡散時間を制御することにより、骨格の
表面から内側にかけて任意の深さで拡散浸透させること
ができるので、骨格表面は結晶が繊維状に成長し易い高
Ａｌ濃度を保ち、その一方で骨格内部は耐熱性を保持す
るのに必要なＡｌ量（１重量％）になるように拡散させ
ておくのが望ましい。The alumina fibrous crystal can be heat-treated with Al diffused in the skeleton. Al can be diffused and penetrated at an arbitrary depth from the surface of the skeleton to the inside by controlling the diffusion time during the carolining process, so the skeleton surface maintains a high Al concentration at which crystals grow easily into fibrous form. On the other hand, it is desirable that the inside of the skeleton is diffused so as to have an Al amount (1% by weight) necessary for maintaining heat resistance.
【００１７】アルミナ繊維状結晶のアスペクト比（太さ
に対する長さの比）をより大きくしたい場合には、骨格
表面から深さ０．５μｍまではＡｌ濃度を５％以上にす
ればよい。例えばＮｉ製の三次元網状金属多孔体を用い
て、クロマイズ処理したＮｉ−Ｃｒ三次元網状金属多孔
体を作製後、カロライジング処理によるＡｌ濃縮部を骨
格表面に形成したり、真空蒸着のような気相めっき、あ
るいは湿式めっきにより三次元骨格表面に純Ａｌ金属を
コーティングした後、さらに、不活性雰囲気下での拡散
浸透処理により、骨格表面のＡｌ濃度を適宜コントロー
ルすることができる。When it is desired to increase the aspect ratio (the ratio of the length to the thickness) of the alumina fibrous crystal, the Al concentration should be 5% or more from the skeleton surface to a depth of 0.5 μm. For example, using a Ni three-dimensional reticulated metal porous body, after producing a chromized Ni-Cr three-dimensional reticulated metal porous body, forming an Al-enriched portion on the skeleton surface by calorizing treatment, such as vacuum evaporation After coating the three-dimensional skeleton surface with pure Al metal by vapor phase plating or wet plating, the Al concentration on the skeleton surface can be appropriately controlled by diffusion / penetration treatment in an inert atmosphere.
【００１８】Ｎｉ−Ｃｒ−Ａｌ系の三次元網状金属多孔
体に、先に述べたイットリウム、ネオジウム等の希土類
元素を含有させると耐熱性は更に高まる。この希土類元
素の添加は、クロマイジング、カロライジング、或いは
１段合金化の際、拡散浸透材中に、添加しようとする元
素の粉末を混合しておけばよいが、０．５重量％以上の
添加は後工程における繊維状結晶の生成の妨げになる
し、また、０．０５重量％以下では耐熱性の向上効果が
現れない。If the Ni-Cr-Al-based three-dimensional reticulated metal porous body contains a rare earth element such as yttrium or neodymium as described above, the heat resistance is further enhanced. The addition of the rare earth element may be performed by mixing the powder of the element to be added into the diffusion infiltration material during chromizing, calorizing, or one-step alloying. The addition hinders the formation of fibrous crystals in the subsequent step, and the effect of improving heat resistance does not appear at 0.05% by weight or less.
【００１９】大気中又は酸化雰囲気中でアルミナ繊維状
結晶を生成するときの温度も、８２０〜９７０℃の範囲
でないとアスペクト比の大きな繊維状結晶が得られな
い。アスペクト比の大きなものを得るための特に好まし
い温度は８５０〜９５０℃であり、８５０℃では１０時
間以上、９５０℃では２時間以上あれば十分である。１
０００℃以上では凹凸の小さい平坦に近い酸化皮膜にな
り易く、生成した酸化皮膜の比表面積が小さ過ぎて担持
体の役目をするには適さない。また、８２０℃未満では
原子拡散の遅延により酸化の進行が遅れ、所望のウイス
カーに成長させるのに長時間の加熱が必要になる。If the temperature at which the alumina fibrous crystals are formed in the atmosphere or in an oxidizing atmosphere is not in the range of 820-970 ° C., a fibrous crystal having a large aspect ratio cannot be obtained. A particularly preferable temperature for obtaining a large aspect ratio is 850 to 950 ° C., and at 850 ° C., 10 hours or more, and at 950 ° C., 2 hours or more are sufficient. 1
If the temperature is higher than 000 ° C., the oxide film tends to become a nearly flat oxide film with small irregularities, and the specific surface area of the generated oxide film is too small to be used as a carrier. If the temperature is lower than 820 ° C., the progress of oxidation is delayed due to the delay of atomic diffusion, and long-time heating is required to grow a desired whisker.
【００２０】[0020]
【実施例】以下に、この発明の具体例を示す。The following is a specific example of the present invention.
【００２１】（実験例１）Ｎｉ目付け量１１００ｇ／ｍ
2 のＮｉ製三次元網状金属多孔体を拡散浸透法で合金化
処理してＮｉ−Ｃｒ（２５重量％）−Ａｌ（６重量％）
の三次元網状金属多孔体となし、次に、これを大気中８
７５℃で５時間加熱して骨格表面にアルミナ繊維状結晶
を成長させ、その後湿式法により触媒を担持させて排気
ガス浄化用フィルタ材（発明品１）を得た。(Experimental Example 1) Ni basis weight 1100 g / m
(2 ) Ni-Cr (25 wt%)-Al (6 wt%)
A three-dimensional reticulated metal porous body,
By heating at 75 ° C. for 5 hours, alumina fibrous crystals were grown on the skeleton surface, and then a catalyst was supported by a wet method to obtain an exhaust gas purifying filter material (Invention Product 1).
【００２２】また、比較のため、発明品１と同じ方法で
合金化した同一組成の三次元網状金属多孔体を大気中１
０５０℃で３時間加熱後、湿式法により触媒を担持させ
たもの（比較品１）も作った。これ等の触媒を担持させ
る前の骨格表面の走査型電子顕微鏡写真を熱処理前の骨
格表面状況写真（図１）と併せて図２、図３に示す。図
２から判るように、発明品１の骨格表面には、約３μｍ
長さのアルミナの繊維状結晶が密に生成しているが、比
較品１の骨格表面には図３に示すように繊維状結晶は見
られず、粒状結晶ができている。For comparison, a three-dimensional reticulated metal porous body of the same composition alloyed in the same manner as the invention 1 was used in air 1
After heating at 050 ° C. for 3 hours, a catalyst-supported product (comparative product 1) was also prepared by a wet method. FIGS. 2 and 3 show scanning electron micrographs of the skeleton surface before supporting these catalysts together with photographs of the skeleton surface before heat treatment (FIG. 1). As can be seen from FIG. 2, about 3 μm
Although fibrous crystals of alumina having a length are densely formed, fibrous crystals are not seen on the skeleton surface of the comparative product 1 as shown in FIG. 3, and granular crystals are formed.
【００２３】次に、これ等の試料について、白金−パラ
ジウム触媒を担持できる量を試験して調べたところ、発
明品１の能力が比較品１のそれよりもはるかに優れてい
た。Next, these samples were tested and examined for the amount capable of supporting the platinum-palladium catalyst. As a result, the performance of the invention product 1 was far superior to that of the comparison product 1.
【００２４】（実験例２）Ｎｉ目付け量１１００ｇ／ｍ
2 のＮｉ製三次元網状金属多孔体を拡散浸透法で合金化
処理して表１の組成となし、次いで、この金属多孔体を
ＡｒとＯ2 の混合ガス中で加熱した。このときのＯ2 分
圧は２０％一定とし、熱処理温度、熱処理時間を表１の
通りに変えた。そして、さらに湿式法により触媒を担持
させて発明品２〜９のフィルタ材を得た。(Experimental Example 2) Ni basis weight 1100 g / m
The Ni three-dimensional mesh porous metal body 2 was alloyed by a diffusion infiltration method to obtain the composition shown in Table 1, and then the porous metal body was heated in a mixed gas of Ar and O 2 . At this time, the O 2 partial pressure was kept constant at 20%, and the heat treatment temperature and the heat treatment time were changed as shown in Table 1. Then, a catalyst was further supported by a wet method to obtain filter materials of Invention Products 2 to 9.
【００２５】比較のため、発明品２〜９に用いたものと
同一組成の三次元網状金属多孔体を８００℃以下或いは
１０００℃以上の温度で加熱し、さらに、湿式法で触媒
を担持させた比較品２〜９も作成した。For comparison, a three-dimensional reticulated metal porous body having the same composition as that used in Invention Products 2 to 9 was heated at a temperature of 800 ° C. or less or 1000 ° C. or more, and further, a catalyst was supported by a wet method. Comparative products 2 to 9 were also prepared.
【００２６】また、Ｙ或いはＮｄの添加量を０．５重量
％以上にして熱処理条件は発明品と同じにした別の比較
品も作った。Further, another comparative product was prepared in which the amount of Y or Nd added was 0.5% by weight or more and the heat treatment conditions were the same as those of the invention product.
【００２７】[0027]
【表１】 発明品２〜９の骨格表面には、太さ０．２〜０．３μ
ｍ、長さ１〜５μｍのアルミナ繊維状結晶が成長してい
たが、比較品２〜９にはこのような結晶は無く、平滑な
結晶しか見られなかった。[Table 1] Inventive products 2 to 9 have a thickness of 0.2 to 0.3 μm on the skeleton surface.
Although alumina fibrous crystals having a length of m and a length of 1 to 5 μm were grown, Comparative Examples 2 to 9 did not have such crystals, and only smooth crystals were observed.
【００２８】また、Ｙ、Ｎｄの含有量を０．５重量％以
上にしたものは、熱処理条件が本発明品と同じであるに
も拘らず、繊維長の短い結晶になっており、Ｙ、Ｎｄの
過剰添加が結晶の成長をかえって阻害することが判っ
た。Further, those having a Y and Nd content of 0.5% by weight or more are crystals having a short fiber length, despite the heat treatment conditions being the same as those of the product of the present invention. It has been found that excessive addition of Nd rather inhibits crystal growth.
【００２９】次に、骨格表面に白金−ロジウム系の触媒
を担持させてある発明品２〜９を試料としてこれ等に１
０００℃、３０分加熱−冷却のサイクルを５００回加え
たが、触媒脱落や欠損、外観の変化はなかった。これに
対し、比較品２〜９は、触媒の担持量自体が本発明品よ
りも少なく、また、熱サイクルが５００回に達する前に
触媒の剥落等が起こり、排気ガス浄化用フィルタ材とし
て適したものになっていなかった。Next, invention samples 2 to 9 having a platinum-rhodium catalyst supported on the surface of the skeleton were used as samples.
After 500 cycles of heating-cooling at 000 ° C. for 30 minutes, the catalyst did not fall off, was missing, or did not change its appearance. On the other hand, the comparative products 2 to 9 have a smaller amount of supported catalyst than the product of the present invention, and the catalyst comes off before the thermal cycle reaches 500 times, and is suitable as a filter material for exhaust gas purification. Was not what it was.
【００３０】なお、発明品１〜９と比較品１〜９につい
て、排ガス中の「すす」の物理的捕集能力についても調
べた。触媒を担持させる前の試料を用いて同一構造のフ
ィルタを作り、ディーゼルエンジン車の排ガス中のすす
を捕集したところ、発明品の捕集量は対応する比較品の
２〜５倍に達していた。これから、骨格表面に繊維状結
晶を生じさせて触媒を強固に担持させてあるこの発明の
フィルタ材は、触媒による浄化効果だけでなく、ろ過に
よる浄化効果も充分に高まることが証明された。The invention product 1 to 9 and the comparison product 1 to 9 were also examined for their ability to physically collect soot in the exhaust gas. A filter having the same structure was made using the sample before supporting the catalyst, and soot in the exhaust gas of a diesel engine vehicle was collected. The amount of the invention product collected reached 2 to 5 times that of the corresponding comparative product. Was. From this, it was proved that the filter material of the present invention in which fibrous crystals were generated on the surface of the skeleton to firmly support the catalyst not only had a purifying effect by the catalyst but also a purifying effect by filtration was sufficiently enhanced.
【００３１】[0031]
【発明の効果】以上述べたように、この発明によれば、
三次元網状金属多孔体の三次元骨格表面にアルミナ繊維
状結晶を生成し、その結晶に絡ませて骨格表面に触媒を
担持させたので、担持が強固になり、高温下での加熱冷
却の繰り返しによる温度変化や振動によって触媒が簡単
に剥落することが無くなる。As described above, according to the present invention,
Alumina fibrous crystals were generated on the three-dimensional skeleton surface of the three-dimensional mesh-like metal porous body, and the catalyst was supported on the skeleton surface by being entangled with the crystals, so that the support became strong and repeated heating and cooling at high temperatures The catalyst does not easily peel off due to temperature change or vibration.
【００３２】また、三次元網状構造をしていることに加
え、表面積が大きくなることから、触媒の担持される量
も大巾に増加し、従って、触媒による浄化効果が強力に
発揮され、また、その効果が長期にわたって維持され、
物理的捕集能力も高まると云う効果が得られる。Further, in addition to having a three-dimensional network structure, the surface area is increased, so that the amount of the supported catalyst is greatly increased. Therefore, the purifying effect of the catalyst is strongly exerted. , Its effect is maintained for a long time,
The effect of increasing the physical trapping ability is obtained.
【図１】Ｎｉ−Ｃｒ（２５重量％）−Ａｌ（６重量％）
系の三次元網状金属多孔体の骨格表面状況を示す走査型
電子顕微鏡写真。FIG. 1—Ni—Cr (25% by weight) —Al (6% by weight)
Scanning electron micrograph showing the state of the skeleton surface of a three-dimensional reticulated porous metal body.
【図２】図１の三次元網状金属多孔体を用いて作られた
この発明の排気ガス浄化用フィルタ材の触媒担持前の骨
格表面の走査型電子顕微鏡写真。FIG. 2 is a scanning electron microscope photograph of a skeleton surface of the filter material for purifying exhaust gas of the present invention, which is formed by using the three-dimensional porous metal body of FIG. 1, before carrying a catalyst.
【図３】図１の三次元網状金属多孔体を用いて作られた
比較品の触媒担持前の骨格表面の走査型電子顕微鏡写
真。FIG. 3 is a scanning electron micrograph of a skeleton surface of a comparative product prepared using the three-dimensional porous metal body of FIG. 1 before supporting a catalyst.
Claims (5)
孔体の三次元骨格表面に、アルミナ繊維状結晶を有し、
この結晶に触媒を絡ませて担持させてある排気ガス浄化
用フィルタ材。An alumina fibrous crystal is provided on the surface of a three-dimensional skeleton of a Ni-Cr-Al-based three-dimensional reticulated metal porous body,
A filter material for purifying exhaust gas in which a catalyst is entangled and supported on these crystals.
格表面から深さ０．５μｍまでのＡｌ濃度が５重量％以
上であるものを用いた請求項１記載の排気ガス浄化用フ
ィルタ材。2. The filter material for purifying exhaust gas according to claim 1, wherein the three-dimensional porous metal body has an Al concentration of 5% by weight or more from the surface of the three-dimensional skeleton to a depth of 0.5 μm.
５〜４０重量％、Ａｌ：１〜８重量％、残部：Ｎｉ及び
不可避成分から成るものを用いた請求項１記載の排気ガ
ス浄化用フィルタ材。3. A three-dimensional mesh-like porous metal material, comprising: Cr: 1
The exhaust gas purifying filter material according to claim 1, wherein 5 to 40% by weight, Al: 1 to 8% by weight, balance: Ni and inevitable components are used.
記載の多孔体に更にイットリウム、ネオジウム等の希土
類元素の１種もしくは２種以上を０．０５〜０．５重量
％含有させたものを用いた請求項１記載の排気ガス浄化
用フィルタ材。4. A three-dimensional reticulated porous metal body.
2. The exhaust gas purifying filter material according to claim 1, wherein said porous material further contains one or more rare earth elements such as yttrium and neodymium in an amount of 0.05 to 0.5% by weight.
囲気中で８２０〜９７０℃に加熱して前記アルミナ繊維
状結晶を生じさせてある請求項２乃至４のいずれかに記
載の排気ガス浄化用フィルタ材。5. The exhaust gas according to claim 2, wherein the alumina fibrous crystal is generated by heating the three-dimensional network porous metal body to 820 to 970 ° C. in an oxidizing atmosphere. Filter material for purification.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27113892A JP3211409B2 (en) | 1992-09-14 | 1992-09-14 | Exhaust gas purification filter material |
| EP93919657A EP0626188A4 (en) | 1992-09-14 | 1993-09-13 | Exhaust gas cleaning filter medium and method of manufacturing the same. |
| PCT/JP1993/001308 WO1994006538A1 (en) | 1992-09-14 | 1993-09-13 | Exhaust gas cleaning filter medium and method of manufacturing the same |
| US08/390,995 US5830415A (en) | 1992-09-14 | 1995-02-21 | Filter member for purifying exhaust gas and method for manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27113892A JP3211409B2 (en) | 1992-09-14 | 1992-09-14 | Exhaust gas purification filter material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06190222A JPH06190222A (en) | 1994-07-12 |
| JP3211409B2 true JP3211409B2 (en) | 2001-09-25 |
Family
ID=17495850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27113892A Expired - Lifetime JP3211409B2 (en) | 1992-09-14 | 1992-09-14 | Exhaust gas purification filter material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3211409B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006130463A (en) * | 2004-11-09 | 2006-05-25 | Nissan Motor Co Ltd | Purification filter, production method for the same, and exhaust gas purification apparatus |
-
1992
- 1992-09-14 JP JP27113892A patent/JP3211409B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06190222A (en) | 1994-07-12 |
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