JPH08141408A - Catalyst carrier with resistance regulation type heater for purification of exhaust gas and production - Google Patents
Catalyst carrier with resistance regulation type heater for purification of exhaust gas and productionInfo
- Publication number
- JPH08141408A JPH08141408A JP6289808A JP28980894A JPH08141408A JP H08141408 A JPH08141408 A JP H08141408A JP 6289808 A JP6289808 A JP 6289808A JP 28980894 A JP28980894 A JP 28980894A JP H08141408 A JPH08141408 A JP H08141408A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst carrier
- resistance
- exhaust gas
- honeycomb structure
- heater
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000000746 purification Methods 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000203 mixture Substances 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- JHJNPOSPVGRIAN-SFHVURJKSA-N n-[3-[(1s)-1-[[6-(3,4-dimethoxyphenyl)pyrazin-2-yl]amino]ethyl]phenyl]-5-methylpyridine-3-carboxamide Chemical compound C1=C(OC)C(OC)=CC=C1C1=CN=CC(N[C@@H](C)C=2C=C(NC(=O)C=3C=C(C)C=NC=3)C=CC=2)=N1 JHJNPOSPVGRIAN-SFHVURJKSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、排ガス浄化用抵抗調整
型ヒータ付触媒担体およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resistance-adjustable heater-equipped catalyst carrier for exhaust gas purification and a method for producing the same.
【０００２】[0002]
【従来の技術】自動車排ガス浄化用の触媒担体として、
多数の貫通孔を有するハニカム構造体に通電のための２
以上の電極を設けたヒータ付触媒担体が知られている。
ヒータ付とした理由は、ＬＡ４モード等のコールドスタ
ート時に初期の排ガス中に比較的高濃度に含まれる炭化
水素や一酸化炭素を除去する必要があり、担体の一部を
通電により早期に昇温させ触媒を有効に作用させるため
である。また、担体全体の昇温を早めるには、小型化に
より熱容量を小さくすることも行われている。2. Description of the Related Art As a catalyst carrier for purifying automobile exhaust gas,
2 for energizing a honeycomb structure having a large number of through holes
A catalyst carrier with a heater provided with the above electrodes is known.
The reason for using a heater is that it is necessary to remove hydrocarbons and carbon monoxide contained in relatively high concentration in the initial exhaust gas during cold start in LA4 mode, etc. This is to allow the catalyst to act effectively. In addition, in order to accelerate the temperature rise of the entire carrier, it has been attempted to reduce the heat capacity by downsizing.
【０００３】従来のヒータ付触媒担体の一つとしては、
中心電極棒に一端を溶接した耐熱金属箔の平板と波板を
熱処理して表面に酸化絶縁皮膜を形成した後、筒状に巻
き付けてハニカム筒体とし、中心電極と外周との間で通
電して加熱する方式のものがあった。このタイプの部分
通電法では、抵抗が材質と寸法によって決まるため、中
心部および外周部では金属の平板と波板を直接溶接して
低抵抗とし、中間部では金属の平板と波板とを酸化絶縁
皮膜を介して単に接触させるが溶接はせず高抵抗とする
方法が採られていた。しかし、高温の排ガスに晒される
と熱膨張により波板の山が潰れ、非溶接部である中間部
が抜け出るテレスコープ現象が起きる上、中心電極と溶
接部の存在により排ガスの圧損が増すという問題があっ
た。As one of the conventional catalyst carriers with a heater,
A heat-resistant metal foil flat plate with one end welded to the center electrode rod and a corrugated plate are heat-treated to form an oxide insulation film on the surface, and then wound in a tubular shape to form a honeycomb tubular body, and electricity is applied between the central electrode and the outer periphery. There was a method of heating by heating. In this type of partial energization method, the resistance is determined by the material and dimensions.Therefore, the flat metal plate and the corrugated plate are directly welded to reduce the resistance in the central part and the outer peripheral part, and the flat metal plate and corrugated plate are oxidized in the middle part. A method has been adopted in which it is simply contacted via an insulating film, but is not welded and has high resistance. However, when exposed to high-temperature exhaust gas, the crest of the corrugated sheet collapses due to thermal expansion, a telescope phenomenon occurs in which the middle part that is the non-welded part comes out, and the pressure loss of the exhaust gas increases due to the presence of the center electrode and the welded part. was there.
【０００４】また、特開平３−２９５１８４号公報に
は、金属粉末を押し出し成形し焼結した一体型のハニカ
ム構造体における部分通電法が開示されており、セルを
一部切り取ったり、ハニカムにスリットを入れて絶縁体
を挿入し、通電経路を制御することを提案している。し
かしこの場合、ハニカム構造体が強度的に弱くなるとい
う欠点がある。Further, Japanese Laid-Open Patent Publication No. 3-295184 discloses a partial energization method in an integral type honeycomb structure obtained by extrusion-molding metal powder and sintering it. For example, a cell is partially cut or a honeycomb is slit. It has been proposed to put an insulator in between and to control the energization path. However, in this case, there is a drawback that the honeycomb structure becomes weak in strength.
【０００５】このように従来の抵抗調整型ヒータ付触媒
担体は、ハニカム構造体に部分通電箇所を規定する手段
として、構成部材の接合を一部欠いたり、構成部材自体
を一部欠くことを必要としたため、これらが必然的に局
所的な脆弱部となり、機械構造として全体の強度が低下
することが避けられなかった。As described above, in the conventional catalyst carrier with a resistance adjustment heater, it is necessary to partially lack the joining of the constituent members or partially lack the constituent members themselves as means for defining the partially energized portion in the honeycomb structure. Therefore, these inevitably become local weakened portions, and it is unavoidable that the mechanical strength of the entire structure decreases.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記従来技
術の欠点を解消し、機械構造として脆弱部を含むことが
なく強度的に安定した排ガス浄化用抵抗調整型ヒータ付
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。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, and has a resistance-adjustable heater catalyst carrier for exhaust gas purification that does not include a fragile part as a mechanical structure and is stable in strength, and its manufacture. The purpose is to provide a method.
【０００７】[0007]
【課題を解決するための手段】上記課題を解決するため
に、本発明によれば、多数の貫通孔を有するハニカム構
造体に通電のための２以上の電極を設けた排ガス浄化用
ヒータ付触媒担体であって、該ハニカム構造体は組成比
により比抵抗を変えた部分を備えていることを特徴とす
る排ガス浄化用抵抗調整型ヒータ付触媒担体が提供され
る。In order to solve the above-mentioned problems, according to the present invention, a catalyst with a heater for exhaust gas purification in which two or more electrodes for energization are provided in a honeycomb structure having a large number of through holes. A catalyst carrier with a resistance adjusting heater for exhaust gas purification, which is a carrier, wherein the honeycomb structure has a portion whose specific resistance is changed according to a composition ratio.
【０００８】[0008]
【作用】本発明の排ガス浄化用抵抗調整型ヒータ付触媒
担体は、ハニカム構造体が組成比により比抵抗を変えた
部分を備えているので、通電により比抵抗の低い部分が
選択的に発熱して早期に触媒作用が開始する。これによ
り、従来のように機械構造として脆弱部を設けることな
く、コールドスタート時初期の排ガス中に比較的高濃度
に含まれる炭化水素や一酸化炭素を除去することができ
る。In the exhaust gas purifying resistance-adjustable heater-equipped catalyst carrier of the present invention, since the honeycomb structure has a portion whose specific resistance is changed depending on the composition ratio, a portion having a low specific resistance selectively generates heat by energization. And the catalytic action starts early. As a result, it is possible to remove hydrocarbons and carbon monoxide contained in a relatively high concentration in the exhaust gas at the initial stage of cold start without providing a fragile portion as a mechanical structure as in the conventional case.
【０００９】本発明のハニカム構造体は、ペロブスカイ
ト系、スピネル系等の従来公知の導電性セラミックス材
料で作製することができる。これらの内、特にペロブス
カイト材料は比抵抗が１０〜０．０１Ωで、ハニカム体
にしたときの抵抗値が調整しやすい。またハニカム表面
に設ける触媒担持物質として上記導電性セラミックスを
用いてもよく、一般にはγ−Ａｌ2 Ｏ3 が用いられる。
実際に触媒として作用する触媒活性物質としては、Ｐ
ｔ、Ｐｄ、Ｒｈ等の貴金属、Ｃｕ、Ｎｉ、Ｃｒ、Ｃｏ等
の卑金属が従来から知られている。The honeycomb structure of the present invention can be made of a conventionally known conductive ceramic material such as a perovskite type or a spinel type. Among these, the perovskite material has a specific resistance of 10 to 0.01 Ω, and the resistance value of the honeycomb body can be easily adjusted. The conductive ceramics may be used as the catalyst supporting material provided on the surface of the honeycomb, and γ-Al 2 O 3 is generally used.
As a catalytically active substance that actually acts as a catalyst, P
Noble metals such as t, Pd, and Rh and base metals such as Cu, Ni, Cr, and Co have been conventionally known.
【００１０】本発明のハニカム構造体に用いる導電性ペ
ロブスカイト材料として典型的なものは、組成式（Ｌａ
1-x Ａｄx ）y ＭｎＯ3 〔但しＡｄはアルカリ土類金
属〕で表されるものであり、ｘおよびｙの値により組成
比を変えることにより、比抵抗を変えることができる。A typical conductive perovskite material used in the honeycomb structure of the present invention has a composition formula (La).
1-x Ad x ) y MnO 3 [where Ad is an alkaline earth metal], and the specific resistance can be changed by changing the composition ratio depending on the values of x and y.
【００１１】本発明のハニカム構造体は、その前駆体と
しての仮焼成体を形成し、それとは異なる組成比の溶液
を仮焼成体の所定部位に含浸させた後に、焼成して作製
することができる。これにより、ハニカム構造体の所定
部分の組成比を変えて、その部分と他の部分とで比抵抗
を変えることができる。以下に、添付図面を参照して、
実施例により本発明を更に詳細に説明する。The honeycomb structure of the present invention can be produced by forming a calcined body as a precursor thereof, impregnating a predetermined portion of the calcined body with a solution having a different composition ratio, and then calcining the solution. it can. This makes it possible to change the composition ratio of a predetermined portion of the honeycomb structure and change the specific resistance between that portion and another portion. Below, referring to the attached drawings,
The present invention will be described in more detail by way of examples.
【００１２】[0012]
〔実施例１〕導電性ペロブスカイト材料を用いて以下の
手順で本発明のハニカム構造体を作製した。まず、Ｌａ
2 Ｏ3 粉末、ＳｒＣＯ3 粉末、Ｍｎ2 Ｏ3 粉末を組成式
（Ｌａ0.7Ｓｒ0.3)ＭｎＯ3 の組成比となるように秤量
し、ボールミルにて２４時間湿式混合した。得られた混
合物を１５０℃で２４時間乾燥してから、アルミナ坩堝
中で９００℃で７時間仮焼成した。得られた粉末をボー
ルミルにて２４時間粉砕乾燥して原料粉末とした。[Example 1] A honeycomb structure of the present invention was produced using a conductive perovskite material by the following procedure. First, La
2 O 3 powder, SrCO 3 powder, and Mn 2 O 3 powder were weighed so as to have a composition ratio of (La 0.7 Sr 0.3 ) MnO 3 and wet-mixed in a ball mill for 24 hours. The obtained mixture was dried at 150 ° C. for 24 hours, and then calcined in an alumina crucible at 900 ° C. for 7 hours. The obtained powder was ground and dried in a ball mill for 24 hours to obtain a raw material powder.
【００１３】この原料粉末に、メチルセルロース（例え
ば信越化学工業(株)製６５ＳＨ１５０００）、グリセリ
ン、およびイオン交換水を加え混練機にて混練して粘土
状とし、ロータリーポンプによる減圧下で圧縮成形し丸
棒とした。Methyl cellulose (for example, 65SH15000, manufactured by Shin-Etsu Chemical Co., Ltd.), glycerin, and ion-exchanged water are added to this raw material powder, and the mixture is kneaded in a kneader to form a clay, which is compression-molded under reduced pressure by a rotary pump into a circle. It was a stick.
【００１４】この丸棒をハニカム成形型（例えば＃４０
０、壁厚０．４ｍｍ）を通して押し出し成形し、乾燥後
切断して所定の形状（例えばφ８６×ｔ２０）とした。
これを１０００℃で脱脂および仮焼成することにより、
図１に示したハニカム構造体１の前駆体としてハニカム
成形体を得た。This round bar is formed into a honeycomb forming die (for example, # 40).
0, wall thickness 0.4 mm), extrusion molding, drying and cutting into a predetermined shape (for example, φ86 × t20).
By degreasing and calcining this at 1000 ° C.,
A honeycomb formed body was obtained as a precursor of the honeycomb structure 1 shown in FIG.
【００１５】このハニカム成形体の両端面を２〜４ｍｍ
の深さで硝酸マンガン３０％水溶液に浸漬した後、乾燥
した。これにより、ハニカム成形体の両端面は、前記組
成式で示される組成比に対してマンガン量が高い組成比
となった。ハニカム成形体の他の部分は前記組成式で示
される組成比になっている。Both end faces of this honeycomb formed body are 2 to 4 mm
It was dipped in a 30% aqueous solution of manganese nitrate at a depth of 1 and then dried. As a result, both end faces of the honeycomb formed body had a composition ratio in which the amount of manganese was higher than the composition ratio represented by the composition formula. The other portion of the honeycomb formed body has the composition ratio represented by the above composition formula.
【００１６】次に、空気中１３００〜１４００℃で４時
間焼結し、図１に示した両端部に低比抵抗部２ａおよび
２ｂを備えたハニカム構造体１を得た。Next, it was sintered in air at 1300 to 1400 ° C. for 4 hours to obtain a honeycomb structure 1 having the low specific resistance portions 2a and 2b at both ends shown in FIG.
【００１７】このハニカム構造体１の両端面に、リード
部を持つＰｔ電極３をそれぞれ設け、抵抗調整型ヒータ
とした。Pt electrodes 3 having lead portions were provided on both end faces of the honeycomb structure 1 to form a resistance adjustment type heater.
【００１８】この抵抗調整型ヒータに触媒活性物質（例
えばＰｔ、Ｒｈ、Ｐｄ等の貴金属）を担持させて抵抗調
整型ヒータ付触媒担体５とした。A catalytically active substance (for example, a noble metal such as Pt, Rh, or Pd) is carried on the resistance-adjustable heater to obtain a resistance-adjustable heater-equipped catalyst carrier 5.
【００１９】〔実施例２〕実施例１の脱脂および仮焼成
したハニカム成形体の両端面を２〜４ｍｍの深さで硝酸
マンガン３０％水溶液に浸漬した後、乾燥した。これに
より、ハニカム成形体の両端面は、前記組成式で示され
る組成比に対してマンガン含有量が多い組成比となっ
た。ハニカム成形体の他の部分は前記組成式で示される
組成比になっている。Example 2 The degreased and pre-baked honeycomb molded body of Example 1 was immersed in a 30% aqueous solution of manganese nitrate at a depth of 2 to 4 mm and then dried. As a result, both end faces of the honeycomb formed body had a composition ratio higher in manganese content than the composition ratio represented by the composition formula. The other portion of the honeycomb formed body has the composition ratio represented by the above composition formula.
【００２０】次に、一般試薬のパラフィン（融点６８〜
７０℃）で、図２に示したように両端面の中央部７以外
の外周部をマスクし、硝酸ストロンチウム２０％水溶液
に含浸した後、乾燥した。これにより、両端面は中央部
７が外周部よりも更にマンガン含有量が多い組成比とな
った。Next, paraffin of a general reagent (melting point 68 to
At 70 ° C., as shown in FIG. 2, the outer peripheral portions other than the central portion 7 of both end faces were masked, impregnated with a 20% strontium nitrate aqueous solution, and then dried. As a result, the composition ratio of the central portion 7 of both end faces was higher than that of the outer peripheral portion.
【００２１】次に、空気中１３００〜１４００℃で４時
間焼結し、図２に示した両端部に低比抵抗部２ａおよび
２ｂを備え且つ外周部よりも中央部が更に低比抵抗の発
熱部７を備えたハニカム構造体１を得た。Next, it is sintered in air at 1300 to 1400 ° C. for 4 hours, and has low specific resistance portions 2a and 2b at both ends shown in FIG. 2 and heat generation having a lower specific resistance in the central portion than in the outer peripheral portion. A honeycomb structure 1 including the part 7 was obtained.
【００２２】このハニカム構造体１の両端面に、リード
部を持つＰｔ電極３をそれぞれ設け、抵抗調整型ヒータ
とした。Pt electrodes 3 having lead portions were provided on both end faces of the honeycomb structure 1 to form a resistance adjustment type heater.
【００２３】この抵抗調整型ヒータに触媒活性物質（例
えばＰｔ、Ｒｈ、Ｐｄ等の貴金属）を担持させて抵抗調
整型ヒータ付触媒担体５とした。A catalytically active substance (for example, a noble metal such as Pt, Rh, or Pd) is carried on the resistance-adjustable heater to obtain a resistance-adjustable heater-equipped catalyst carrier 5.
【００２４】〔実施例３〕実施例１の脱脂および仮焼成
したハニカム成形体の片端面の図３に示した領域８を一
般試薬パラフィン（融点６８〜７０℃）でマスクし、２
〜４ｍｍの深さで硝酸マンガン３０％水溶液に浸漬した
後、乾燥した。これにより、ハニカム成形体の片端面
は、マスクした領域８以外の領域９においては、ハニカ
ム成形体の他の部分によりもマンガン含有量が多い組成
比となった。ハニカム成形体の他の部分は前記組成式で
示される組成比になっている。Example 3 A region 8 shown in FIG. 3 on one end face of the degreased and pre-fired honeycomb molded body of Example 1 was masked with a general reagent paraffin (melting point 68 to 70 ° C.), and 2
It was immersed in a 30% manganese nitrate aqueous solution at a depth of ˜4 mm and then dried. As a result, the one end surface of the honeycomb formed body had a composition ratio in which the manganese content was higher in the other regions of the honeycomb formed body in the regions 9 other than the masked region 8. The other portion of the honeycomb formed body has the composition ratio represented by the above composition formula.
【００２５】次に、空気中１３００〜１４００℃で４時
間焼結し、片端面に高比抵抗部８と低比抵抗部９とを備
えたハニカム構造体１を得た。Next, it was sintered in air at 1300 to 1400 ° C. for 4 hours to obtain a honeycomb structure 1 having a high specific resistance portion 8 and a low specific resistance portion 9 on one end surface.
【００２６】このハニカム構造体１の片端面の低比抵抗
部９内の２か所に、リード部を持つＰｔ電極３をそれぞ
れ設け、抵抗調整型ヒータとした。A Pt electrode 3 having a lead portion was provided at each of two places in the low specific resistance portion 9 on one end surface of the honeycomb structure 1 to form a resistance adjustment type heater.
【００２７】この抵抗調整型ヒータに触媒活性物質（例
えばＰｔ、Ｒｈ、Ｐｄ等の貴金属）を担持させて抵抗調
整型ヒータ付触媒担体５とした。A catalytically active substance (for example, a noble metal such as Pt, Rh, or Pd) was carried on this resistance-adjustable heater to obtain a resistance-adjustable heater-equipped catalyst carrier 5.
【００２８】上記実施例１〜３で作製した本発明の触媒
担体の昇温性能テストを行った。図４に、本発明の抵抗
調整型ヒータ付触媒担体５を排気経路に搭載した状態を
示す。左方に配置したエンジン（図示せず）の排ガス
は、排気管４から本発明の触媒担体５を通ってから触媒
担体６を通り、右方の外部へ排出される。即ち本発明の
抵抗調整型ヒータ付触媒担体５はメイン触媒担体６より
も排ガス流に関して上流側に配置してある。A temperature raising performance test was conducted on the catalyst carriers of the present invention produced in Examples 1 to 3 above. FIG. 4 shows a state in which the resistance-adjustable heater-equipped catalyst carrier 5 of the present invention is mounted in the exhaust path. Exhaust gas from the engine (not shown) arranged on the left side passes through the exhaust pipe 4, the catalyst carrier 5 of the present invention, the catalyst carrier 6, and is discharged to the outside on the right side. That is, the resistance-adjustable heater-equipped catalyst carrier 5 of the present invention is arranged upstream of the main catalyst carrier 6 with respect to the exhaust gas flow.
【００２９】エンジン始動直前に抵抗調整型ヒータ付触
媒担体５に通電して、これを早急に加熱する。これによ
り、排ガスの熱によりメイン触媒担体６が昇温して浄化
作用を開始する前の低温時に、排ガス中の炭化水素ガス
や一酸化炭素ガスを抵抗調整型ヒータ付触媒担体５によ
り除去する。そのためには、低消費電力（１．５ｋＷ以
下）で、触媒活性温度（典型的には３５０℃程度）まで
短時間（７秒以内）で、昇温することが好ましい。Immediately before starting the engine, the catalyst carrier 5 with a resistance-adjustable heater is energized to heat it immediately. As a result, the hydrocarbon gas and carbon monoxide gas in the exhaust gas are removed by the resistance-adjustable heater-equipped catalyst carrier 5 at a low temperature before the temperature of the main catalyst carrier 6 is raised by the heat of the exhaust gas and the purification action is started. For that purpose, it is preferable to raise the temperature to a catalyst activation temperature (typically about 350 ° C.) in a short time (within 7 seconds) with low power consumption (1.5 kW or less).
【００３０】実施例１で作製した、両端面を低比抵抗と
した抵抗調整型ヒータ付触媒担体５は、中央部を３５０
℃まで７秒で昇温させるのに要した消費電力は１．５ｋ
Ｗであった。The resistance-adjustable heater-supported catalyst carrier 5 having a low specific resistance on both end surfaces produced in Example 1 has a central portion of 350.
Power consumption required to heat up to ℃ in 7 seconds is 1.5k
It was W.
【００３１】実施例２で作製した、両端面を低比抵抗と
した上で中央部７の比抵抗を更に低くした抵抗調整型ヒ
ータ付触媒担体５は、中央部７に電流が集中して選択的
に急速昇温される。この場合、中央部７を３５０℃まで
７秒で昇温させるのに要した消費電力は０．８ｋＷであ
った。The resistance-adjustable heater-equipped catalyst carrier 5 produced in Example 2 in which both end faces have a low specific resistance and the central part 7 has a lower specific resistance is selected because the central part 7 has a concentrated current. Temperature is rapidly increased. In this case, the power consumption required to raise the temperature of the central portion 7 to 350 ° C. in 7 seconds was 0.8 kW.
【００３２】実施例３で作製した、片端面に高比抵抗部
８と低比抵抗部９とを設けた抵抗調整型ヒータ付触媒担
体５は、低比抵抗部９を電流が流れて部分加熱される。
この場合、低比抵抗部９の中央部を３５０℃まで７秒で
昇温させるのに要した消費電力は０．５ｋＷであった。The resistance-adjustable heater-equipped catalyst carrier 5 having the high specific resistance portion 8 and the low specific resistance portion 9 provided on one end face, which was produced in Example 3, was partially heated by the current flowing through the low specific resistance portion 9. To be done.
In this case, the power consumption required to raise the central portion of the low specific resistance portion 9 to 350 ° C. in 7 seconds was 0.5 kW.
【００３３】以上説明した実施例においては、組成式
（Ｌａ0.7 Ｓｒ0.3)ＭｎＯ3 で表されるペロブスカイト
材料を部分的にＭｎ含有量を高め、その部分を低比抵抗
化したが、Ｌａ、Ｓｒ、Ｍｎの３元素について前記組成
式に対してそれぞれ含有量を増減して組成比を調整し、
比抵抗の高い部分、低い部分を形成することができるこ
とは勿論である。In the examples described above, the perovskite material represented by the composition formula (La 0.7 Sr 0.3 ) MnO 3 was partially increased in Mn content to lower the specific resistance. The composition ratios of the three elements of Mn and
Of course, it is possible to form a portion having a high specific resistance and a portion having a low specific resistance.
【００３４】[0034]
【発明の効果】以上説明したように、本発明によれば、
従来のように機械構造として脆弱部を含むことがなく、
強度的に安定した排ガス浄化用抵抗調整型ヒータ付触媒
担体が得られる。As described above, according to the present invention,
Unlike conventional machines, it does not include a fragile part as a mechanical structure,
A resistance-adjustable heater-equipped catalyst carrier for exhaust gas purification that is stable in strength can be obtained.
【図１】本発明の実施例１による排ガス浄化用抵抗調整
型ヒータ付触媒担体を示す斜視図である。FIG. 1 is a perspective view showing a catalyst carrier with a resistance adjustment type heater for exhaust gas purification according to a first embodiment of the present invention.
【図２】本発明の実施例２による排ガス浄化用抵抗調整
型ヒータ付触媒担体を示す斜視図である。FIG. 2 is a perspective view showing a catalyst carrier with a resistance adjusting heater for exhaust gas purification according to a second embodiment of the present invention.
【図３】本発明の実施例３による排ガス浄化用抵抗調整
型ヒータ付触媒担体を示す斜視図である。FIG. 3 is a perspective view showing a catalyst carrier with a resistance adjusting heater for exhaust gas purification according to a third embodiment of the present invention.
【図４】本発明の実施例１〜３による排ガス浄化用抵抗
調整型ヒータ付触媒担体を排気経路に搭載した状態を示
す断面図である。FIG. 4 is a cross-sectional view showing a state in which a resistance-adjustable heater-equipped catalyst carrier for exhaust gas purification according to Examples 1 to 3 of the present invention is mounted in an exhaust path.
１…ハニカム構造体 ２ａ、２ｂ…溶液含浸による低比抵抗部 ３…ハニカム構造体に通電するための電極 ７…溶液を再度含浸させて更に低比抵抗にした部分 ８…溶液を含浸させずに残した高抵抗部 DESCRIPTION OF SYMBOLS 1 ... Honeycomb structure 2a, 2b ... Low specific resistance part by solution impregnation 3 ... Electrode for energizing a honeycomb structure 7 ... Part which was further impregnated with solution to further lower specific resistance 8 ... Without impregnating solution High resistance part left
Claims (4)
通電のための２以上の電極を設けた排ガス浄化用ヒータ
付触媒担体であって、該ハニカム構造体は組成比により
比抵抗を変えた部分を備えていることを特徴とする排ガ
ス浄化用抵抗調整型ヒータ付触媒担体。1. A catalyst carrier with a heater for exhaust gas purification, comprising a honeycomb structure having a large number of through holes and two or more electrodes for energization, the honeycomb structure having a specific resistance varied depending on a composition ratio. A resistance-adjustable heater-equipped catalyst carrier for exhaust gas purification, characterized by comprising a portion.
スであることを特徴とする請求項１記載の触媒担体。2. The catalyst carrier according to claim 1, wherein the honeycomb structure is a conductive ceramic.
ト形結晶構造を有することを特徴とする請求項２記載の
触媒担体。3. The catalyst carrier according to claim 2, wherein the conductive ceramic has a perovskite type crystal structure.
載の触媒担体を製造する方法であって、前記ハニカム構
造体の前駆体としての仮焼成体を形成し、該ハニカム構
造体とは異なる組成比の溶液を該仮焼成体の所定部位に
含浸させた後に、焼成することを特徴とする排ガス浄化
用抵抗調整型ヒータ付触媒担体の製造方法。4. A method for producing the catalyst carrier according to claim 1, wherein a calcinated body is formed as a precursor of the honeycomb structure, Is a method for producing a catalyst carrier with a resistance-adjustable heater for exhaust gas purification, which comprises: impregnating a predetermined portion of the calcined body with a solution having a different composition ratio and then calcining the solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6289808A JPH08141408A (en) | 1994-11-24 | 1994-11-24 | Catalyst carrier with resistance regulation type heater for purification of exhaust gas and production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6289808A JPH08141408A (en) | 1994-11-24 | 1994-11-24 | Catalyst carrier with resistance regulation type heater for purification of exhaust gas and production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08141408A true JPH08141408A (en) | 1996-06-04 |
Family
ID=17748043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6289808A Withdrawn JPH08141408A (en) | 1994-11-24 | 1994-11-24 | Catalyst carrier with resistance regulation type heater for purification of exhaust gas and production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08141408A (en) |
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| JP2015535796A (en) * | 2012-10-02 | 2015-12-17 | コンチネンタル オートモーティヴ ゲゼルシャフト ミット ベシュレンクテル ハフツングＣｏｎｔｉｎｅｎｔａｌ Ａｕｔｏｍｏｔｉｖｅ ＧｍｂＨ | An electrically heatable honeycomb body extruded from a ceramic material |
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