JP4358054B2 - Exhaust gas purification honeycomb structure - Google Patents

Exhaust gas purification honeycomb structure Download PDF

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JP4358054B2
JP4358054B2 JP2004209963A JP2004209963A JP4358054B2 JP 4358054 B2 JP4358054 B2 JP 4358054B2 JP 2004209963 A JP2004209963 A JP 2004209963A JP 2004209963 A JP2004209963 A JP 2004209963A JP 4358054 B2 JP4358054 B2 JP 4358054B2
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honeycomb structure
exhaust gas
superporous
honeycomb
porosity
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JP2004301130A (en
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健二 荒川
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Toyota Motor Corp
Nippon Steel Chemical and Materials Co Ltd
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Description

本発明は、ディーゼルエンジンなどから排出される排ガス中の粒子状物質(以下PMという)を捕集できるフロースルー型の排ガス浄化ハニカム構造体に関する。   The present invention relates to a flow-through type exhaust gas purification honeycomb structure capable of collecting particulate matter (hereinafter referred to as PM) in exhaust gas discharged from a diesel engine or the like.

ディーゼルエンジンの排ガス中には、カーボン、 SOF(Soluble Organic Fraction)、高分子有機化合物、硫酸ミストなどからなるPMが含まれ、大気汚染及び人体への悪影響の面からPMの排出を抑制しようとする動きが高まっている。PMの排出を抑制するには、フィルタによってPMを捕集する方法と、フロースルー型の触媒を用いてPMを燃焼除去する方法の2種類があり、それぞれのあるいは両方を組み合わせた技術開発が進められている。   Diesel engine exhaust gas contains PM composed of carbon, SOF (Soluble Organic Fraction), polymer organic compounds, sulfuric acid mist, etc., and tries to suppress PM emissions from the viewpoint of air pollution and adverse effects on the human body. The movement is growing. There are two ways to suppress PM emissions: a method of collecting PM using a filter and a method of burning and removing PM using a flow-through type catalyst. It has been.

フィルタとしては、ハニカム形状の耐熱性基材あるいはメタルハニカム体の両端開口を互い違いに市松状に閉塞したものが用いられている。このフィルタでは、セル隔壁を多孔質として通気性を付与し、セル隔壁を排ガスが通過する際にPMを濾過して捕集する。そして捕集されたPMは、排ガスの熱によってあるいは外部から加熱することによって燃焼され、これによってフィルタを再生している。   As the filter, a honeycomb-shaped heat-resistant substrate or a metal honeycomb body in which both end openings are alternately closed in a checkered pattern is used. In this filter, the cell partition walls are made porous to provide air permeability, and when exhaust gas passes through the cell partition walls, PM is filtered and collected. The collected PM is burned by the heat of exhaust gas or by heating from the outside, thereby regenerating the filter.

例えば特開平09−262415号公報には、金属質多孔体製平板と金属製波板を重ねてロール巻きし、入口開口と出口開口を互い違いに目止めしてなるフィルタが開示されている。このように熱電導性の高い金属製のフィルタとすることで、捕集されたPMの燃焼を均一に効率よく行うことができ、フィルタの溶損やクラックの発生を防止できる。また触媒コンバータと一体化できるので、振動などに対する強度が向上するという利点もある。   For example, Japanese Patent Application Laid-Open No. 09-262415 discloses a filter in which a metallic porous plate and a metal corrugated plate are overlapped and wound, and the inlet opening and the outlet opening are alternately staggered. Thus, by using a metal filter with high thermal conductivity, the collected PM can be burned uniformly and efficiently, and the filter can be prevented from being melted or cracked. Further, since it can be integrated with the catalytic converter, there is an advantage that the strength against vibration and the like is improved.

またフロースルー型の触媒はPMを濾し取る構造になっておらず、PMの粒径に対して十分大きい直径0.05mm、好ましくは 0.2mm以上の連通口を有し、貴金属を担持したアルミナなどからなる触媒コート層が連通路に形成されている。このフロースルー型の触媒は、ペレット状、フォーム状、ハニカム状など種々の形状とされている。   Further, the flow-through type catalyst does not have a structure for filtering out PM, and has a communication port having a sufficiently large diameter of 0.05 mm, preferably 0.2 mm or more with respect to the particle size of PM, and is made of alumina or the like supporting noble metal. A catalyst coat layer is formed in the communication path. This flow-through type catalyst has various shapes such as pellets, foams, and honeycombs.

そしてセル隔壁に貴金属を担持したフィルタも開発されている。このような触媒付フィルタによれば、捕集されたPMをより低温から燃焼させることができ、再生効率が高まる。また触媒によってPM以外のHC,COあるいはNOx を浄化することもできる。   A filter in which a noble metal is supported on a cell partition wall has also been developed. According to such a filter with a catalyst, the collected PM can be burned from a lower temperature, and the regeneration efficiency is increased. In addition, HC, CO or NOx other than PM can be purified by a catalyst.

ところが従来のフィルタでは、セル隔壁でPMを濾過する構造であるために、セル隔壁の細孔径を小さくしないとPMを捕集することができない。しかしセル隔壁の細孔径を小さくすると、圧損が増大するという不具合がある。またPMが堆積すると圧損がさらに増大してしまう。そこで圧損の増大を防止しつつPMを捕集するには、セル隔壁の面積を大きくすることが考えられるが、そうするとフィルタのサイズが大きくなり自動車の排気系への装着が困難となることもある。   However, since the conventional filter has a structure in which PM is filtered by the cell partition walls, PM cannot be collected unless the pore diameter of the cell partition walls is reduced. However, when the pore diameter of the cell partition is reduced, there is a problem that the pressure loss increases. Further, when PM is deposited, the pressure loss further increases. Therefore, in order to collect PM while preventing an increase in pressure loss, it is conceivable to increase the area of the cell partition wall, but doing so may increase the size of the filter and make it difficult to mount it on the exhaust system of an automobile. .

また貴金属を担持したフィルタにあっては、フィルタのサイズが大きくなると触媒効率が低下し、それを防ぐためには貴金属の担持量を多くしなければならずコストが高くなるという問題がある。   Further, a filter carrying a noble metal has a problem that when the size of the filter is increased, the catalyst efficiency is lowered, and in order to prevent this, the amount of the noble metal carried must be increased and the cost is increased.

一方、従来のフロースルー型の触媒では、圧損の増大という問題は生じないもののPMを捕集することが困難であり、フロースルー型の触媒を用いる場合には、PMを濾過するための手段が別に必要となるという問題がある。
特開平09−262415号公報
On the other hand, the conventional flow-through type catalyst does not cause an increase in pressure loss, but it is difficult to collect PM. When a flow-through type catalyst is used, there is no means for filtering the PM. There is a problem that it is necessary separately.
JP 09-262415 A

本発明は上記した事情に鑑みてなされたものであり、フロースルー型であってもPMを捕集できるようにすることを目的とする。   The present invention has been made in view of the above circumstances, and an object thereof is to enable PM to be collected even in a flow-through type.

上記課題を解決する本発明の排ガス浄化ハニカム構造体の特徴は、排ガスの入口と出口を連通する複数のハニカムセル内を排ガスが流通するフロースルー型の金属製ハニカム構造体であって、ハニカムセルの内壁の少なくとも一部は金属製不織布又はパンチングメタルよりなり孔径が零を超え 500μm以下、気孔率が55〜95%である超多孔質部をもつ多孔質金属板から形成され、超多孔質部で排ガス中の粒子状物質を捕集することにある。 A feature of the exhaust gas purification honeycomb structure of the present invention that solves the above problems is a flow-through type metal honeycomb structure in which exhaust gas flows through a plurality of honeycomb cells that communicate with the inlet and outlet of the exhaust gas. At least a part of the inner wall is made of a metallic nonwoven fabric or punched metal, and is formed from a porous metal plate having a superporous part with a pore diameter exceeding zero and not more than 500 μm and a porosity of 55 to 95%. The purpose is to collect particulate matter in the exhaust gas.

上記排ガス浄化ハニカム構造体では、ハニカムセルの内壁には、多孔質酸化物に貴金属を担持してなる触媒層が形成されていることが望ましい。   In the exhaust gas purifying honeycomb structure, it is desirable that a catalyst layer in which a noble metal is supported on a porous oxide is formed on the inner wall of the honeycomb cell.

本発明のハニカム構造体によれば、フロースルー型であってもPMを捕集することができるので、排ガスの流通抵抗はきわめて小さく、PMが超多孔質部に堆積したとしても圧損の増大はほとんど無い。また超多孔質部は金属製であるので、PMが堆積した後にPMを燃焼させる再生時における熱伝導性が高く、再生に要する時間を短縮することができる。さらに、触媒層を形成した場合は、排ガスの熱及びPMの酸化による発熱が伝導しやすく、低温域でPMを除去することができ低温域での再生も可能となる。   According to the honeycomb structure of the present invention, since PM can be collected even in the flow-through type, the flow resistance of the exhaust gas is extremely small, and even if PM accumulates in the superporous portion, the increase in pressure loss does not increase. almost none. Further, since the superporous portion is made of metal, the thermal conductivity during regeneration in which PM is burned after PM is deposited is high, and the time required for regeneration can be shortened. Furthermore, when the catalyst layer is formed, the heat of the exhaust gas and the heat generated by the oxidation of PM are easily conducted, PM can be removed at a low temperature range, and regeneration at a low temperature range is also possible.

本発明の排ガス浄化ハニカム構造体は、ハニカムセルの内壁の少なくとも一部には孔径が 500μm以下、気孔率が55〜95%で金属製の超多孔質部が形成されている。現象の詳細はまだ不明であるが、排ガスがハニカムセル内を通過する際に、排ガス流れと並行する極めて高い気孔率の超多孔質部がPMを捕集する作用をもつと考えられ、PMを30〜50%という高い捕集率で捕集することができる。そしてフロースルー型であるので、排ガスの流通抵抗はきわめて小さく、PMが超多孔質部に堆積したとしても圧損の増大はほとんど無い。   In the exhaust gas purifying honeycomb structure of the present invention, a metal superporous portion having a pore diameter of 500 μm or less and a porosity of 55 to 95% is formed on at least a part of the inner wall of the honeycomb cell. Although the details of the phenomenon are still unclear, it is thought that when the exhaust gas passes through the honeycomb cell, an extremely porous portion having a very high porosity parallel to the exhaust gas flow has an action of collecting PM. It can be collected at a high collection rate of 30-50%. And since it is a flow-through type, the flow resistance of the exhaust gas is extremely small, and even if PM accumulates in the superporous portion, there is almost no increase in pressure loss.

超多孔質部の孔径が 500μmより大きくなると細孔に捕集されたPMが容易に離脱して排出されてしまうため、孔径は 500μm以下とすることが必要である。孔径の下限は特に制限されないが、PMの最小粒径以上とすることが好ましい。また気孔率が55%未満ではPMの捕集が困難となり、95%を超えると超多孔質部の強度が不足して使用中に破損などの不具合が生じる。   When the pore diameter of the superporous portion is larger than 500 μm, PM trapped in the pores is easily detached and discharged, so the pore diameter needs to be 500 μm or less. The lower limit of the pore diameter is not particularly limited, but it is preferable to set it to the minimum particle diameter of PM or more. Further, when the porosity is less than 55%, it is difficult to collect PM, and when it exceeds 95%, the strength of the superporous portion is insufficient and problems such as breakage occur during use.

超多孔質部は、ハニカムセルの内壁の少なくとも一部に形成されている。例えばハニカムセルの内壁の表面に形成されていてもよいし、セル隔壁の厚さ方向の全体を超多孔質部とすることもできる。超多孔質部を内壁の表面に形成すれば、セル隔壁自体は気孔率を低く緻密に形成できるので、ハニカム構造体の強度が向上する。またセル壁厚を薄くしても十分な強度を有するようになるため、セル密度を高くすることができ排ガスとの接触面積が増大するため浄化能が向上する。 The superporous portion is formed on at least a part of the inner wall of the honeycomb cell. For example, it may be formed on the surface of the inner wall of the honeycomb cell, or the entire cell partition wall in the thickness direction may be a superporous portion. If the superporous portion is formed on the surface of the inner wall, the cell partition wall itself can be densely formed with a low porosity, thereby improving the strength of the honeycomb structure. Moreover, even if the cell wall thickness is reduced, the cell wall has sufficient strength, so that the cell density can be increased and the contact area with the exhaust gas is increased, so that the purification performance is improved.

またハニカム構造体の排ガス流れ方向における超多孔質部の位置は、上流側、中央部、下流部あるいはこれらの組合せから自由に選択することができ、排ガス流れ方向と垂直方向の位置は、中心部、外周部あるいは全体から自由に選択することができる。   Further, the position of the superporous portion in the exhaust gas flow direction of the honeycomb structure can be freely selected from the upstream side, the center portion, the downstream portion, or a combination thereof, and the position in the direction perpendicular to the exhaust gas flow direction is the center portion. , Can be freely selected from the outer periphery or the whole.

超多孔質部を排ガス流れ方向の上流部に形成した場合には、上流部でPMが捕集される。したがってハニカムセルの内壁に触媒層をもつ場合には、下流部において貴金属にPMが付着するのが抑制されるため、触媒層の活性低下を抑制することができる。また超多孔質部を排ガス流れ方向の下流部に形成した場合には、上流部の触媒層による低温始動時の性能悪化を抑制することができる。そして超多孔質部を排ガス流れ方向の中央部に形成した場合には、PM燃焼時の熱歪みが緩和されるため構造の信頼性が向上する。   When the superporous part is formed in the upstream part in the exhaust gas flow direction, PM is collected in the upstream part. Therefore, when the catalyst layer is provided on the inner wall of the honeycomb cell, the PM is prevented from adhering to the noble metal in the downstream portion, so that the decrease in the activity of the catalyst layer can be suppressed. Further, when the superporous portion is formed in the downstream portion in the exhaust gas flow direction, it is possible to suppress performance deterioration at the time of low temperature start-up by the upstream catalyst layer. When the superporous portion is formed in the center portion in the exhaust gas flow direction, the thermal distortion during PM combustion is alleviated, so that the reliability of the structure is improved.

さらに超多孔質部を外周部に形成した場合には、HC,CO,NOx の浄化性能が向上し、内周部に形成した場合には、捕集したPMが燃焼し易いという効果が得られる。 Further, when the superporous part is formed on the outer peripheral part, the purification performance of HC, CO, and NO x is improved, and when it is formed on the inner peripheral part, the collected PM is easily burned. It is done.

ハニカム構造体としては、金属製の波板と平板を重ねてロール状に巻回したものなどを用いることができる。平板及び波板の少なくとも一方の少なくとも一部に多孔質金属板を用いることで、超多孔質部を形成することができる。また平板及び波板全てを超多孔質部とすることもできる。平板を超多孔質部とすれば低圧損とすることができ、波板を超多孔質部とすればPM捕集率が向上する。 As the honeycomb structure , a metal corrugated plate and a flat plate rolled up in a roll shape can be used . By using a porous metal plate for at least a part of at least one of the flat plate and the corrugated plate, the superporous portion can be formed. Further, all of the flat plate and the corrugated plate can be made into a superporous portion. If the flat plate is a superporous portion, low pressure loss can be achieved, and if the corrugated plate is a superporous portion, the PM collection rate is improved.

多孔質金属板としてはメタル不織布、パンチングメタルなどを利用することができ、その孔径と気孔率が上記範囲となるようにすればよい。   As the porous metal plate, a metal nonwoven fabric, a punching metal or the like can be used, and the pore diameter and the porosity may be in the above range.

本発明のハニカム構造体の使用時には、超多孔質部にPMが堆積するため定期的に堆積したPM燃焼除去してPM捕集能を回復させる必要がある。これは高温の排ガスを供給する方法、あるいは外部ヒータなどで加熱する方法など、従来のフィルタと同様に行うことができる。触媒層をもたない場合には、 600〜 650℃でPMを燃焼除去してPM捕集能を回復することができる。   When the honeycomb structure of the present invention is used, since PM accumulates in the superporous portion, it is necessary to recover PM trapping ability by periodically removing the PM deposited. This can be performed in the same manner as a conventional filter, such as a method of supplying high-temperature exhaust gas or a method of heating with an external heater. If the catalyst layer is not provided, PM can be recovered by burning and removing PM at 600 to 650 ° C.

さらに本発明の排ガス浄化ハニカム構造体では、ハニカムセルの内壁には、多孔質酸化物に貴金属を担持してなる触媒層が形成されていることが望ましい。これにより排ガス中のHC,CO及びNOx を浄化することができ、排ガス浄化用触媒としても利用することができる。 Furthermore, in the exhaust gas purification honeycomb structure of the present invention, it is desirable that a catalyst layer in which a noble metal is supported on a porous oxide is formed on the inner wall of the honeycomb cell. Accordingly HC in the exhaust gas, it is possible to purify CO and NO x, it can be utilized as a catalyst for purifying an exhaust gas.

また触媒層は、少なくとも超多孔質部に形成されていることが望ましい。このような触媒層をもてば、捕集されたPMを 200〜 300℃の低温域から速やかに燃焼除去することができ、PM捕集能を連続的に回復させることができる。この触媒層は、担体粉末に貴金属を担持してなる触媒粉末をハニカムセルの内壁にコートして形成することができる。   The catalyst layer is desirably formed at least in the superporous portion. With such a catalyst layer, the collected PM can be quickly burned and removed from a low temperature range of 200 to 300 ° C., and the PM collecting ability can be continuously recovered. This catalyst layer can be formed by coating the inner wall of a honeycomb cell with a catalyst powder obtained by supporting a noble metal on a carrier powder.

担体粉末としては Al2O3,SiO2,TiO2,CeO2,ZrO2などを用いることができ、貴金属にはPt,Pd,Rh,Irなどを用いることができる。中でも特に活性が高いPtが好ましい。また触媒層を形成するには、担体粉末に予め貴金属を担持した触媒粉末をハニカム構造体にコートしてもよいし、先ず担体粉末からコート層を形成しそれに貴金属を担持することもできる。またアルカリ金属,アルカリ土類金属あるいは希土類元素から選ばれるNOx 吸蔵材をさらに担持すれば、排ガス中のNOx も効率よく浄化することができる。 Al 2 O 3 , SiO 2 , TiO 2 , CeO 2 , ZrO 2 or the like can be used as the carrier powder, and Pt, Pd, Rh, Ir or the like can be used as the noble metal. Among them, Pt having particularly high activity is preferable. In order to form the catalyst layer, the honeycomb structure may be coated with a catalyst powder in which a noble metal is previously supported on a carrier powder. Alternatively, a coating layer may be first formed from a carrier powder and a noble metal may be supported thereon. Further, if a NO x storage material selected from alkali metals, alkaline earth metals or rare earth elements is further supported, NO x in the exhaust gas can also be efficiently purified.

以下、実施例及び比較例により本発明を具体的に説明する。   Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

(実施例1)
図1に本実施例のハニカム構造体の要部断面図を示す。このハニカム構造体は厚さ 250μmのステンレス製不織布からなる平板1と、平板1から波形状に形成された波板2を重ねて、直径 103mm、長さ 155mmのロール状に巻回されてなり、平板1及び波板2はロウ付け接合されている。平板1と波板2とで形成されたセルの密度は 400/in2 である。また平板1及び波板2は共に気孔径が 100μm以下、気孔率が65%であり、ハニカム構造体の全体が本発明にいう超多孔質部となっている。
(Example 1)
FIG. 1 shows a cross-sectional view of the main part of the honeycomb structure of the present example. This honeycomb structure is formed by laminating a flat plate 1 made of a stainless non-woven fabric with a thickness of 250 μm and a corrugated plate 2 formed into a wave shape from the flat plate 1 into a roll having a diameter of 103 mm and a length of 155 mm. The flat plate 1 and the corrugated plate 2 are joined by brazing. The density of the cell formed by the flat plate 1 and the corrugated plate 2 is 400 / in 2 . Further, both the flat plate 1 and the corrugated plate 2 have a pore diameter of 100 μm or less and a porosity of 65%, and the entire honeycomb structure is the superporous portion referred to in the present invention.

(実施例2)
図2に本実施例のハニカム構造体の斜視図を示す。このハニカム構造体は、気孔率が異なること以外は実施例1と同様の平板1及び波板2から同様に形成された上流部3と、厚さ50μmのステンレス製金属箔からなる平板と波板を重ねてロール状に巻回されてなる下流部4とから構成されている。
(Example 2)
FIG. 2 shows a perspective view of the honeycomb structure of the present example. This honeycomb structure has an upstream portion 3 that is similarly formed from the flat plate 1 and the corrugated plate 2 similar to those of Example 1 except that the porosity is different, and a flat plate and corrugated plate that are made of a stainless steel metal foil having a thickness of 50 μm. And a downstream portion 4 wound in a roll shape.

上流部3は直径 103mm、長さ80mm、下流部4は直径 103mm、長さ75mmに形成され、ロウ付けによって互いに接合されている。上流部3及び下流部4は、共にセルの密度は 400/in2 である。また上流部3の平板及び波板は共に気孔径が 100μm以下、気孔率が85%であり、上流部3が本発明にいう超多孔質部となっている。 The upstream portion 3 is formed with a diameter of 103 mm and a length of 80 mm, and the downstream portion 4 is formed with a diameter of 103 mm and a length of 75 mm, and is joined to each other by brazing. Both the upstream part 3 and the downstream part 4 have a cell density of 400 / in 2 . Further, both the flat plate and the corrugated plate of the upstream portion 3 have a pore diameter of 100 μm or less and a porosity of 85%, and the upstream portion 3 is a superporous portion referred to in the present invention.

(実施例3)
図3に本実施例のハニカム構造体の斜視図を示す。このハニカム構造体は、厚さ50μmのステンレス製金属箔からなる平板と波板を重ねてロール状に巻回されてなる上流部5と、気孔率が異なること以外は実施例1と同様の平板1及び波板2から同様に形成された下流部6とから構成されている。
(Example 3)
FIG. 3 shows a perspective view of the honeycomb structure of the present example. This honeycomb structure is the same flat plate as in Example 1 except that the porosity is different from the upstream portion 5 in which a flat plate made of a stainless steel metal foil having a thickness of 50 μm and a corrugated plate are wound in a roll shape. 1 and a downstream portion 6 formed similarly from the corrugated plate 2.

上流部5は直径 103mm、長さ 100mm、下流部6は直径 103mm、長さ55mmに形成され、ロウ付けによって互いに接合されている。上流部5及び下流部6は、共にセルの密度は 400/in2 である。また下流部6の平板及び波板は共に気孔径が 100μm以下、気孔率が85%であり、下流部6が本発明にいう超多孔質部となっている。 The upstream portion 5 has a diameter of 103 mm and a length of 100 mm, and the downstream portion 6 has a diameter of 103 mm and a length of 55 mm, and is joined to each other by brazing. Both the upstream part 5 and the downstream part 6 have a cell density of 400 / in 2 . The flat plate and corrugated plate of the downstream portion 6 both have a pore diameter of 100 μm or less and a porosity of 85%, and the downstream portion 6 is a superporous portion according to the present invention.

(実施例4)
図4に本実施例のハニカム構造体の斜視図を示す。このハニカム構造体は、厚さ50μmのステンレス製金属箔からなる平板と波板を重ねてロール状に巻回されてなる上流部7と、気孔率が異なること以外は実施例1と同様の平板1及び波板2から同様に形成された中央部8と、上流部7と同様に形成された下流部9から構成されている。
(Example 4)
FIG. 4 shows a perspective view of the honeycomb structure of the present example. This honeycomb structure is the same flat plate as in Example 1 except that the porosity is different from the upstream portion 7 formed by rolling a flat plate made of a stainless steel metal foil having a thickness of 50 μm and a corrugated plate into a roll shape. 1 and a central portion 8 formed similarly from the corrugated plate 2 and a downstream portion 9 formed similarly to the upstream portion 7.

上流部7は直径 103mm、長さ50mm、中央部8は直径 103mm、長さ55mm、下流部9は直径103mm、長さ50mmに形成され、ロウ付けによって互いに接合されている。上流部7、中央部8及び下流部9は、共にセルの密度は 400/in2 である。また中央部8の平板及び波板は共に気孔径が 100μm以下、気孔率が90%であり、中央部8が本発明にいう超多孔質部となっている。 The upstream portion 7 has a diameter of 103 mm and a length of 50 mm, the central portion 8 has a diameter of 103 mm and a length of 55 mm, and the downstream portion 9 has a diameter of 103 mm and a length of 50 mm, and is joined to each other by brazing. The upstream portion 7, the central portion 8 and the downstream portion 9 all have a cell density of 400 / in 2 . The flat plate and corrugated plate of the central portion 8 both have a pore diameter of 100 μm or less and a porosity of 90%, and the central portion 8 is the superporous portion referred to in the present invention.

(実施例5)
図5に本実施例のハニカム構造体の概略断面図を示す。このハニカム構造体は、厚さ50μmのステンレス製金属箔からなる平板と波板を重ねてロール状に巻回されてなる中心部10と、中心部10の外周に巻回され、気孔率が異なること以外は実施例1と同様の平板1及び波板2から同様に形成された外周部11とから構成されている。
(Example 5)
FIG. 5 shows a schematic cross-sectional view of the honeycomb structure of the present example. The honeycomb structure has a central portion 10 formed by rolling a flat plate made of a stainless steel metal foil having a thickness of 50 μm and a corrugated plate, and wound around the outer periphery of the central portion 10, and has different porosity. Except for this, the flat plate 1 and the corrugated plate 2 are the same as those of the first embodiment, and the outer peripheral portion 11 is similarly formed.

中心部10は直径40mm、長さ 155mm、外周部11は外径 103mm、長さ 155mmに形成され、ロウ付けによって互いに接合されている。中心部10及び外周部11は、共にセルの密度が 400/in2 である。また外周部11の平板及び波板は共に気孔径が 100μm以下、気孔率が75%であり、外周部11が本発明にいう超多孔質部となっている。 The central portion 10 has a diameter of 40 mm and a length of 155 mm, and the outer peripheral portion 11 has an outer diameter of 103 mm and a length of 155 mm, and is joined to each other by brazing. Both the central portion 10 and the outer peripheral portion 11 have a cell density of 400 / in 2 . Further, both the flat plate and the corrugated plate of the outer peripheral portion 11 have a pore diameter of 100 μm or less and a porosity of 75%, and the outer peripheral portion 11 is a superporous portion referred to in the present invention.

(実施例6)
図6に本実施例のハニカム構造体の概略断面図を示す。このハニカム構造体は、気孔率が異なること以外は実施例1と同様の平板1及び波板2から同様に形成された中心部12と、中心部12の外周に巻回され、厚さ50μmのステンレス製金属箔からなる平板と波板を重ねてロール状に巻回されてなる外周部13とから構成されている。
(Example 6)
FIG. 6 shows a schematic cross-sectional view of the honeycomb structure of the present example. This honeycomb structure is wound around the central portion 12 similarly formed from the flat plate 1 and the corrugated plate 2 similar to those in Example 1 except that the porosity is different, and is wound around the outer periphery of the central portion 12 and has a thickness of 50 μm. It is composed of a flat plate made of stainless steel metal foil and an outer peripheral portion 13 which is formed by rolling a corrugated plate into a roll shape.

中心部12は直径80mm、長さ 155mm、外周部13は外径 103mm、長さ 155mmに形成され、ロウ付けによって互いに接合されている。中心部12及び外周部13は、共にセルの密度が 400/in2 である。また中心部12の平板及び波板は共に気孔径が 100μm以下、気孔率が90%であり、外周部11が本発明にいう超多孔質部となっている。 The central portion 12 is formed with a diameter of 80 mm and a length of 155 mm, and the outer peripheral portion 13 is formed with an outer diameter of 103 mm and a length of 155 mm, and is joined to each other by brazing. Both the central portion 12 and the outer peripheral portion 13 have a cell density of 400 / in 2 . The flat plate and corrugated plate of the central portion 12 both have a pore diameter of 100 μm or less and a porosity of 90%, and the outer peripheral portion 11 is a superporous portion referred to in the present invention.

(実施例7)
図7に本実施例のハニカム構造体の要部断面図を示す。このハニカム構造体は、気孔率が異なること以外は実施例1と同様の平板14を用い、波板15を厚さ50μmのステンレス製金属箔から形成したこと以外は実施例1と同様の構成である。平板14が本発明にいう超多孔質部となっている。
(Example 7)
FIG. 7 shows a cross-sectional view of the main part of the honeycomb structure of the present example. This honeycomb structure has the same configuration as in Example 1 except that the flat plate 14 is the same as that in Example 1 except that the porosity is different, and the corrugated sheet 15 is formed of a stainless steel metal foil having a thickness of 50 μm. is there. The flat plate 14 is the superporous portion referred to in the present invention.

(実施例8)
図8に本実施例のハニカム構造体の要部断面図を示す。このハニカム構造体は、気孔率が異なること以外は実施例1と同様の波板16を用い、平板17を厚さ50μmのステンレス製金属箔から形成したこと以外は実施例1と同様の構成である。波板16が本発明にいう超多孔質部となっている。
(Example 8)
FIG. 8 shows a cross-sectional view of the main part of the honeycomb structure of the present example. This honeycomb structure has the same configuration as in Example 1 except that the corrugated plate 16 is the same as in Example 1 except that the porosity is different, and the flat plate 17 is formed of a stainless steel metal foil having a thickness of 50 μm. is there. The corrugated plate 16 is the superporous portion referred to in the present invention.

(比較例1)
コージェライト製でハニカム形状の耐熱性基材の両端開口を互い違いに市松状に閉塞した市販のディーゼルパティキュレートフィルタを比較例1のハニカム構造体とした。このハニカム構造体は、直径 103mm、長さ 155mm、セル密度 400/in2 であり、セル隔壁の気孔率は50%である。
(Comparative Example 1)
A commercially available diesel particulate filter made of cordierite in which the openings at both ends of the honeycomb-shaped heat-resistant substrate are alternately closed in a checkered pattern was used as the honeycomb structure of Comparative Example 1. This honeycomb structure has a diameter of 103 mm, a length of 155 mm, a cell density of 400 / in 2 and a cell partition wall porosity of 50%.

(比較例2)
コージェライト製のフロースルー型のモノリス基材を比較例2のハニカム構造体とした。このハニカム構造体は、直径 103mm、長さ 155mm、セル密度 400/in2 であり、ハニカムセル隔壁の気孔率は30%である。
(Comparative Example 2)
A cordierite flow-through monolith substrate was used as the honeycomb structure of Comparative Example 2. This honeycomb structure has a diameter of 103 mm, a length of 155 mm, a cell density of 400 / in 2 , and the porosity of the honeycomb cell partition walls is 30%.

(比較例3)
金属製網体を積層して巻回してなる巻回体を比較例3のハニカム構造体とした。このハニカム構造体の気孔率は70%、目開き(気孔径)は1mmである。
(Comparative Example 3)
A wound structure obtained by stacking and winding metal nets was used as the honeycomb structure of Comparative Example 3. The honeycomb structure has a porosity of 70% and an opening (pore diameter) of 1 mm.

<試験・評価>
上記実施例及び比較例のハニカム構造体を排気量2Lのディーゼルエンジンの排気系に装着し、2000回転程度の低速運転時におけるハニカム構造体前後の排ガス中のPM濃度を測定して、ハニカム構造体に捕集されたPMの捕集率を求めた。また同時にハニカム構造体前後の排ガス圧力を測定し、差圧から圧損を求めた。結果をそれぞれ表1に示す。
<Test and evaluation>
The honeycomb structures of the above examples and comparative examples are mounted on the exhaust system of a diesel engine with a displacement of 2 L, and the PM concentration in the exhaust gas before and after the honeycomb structure is measured at a low speed operation of about 2000 revolutions. The collection rate of PM collected in the above was determined. At the same time, the exhaust gas pressure before and after the honeycomb structure was measured, and the pressure loss was determined from the differential pressure. The results are shown in Table 1, respectively.

Figure 0004358054
Figure 0004358054

表1より、各実施例のハニカム構造体は、フロースルー型でありながらPM捕集率が35%以上と高効率でPMを捕集することができ、かつ圧損も十分に低いことが明らかである。   From Table 1, it is clear that the honeycomb structure of each example is a flow-through type and can collect PM with a high efficiency of 35% or more and a sufficiently low pressure loss. is there.

実施例1のハニカム構造体の要部断面図である。3 is a cross-sectional view of a main part of a honeycomb structure of Example 1. FIG. 実施例2のハニカム構造体の概略斜視図である。3 is a schematic perspective view of a honeycomb structure of Example 2. FIG. 実施例3のハニカム構造体の概略斜視図である。4 is a schematic perspective view of a honeycomb structure of Example 3. FIG. 実施例4のハニカム構造体の概略斜視図である。6 is a schematic perspective view of a honeycomb structure of Example 4. FIG. 実施例5のハニカム構造体の概略断面図である。6 is a schematic cross-sectional view of a honeycomb structure of Example 5. FIG. 実施例6のハニカム構造体の概略断面図である。6 is a schematic cross-sectional view of a honeycomb structure of Example 6. FIG. 実施例7のハニカム構造体の要部断面図である。10 is a cross-sectional view of a main part of a honeycomb structure of Example 7. FIG. 実施例8のハニカム構造体の要部断面図である。10 is a cross-sectional view of a main part of a honeycomb structure of Example 8. FIG.

符号の説明Explanation of symbols

1:平板(超多孔質部) 2:波板(超多孔質部)
3:上流部(超多孔質部) 4:下流部
1: Flat plate (superporous part) 2: Corrugated plate (superporous part)
3: Upstream part (superporous part) 4: Downstream part

Claims (2)

排ガスの入口と出口を連通する複数のハニカムセル内を排ガスが流通するフロースルー型の金属製ハニカム構造体であって、該ハニカムセルの内壁の少なくとも一部は金属製不織布又はパンチングメタルよりなり孔径が零を超え 500μm以下、気孔率が55〜95%である超多孔質部をもつ多孔質金属板から形成され、該超多孔質部で排ガス中の粒子状物質を捕集することを特徴とする排ガス浄化ハニカム構造体。 A flow-through type metal honeycomb structure in which exhaust gas circulates in a plurality of honeycomb cells communicating with an inlet and an outlet of exhaust gas, wherein at least a part of the inner wall of the honeycomb cell is made of a metal nonwoven fabric or punching metal and has a pore size Characterized in that it is formed from a porous metal plate having a superporous portion with a porosity exceeding 55 μm and a porosity of 55 to 95% , and collecting particulate matter in exhaust gas at the superporous portion. Exhaust gas purification honeycomb structure. 前記ハニカムセルの内壁には、多孔質酸化物に貴金属を担持してなる触媒層が形成されている請求項1に記載の排ガス浄化ハニカム構造体。   The exhaust gas purifying honeycomb structure according to claim 1, wherein a catalyst layer formed by supporting a noble metal on a porous oxide is formed on an inner wall of the honeycomb cell.
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