JPH03288525A - Honeycomb heater and catalyst converter - Google Patents
Honeycomb heater and catalyst converterInfo
- Publication number
- JPH03288525A JPH03288525A JP2088956A JP8895690A JPH03288525A JP H03288525 A JPH03288525 A JP H03288525A JP 2088956 A JP2088956 A JP 2088956A JP 8895690 A JP8895690 A JP 8895690A JP H03288525 A JPH03288525 A JP H03288525A
- Authority
- JP
- Japan
- Prior art keywords
- honeycomb
- honeycomb structure
- catalyst
- metal
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000005192 partition Methods 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 10
- 230000005611 electricity Effects 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract description 4
- 230000008093 supporting effect Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 3
- 229920000609 methyl cellulose Polymers 0.000 abstract description 3
- 239000001923 methylcellulose Substances 0.000 abstract description 3
- 235000010981 methylcellulose Nutrition 0.000 abstract description 3
- 230000002093 peripheral effect Effects 0.000 abstract description 2
- 238000003466 welding Methods 0.000 abstract description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract 1
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 238000005476 soldering Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- -1 A1120°Cr2O3 Chemical class 0.000 description 2
- 229910017060 Fe Cr Inorganic materials 0.000 description 2
- 229910002544 Fe-Cr Inorganic materials 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 101150002418 cpi-2 gene Proteins 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910008947 W—Co Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Chimneys And Flues (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、金属質ハニカム構造体からなるハニカムヒー
ターと触媒コンバーターに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a honeycomb heater and a catalytic converter made of a metallic honeycomb structure.
これらは温風ヒーターなどの民生用ヒーター自動車の排
気ガス浄化用のプレヒーター等の工業用ヒーターとして
好適に使用てき、また自動車の排気ガス浄化用などの触
媒コンバーターとしても好ましく適用てきる。These can be suitably used as industrial heaters such as pre-heaters for purifying the exhaust gas of automobiles, and also as catalytic converters for purifying the exhaust gas of automobiles.
［従来の技術及び発明が解決しようとする課題］従来よ
り、多孔質セラミックハニカム構造体は、例えば自動車
等の内燃ｍ関から排出される排気ガス中の窒素酸化物、
−酸化炭素、炭化水素を浄化するための触媒、触媒担体
、あるいは微粒子除去用フィルターとして使用されてい
る。[Prior Art and Problems to be Solved by the Invention] Conventionally, porous ceramic honeycomb structures have been used to reduce the amount of nitrogen oxides in exhaust gas emitted from internal combustion engines such as automobiles.
-Used as a catalyst for purifying carbon oxides and hydrocarbons, as a catalyst carrier, or as a filter for removing particulates.
このように多孔質セラミックハニカム構造体は上記の用
途に極めて有用な物質として認識され続けているか、近
年になり過酷な条件下て、より大きな機械的強度、耐熱
性を示す物質の開発か望まれるようになってきた。In this way, porous ceramic honeycomb structures continue to be recognized as extremely useful materials for the above-mentioned applications, and in recent years, it has been desired to develop materials that exhibit greater mechanical strength and heat resistance under harsh conditions. It's starting to look like this.
これとは別に、排ガスの規制強化に伴ない、コールドス
タート時のエミッションを低減するヒーター等の開発も
切望されている。Separately, as exhaust gas regulations become stricter, there is a strong need for the development of heaters that reduce emissions during cold starts.
このようなハニカム構造体として、例えば特開昭６３−
３１０９４２号公報、特公昭５８−２３１３８号公報、
及び実開昭６３−６７６０９号公報に記載のものが提案
されている。As such a honeycomb structure, for example, JP-A-63-
Publication No. 310942, Japanese Patent Publication No. 58-23138,
and the one described in Japanese Utility Model Application Publication No. 63-67609 has been proposed.
特開昭６３−３１０９４２号公報には、重量％てＡｆＬ
か５〜５０％、Ｆｅか３０〜９０％、Ｓｎか０〜１０％
、Ｃｕか０〜１０％、Ｃｒか０〜１０％、および１％以
下のＭｇ及び／又はＣａの組成て構成され、気孔率か約
２５〜７５％て所定のセル密度を有するハニカム構造物
か示されており、ディーゼル・パティキュレートのフィ
ルターとして使用てきることか開示されている。In Japanese Patent Application Laid-Open No. 63-310942, AfL is
5-50%, Fe 30-90%, Sn 0-10%
, 0 to 10% of Cu, 0 to 10% of Cr, and 1% or less of Mg and/or Ca, and has a porosity of about 25 to 75% and a predetermined cell density. It is disclosed that it can be used as a filter for diesel particulates.
しかしなから、特開昭６３−３１０９４２号公報には、
ヒーターあるいは触媒コンバーター等に関し何らの開示
かない。However, in Japanese Patent Application Laid-Open No. 63-310942,
There is no disclosure regarding the heater or catalytic converter.
又、特公昭５８−２３１３８号公報には、フォイルタイ
プの金属ハニカム構造物か示されている。このハニカム
構造物は、平板を機械的に変形して波形としこれを平板
とともに巻き上げて金属基体としているものである。そ
して、金属基体の表面を酸化処理して酸化アルミニウム
被膜を形成し、この被膜にアルミナ等の高表面積酸化物
を担持し、さらに貴金属等を含浸させて、自動車排ガス
浄化用の触媒としているものである。Further, Japanese Patent Publication No. 58-23138 discloses a foil type metal honeycomb structure. This honeycomb structure is made by mechanically deforming a flat plate into a corrugated shape and rolling it up together with the flat plate to form a metal base. Then, the surface of the metal substrate is oxidized to form an aluminum oxide film, and this film supports a high surface area oxide such as alumina, and is further impregnated with precious metals, etc., and is used as a catalyst for purifying automobile exhaust gas. be.
さらに実開昭６３−６７６０９号公報には、メタル担体
にアルミナをコートした電気通電可能なメタルモノリス
触媒をプレヒーターとして使用することか開示されてい
る。Furthermore, Japanese Utility Model Application Publication No. 63-67609 discloses the use of a metal monolithic catalyst, which is a metal carrier coated with alumina and capable of conducting electricity, as a preheater.
しかしなから、特公昭５８−２３１３８号公報に記載の
フォイルタイプの金属ハニカム構造物においては、被膜
を形成した金属基体の多孔性か乏しいため触媒層との密
着性か弱く、かつセラミックたる触媒と金属製基体との
熱膨張差により触媒が剥離し易いという欠点かある。ま
た運転サイクル中に、メタル−メタル接合部が剥離しガ
ス流れ方向に凸部に変形するというテレスコープ現象か
発生し易く、運転上重大な支障となる場合かありさらに
フォイルタイプの金属ハニカム製造てはフォイルの圧延
歩留か低く、製造コストか高くなるという問題かある。However, in the foil-type metal honeycomb structure described in Japanese Patent Publication No. 58-23138, the adhesion with the catalyst layer is weak due to the poor porosity of the metal substrate on which the coating is formed, and the ceramic catalyst and metal The disadvantage is that the catalyst tends to peel off due to the difference in thermal expansion with the substrate. Additionally, during the operation cycle, a telescope phenomenon in which metal-to-metal joints peel off and deform into convex parts in the gas flow direction is likely to occur, which can cause serious operational problems. However, there are problems in that the rolling yield of the foil is low and the manufacturing cost is high.
また実開昭６３−６７６０９号公報のプレヒーターも特
公昭５８−２３１３８号公報と同様に、アルミナとメタ
ル担体との熱膨張差等により触媒か剥離し易いという欠
点かあると同時に、・運転中に金属基体のメタル−メタ
ル接合部か剥離し、絶縁部かできて電流ムラか生じ不均
一な発熱を生ずるという問題かある。In addition, the preheater disclosed in Japanese Utility Model Publication No. 63-67609 has the same disadvantage as that in Japanese Patent Publication No. 58-23138, in that the catalyst tends to peel off due to the difference in thermal expansion between the alumina and the metal carrier. Another problem is that the metal-to-metal joints of the metal substrate peel off, forming insulating parts, causing uneven current flow, and uneven heat generation.
［課題を解決するための手段］
従って、本発明は上記欠点を解消したハニカムヒーター
および触媒コンバーターを提供することを目的とするも
のである。[Means for Solving the Problems] Therefore, it is an object of the present invention to provide a honeycomb heater and a catalytic converter that eliminate the above-mentioned drawbacks.
そしてその目的は１本発明によれば、金属粉末をハニカ
ム状に押出成形し、焼結させた金属質ハニカム構造体に
、通電のための少なくとも２つの電極を設け、該金属質
ハニカム構造体における貫通孔内のガス流体を加熱する
ことを特徴とするハニカムヒーターにより達成すること
かてきる。According to the present invention, at least two electrodes for supplying electricity are provided in a metallic honeycomb structure obtained by extruding metal powder into a honeycomb shape and sintering the metallic honeycomb structure. This can be achieved by a honeycomb heater, which is characterized by heating the gas fluid in the through holes.
また、金属質ハニカム構造体の隔壁及び気孔の表面を耐
熱性金属酸化物て被覆すると、耐熱性、耐食性に優れ好
ましい。Further, it is preferable to coat the surfaces of the partition walls and pores of the metallic honeycomb structure with a heat-resistant metal oxide because of excellent heat resistance and corrosion resistance.
さらに、本発明では、主モノリス触媒の上流側に近接さ
せて、上記のハニカムヒーターを配設した触媒コンバー
ター、および、金属粉末をハニカム状に押出成形し、焼
結させた金属質ハニカム構造体に触媒を担持させるとと
もに、電極を設けてなる触媒コンバーターか提供される
。Furthermore, the present invention includes a catalytic converter in which the honeycomb heater described above is disposed close to the upstream side of the main monolithic catalyst, and a metallic honeycomb structure in which metal powder is extruded into a honeycomb shape and sintered. A catalytic converter is provided in which a catalyst is supported and an electrode is provided.
更にまた、本発明ては、主モノリス触媒の上流側に近接
させて、金属粉末をハニカム状に押出成形し焼結させた
金属質ハニカム構造体に触媒を担持させ且つ通電のため
の少なくとも２つの電極を設けてなるハニカムヒーター
を配設した触媒コンバーターか提供される。Furthermore, in the present invention, a metallic honeycomb structure in which a metal powder is extruded into a honeycomb shape and sintered is placed close to the upstream side of the main monolithic catalyst, and a catalyst is supported thereon. A catalytic converter with a honeycomb heater provided with electrodes is provided.
［作用コ
本発明は、金属粉末をハニカム状に押出成形し、焼結さ
せた金属質ハニカム構造体に電極を設け、ハニカムヒー
ターとする。即ち、いわゆる粉末拍金および押出し成形
性を用いて作製したものて、工程か簡略で低コスト化か
図れる。[Function] In the present invention, electrodes are provided on a metallic honeycomb structure made by extruding metal powder into a honeycomb shape and sintering to obtain a honeycomb heater. That is, by using so-called powder metal and extrusion moldability, the process can be simplified and costs can be reduced.
またこのハニカムヒーターは金属粉末を用いた金属質ハ
ニカム構造体（一体物）であるため、テレスコープ現象
か生しず、均一な発熱を達成でき、好ましい。又、本発
明の触媒コンバーターも、同じく金属粉末を用いた多孔
性に富む金属質ハニカム構造体であるため、これに触媒
を担持する場合てあっても、触媒層との密着性か強く熱
膨張差による触媒の剥離か生ずることがほとんどなくな
る。Further, since this honeycomb heater is a metallic honeycomb structure (integrated body) using metal powder, it is possible to achieve uniform heat generation without causing the telescope phenomenon, which is preferable. In addition, since the catalytic converter of the present invention is also a highly porous metallic honeycomb structure using metal powder, even if a catalyst is supported on this structure, the adhesion with the catalyst layer may be affected by strong thermal expansion. The occurrence of catalyst peeling due to differences is almost eliminated.
なお、本発明のハニカムヒーターは、金属質ハニカム構
造体の隔壁及び気孔の表面をＡ１１２０゜Ｃｒ２Ｏ３等
の耐熱性金属酸化物て被覆することか耐熱性、耐酸化性
、耐食性か向上し好ましい
本発明の基体である金属質ハニカム構造体の構成材料と
しては、発熱材料からなるものてあれば制限はなく、例
えば、ステンレス鋼やＦｅ−ＣｒＡＭ、Ｆｅ−Ｃｒ、Ｆ
ｅ−Ａｎ、Ｆｅ−Ｎｉ、Ｗ−Ｃｏ、Ｎｉ−Ｃｒ等の組成
を有する材料からなるものか挙げられる。上記のうち、
Ｆｅ−Ｃｒ−Ａｎ、Ｆｅ−Ｃｒ、Ｆｅ−Ａｎか耐熱性、
耐酸化性、耐食性に優れ、かつ安価て好ましい。In addition, the honeycomb heater of the present invention has improved heat resistance, oxidation resistance, and corrosion resistance by coating the surfaces of the partition walls and pores of the metallic honeycomb structure with a heat-resistant metal oxide such as A1120°Cr2O3, which is preferable according to the present invention. The constituent material of the metallic honeycomb structure, which is the base body, is not limited as long as it is made of a heat-generating material.
Examples include materials having compositions such as e-An, Fe-Ni, W-Co, and Ni-Cr. Of the above,
Fe-Cr-An, Fe-Cr, Fe-An or heat resistant,
It is preferable because it has excellent oxidation resistance and corrosion resistance, and is inexpensive.
なお、金属質ハニカム構造体において、Ｃｒ含有量は０
〜４０重量％、好ましくは１０〜２５重量％、Ａｎ含有
量は０〜３０重量％、好ましくは５〜２５重量％である
。Ｃｒか４０重量％を超えた場合には脆性か大きくなり
、コストか高くなる。ＡｆＬか３０重量％を超えると脆
性か大きくなり金属としての特質が失われる。Note that in the metallic honeycomb structure, the Cr content is 0.
-40% by weight, preferably 10-25% by weight, and the An content is 0-30% by weight, preferably 5-25% by weight. If the Cr content exceeds 40% by weight, it becomes brittle and increases the cost. If AfL exceeds 30% by weight, it becomes brittle and loses its characteristics as a metal.
次に、本発明の金属ハニカム構造体の製造方法の例を説
明する。Next, an example of a method for manufacturing a metal honeycomb structure of the present invention will be described.
まず、所望の組成となるように、例えばＦｅ粉末、Ａｆ
ｌ粉末、Ｃｒ粉末、又はこれらの合金粉末などにより金
属粉末原料を調製する。次いて、このように調製された
金属粉末原料と、メチルセルロース、ボリヒニルアルコ
ール等の有機ハインタ水を混合した後、この混合物を所
望のハニカム形状に押出成形する。First, to obtain the desired composition, for example, Fe powder, Af
A metal powder raw material is prepared using L powder, Cr powder, or an alloy powder thereof. Next, the metal powder raw material prepared in this manner is mixed with an organic integer such as methyl cellulose or borihinyl alcohol, and then this mixture is extruded into a desired honeycomb shape.
なお、金属粉末原料と有機バインター、水の混合に際し
、水を添加する前に金属粉末にオレイン酸等の酸化防止
剤を混合するか、あるいは予め酸化されない処理を施し
た金属粉末を使用することか好ましい。When mixing metal powder raw materials, organic binder, and water, it is recommended to mix an antioxidant such as oleic acid with the metal powder before adding water, or to use metal powder that has been previously treated to prevent oxidation. preferable.
次に、押出成形されたハニカム成形体を、非酸化雰囲気
下１０００−１４００’Ｃて焼成する。ここで、水素を
含む非酸化雰囲気下において焼成を行なうと、有機バイ
ンターかＦｅｈ４を触媒にして分解除去し、良好な焼結
体を得ることかでき、好ましい。Next, the extruded honeycomb molded body is fired at 1000-1400'C in a non-oxidizing atmosphere. Here, it is preferable to perform the calcination in a non-oxidizing atmosphere containing hydrogen because the organic binder can be decomposed and removed using Feh4 as a catalyst and a good sintered body can be obtained.
焼成温度か１０００’Ｃ未満の場合、成形体か焼結せず
、焼成温度か１４００″Ｃを超えると得られる焼結体か
変形するため、好ましくない。If the firing temperature is less than 1000'C, the molded body will not be sintered, and if the firing temperature exceeds 1400'C, the resulting sintered body will be deformed, which is not preferable.
なあ、望ましくは、次いて、得られた焼結体の隔壁及び
気孔の表面を耐熱性金属酸化物て被覆する。この耐熱性
金属酸化物による被覆方法としては、ド記の方法か好ま
しいものとして挙げられる。Preferably, the surfaces of the partition walls and pores of the obtained sintered body are then coated with a heat-resistant metal oxide. Preferred methods for coating with this heat-resistant metal oxide include the method described below.
■金属ハニカム構造体を酸化雰囲気中７００〜１１００
°Ｃて熱処理する。■Metal honeycomb structure in oxidizing atmosphere 700-1100
Heat treat at °C.
■ＡＭ等を焼結体の隔壁及び気孔の表面にメツキ（例え
ば気相メツキ）し、酸化雰囲気中７００〜１１００℃て
熱処理する。(2) Plating the surfaces of the partition walls and pores of the sintered body with AM or the like (for example, vapor phase plating), and heat-treating at 700 to 1100°C in an oxidizing atmosphere.
■Ａ文等の金属溶湯中に浸漬し、酸化雰囲気中７００〜
１１００’Ｃて熱処理する。■ Immersed in molten metal such as A pattern, 700~ in oxidizing atmosphere
Heat treated at 1100'C.
■アルミナゾル等を用い焼結体の隔壁及び気孔の表面に
被覆し、酸化雰囲気中７００〜１１００°Ｃて熱処理す
る。(2) The surfaces of the partition walls and pores of the sintered body are coated with alumina sol or the like, and heat treated at 700 to 1100°C in an oxidizing atmosphere.
尚、熱処理温度は、耐熱性、耐酸化性の点で９００〜１
１００°Ｃとすることか好ましい。In addition, the heat treatment temperature is 900 to 1 in terms of heat resistance and oxidation resistance.
It is preferable to set the temperature to 100°C.
上記のようにして得られた金属質ハニカム構造体は、通
常その外周部の隔壁または内部に、ろう付け、溶接など
の手段によって電極を設けることにより、本発明のハニ
カムヒーターか作製される。The honeycomb heater of the present invention is produced by providing the metallic honeycomb structure obtained in the above manner with electrodes, usually on the outer peripheral partition wall or inside thereof, by means of brazing, welding, or the like.
この金属質ハニカム構造体はヒーターとして用いる場合
、全体としてその抵抗値か０．００１Ω〜０，５Ωの範
囲となるように形成することが好ましい。When this metallic honeycomb structure is used as a heater, it is preferably formed so that its overall resistance value is in the range of 0.001Ω to 0.5Ω.
また、上記の金属質ハニカム構造体の表面にさらに触媒
を担持させることにより、排気ガスの浄化反応（酸化反
応熱等）による温度上昇が期待てきるため、ヒーターと
して、あるいは触媒コンバーターとして好ましい。Furthermore, by further supporting a catalyst on the surface of the above-mentioned metallic honeycomb structure, a temperature increase due to the exhaust gas purification reaction (heat of oxidation reaction, etc.) can be expected, so it is preferable as a heater or a catalytic converter.
金属質ハニカム構造体の表面に担持する触媒は、大きな
表面積を有する担体に触媒活性物質を担持させたもので
ある。ここで、大きな表面積を有する担体としては、例
えばγ−／Ｍ１２０．系、ＴｉＯ２系、５ｉｆ２−Ａｆ
Ｌ２０：ｌ系などやペロブスカイト系のものか代表的な
ものとして挙げられる。触媒活性物質としては、例えば
Ｐｔ、Ｐｄ、Ｒｈ等の貴金属、Ｃｕ、Ｎｉ、Ｃｒ、Ｃｏ
等の卑金属などを挙げることかできる。上記のうち、γ
−ＡｆＬ２０：ｌ系にＰｔ、Ｐｄを１０〜１００ｇ１ｆ
ｔ３担持したものか好ましい。The catalyst supported on the surface of the metallic honeycomb structure is one in which a catalytically active substance is supported on a carrier having a large surface area. Here, as a carrier having a large surface area, for example, γ-/M120. system, TiO2 system, 5if2-Af
Typical examples include L20:l type and perovskite type. Examples of catalytically active substances include noble metals such as Pt, Pd, and Rh, Cu, Ni, Cr, and Co.
Examples include base metals such as Of the above, γ
-AfL20: 10 to 100 g1f of Pt and Pd to the l system
Preferably, it supports t3.
発明におけるハニカム構造体のハニカム形状としては特
に限定はされないか、具体的には、例えば６〜１５００
セル／Ｉｎ２ （０，９〜２３３セル／Ｃ１）の範囲の
セル密度を有するように形成することか好ましい。又、
隔壁の厚さは５０〜２０００ ｇｗ＋の範囲か好ましい
。The honeycomb shape of the honeycomb structure in the invention is not particularly limited, and specifically, for example, 6 to 1500
It is preferable to form the cell to have a cell density in the range of cell/In2 (0.9 to 233 cells/C1). or,
The thickness of the partition wall is preferably in the range of 50 to 2000 gw+.
また、金属ハニカム構造体の気孔率は制限されないか、
０〜５０％、好ましくは２５％未満の範囲とすることか
強度特性、耐酸化性、耐食性の面から望ましい。また、
触媒を担持する場合には、触媒層との密着性の点から５
％以上の気孔率を有することか好ましい。Also, the porosity of metal honeycomb structures is not limited or
A range of 0 to 50%, preferably less than 25% is desirable from the viewpoint of strength properties, oxidation resistance, and corrosion resistance. Also,
When supporting a catalyst, from the viewpoint of adhesion to the catalyst layer, 5
% or more is preferable.
尚、本発明においてハニカム構造体とは、隔壁により仕
切られた多数の貫通孔を有する一体構造をいい、例えば
貫通孔の断面形状（セル形状）は円形、多角形、コルゲ
ート形等の各種の任意な形状か使用てきる。In the present invention, the honeycomb structure refers to an integral structure having a large number of through holes partitioned by partition walls, and the cross-sectional shape (cell shape) of the through holes may be any arbitrary shape such as circular, polygonal, corrugated, etc. You can use any shape.
［実施例］
以下、本発明を実施例に基づいて更に詳しく説明するが
、本発明はこれらの実施例に限られるものてはない。[Examples] Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.
（実施例１）
平均粒径１０．２０．２２ｐｍのＦｅ粉、Ｆｅ−Ａ文粉
（ＡＭ５０ｗｔＸ ）、Ｆｅ−Ｃｒ粉（Ｃｒ５０ｗｔ＄
）の原料を用い、Ｆｅ−２２Ｃｒ−５Ａ！；Ｌ（重量％
〉の組成になるよう原料を配合し、これに有機バインダ
ー（メチルセルロース）と酸化防止剤（オレイン酸）、
水を添加して坏土を調製し、リフ厚４ｍ１１ 、貫通孔
数４００ ｃｐｉ２の四角セルよりなるハニカムを押出
し成形し、乾燥後Ｈ２雰囲気下１３００’ｃて焼威し、
その後空気中１０００″Ｃて熱処理を行った。得られた
ハニカム構造体の中心軸上に電極をセットし、外周部に
もう一方の電極をセットした。(Example 1) Fe powder, Fe-A powder (AM50wtX), Fe-Cr powder (Cr50wt$) with an average particle size of 10.20.22pm
), Fe-22Cr-5A! ;L (weight%
The raw materials are blended to have the following composition, and an organic binder (methylcellulose), an antioxidant (oleic acid),
A clay was prepared by adding water, and a honeycomb consisting of square cells with a rift thickness of 4 m11 and a number of through holes of 400 cpi2 was extruded, and after drying, it was burned at 1300'C in an H2 atmosphere.
Thereafter, heat treatment was performed in air at 100''C. An electrode was set on the central axis of the obtained honeycomb structure, and the other electrode was set on the outer periphery.
得られたハニカム構造体の気孔率は２２％であり、平均
細孔径は５ｇｍてあった。The obtained honeycomb structure had a porosity of 22% and an average pore diameter of 5 gm.
（実施例２）
実施例１て得られたハニカム構造体に、γΔ文。０３を
被覆コートし、次いて貴金属ｐｔとＰｄを各々２０ｇ／
ｒＬ″担持し、６００℃て焼成することにより、触媒か
担持されたハニカム構造体を得、その後電極を実施例１
と同様にセットした。(Example 2) γΔ texture was added to the honeycomb structure obtained in Example 1. 03 and then 20g/each of precious metals PT and Pd.
By supporting rL'' and firing at 600°C, a catalyst-supported honeycomb structure was obtained, and then an electrode was prepared as in Example 1.
set in the same way.
（実施例３）
Ｆｅ−２５Ａ文の組成になるよう実施例１と同様の方法
てハニカム構造体を得た。このハニカム構造体は気孔率
か２５％、平均細孔径か４ｇｍであった。(Example 3) A honeycomb structure was obtained in the same manner as in Example 1 so as to have a composition of Fe-25A. This honeycomb structure had a porosity of 25% and an average pore diameter of 4 gm.
（実施例４）
実施例３て得られたハニカム構造体に、実施例２と同様
の方法て触媒か担持されたハニカム構造体を得た。(Example 4) A honeycomb structure in which a catalyst was supported on the honeycomb structure obtained in Example 3 in the same manner as in Example 2 was obtained.
（比較例１）
市販のフォイルタイプのメタルハニカム（リフ厚２＋＊
ｉｌ 、貫通孔数４００ ｃｐｉ２、組成Ｆｅ−２０Ｃ
ｒ−５ＡＪＬ）を用い、実施例１と同様の方法で電極を
セットした。(Comparative Example 1) Commercially available foil type metal honeycomb (riff thickness 2+*
il, number of through holes 400 cpi2, composition Fe-20C
r-5AJL), and electrodes were set in the same manner as in Example 1.
（比較例２）
比較例１のサンプルを特公昭５８−２３１３８号公報に
記載の方法で酸化処理し、実施例２の方法と同様の方法
て触媒を担持した。(Comparative Example 2) The sample of Comparative Example 1 was oxidized by the method described in Japanese Patent Publication No. 58-23138, and a catalyst was supported by the same method as in Example 2.
表１
ヒートサイクル耐久試験による触媒重量減少率
［評価コ
（ヒートサイクル耐久試験〉
自動車排ガス用触媒のプレヒーターを想定し、１．０■
’／ｓｉｎの空気を貫通孔内に流入し、１２Ｖのバッテ
リーを用いて３０秒間通電することを３００回繰り返し
た。隔壁の温度は約４００〜５００℃に到達した。Table 1 Catalyst weight reduction rate by heat cycle durability test [Evaluation rate (heat cycle durability test)] Assuming a preheater for a catalyst for automobile exhaust gas, 1.0
Air of '/sin was flowed into the through hole and electricity was applied for 30 seconds using a 12V battery, which was repeated 300 times. The temperature of the septum reached approximately 400-500°C.
（触媒剥離テスト）
ヒートサイクル耐久試験前後の触媒の重量変化率を表１
に、またヒートサイクル試験後のサンプルを超音波洗浄
によって強制的に触媒を剥離させたときの重量変化率を
表２に示す。(Catalyst peeling test) Table 1 shows the weight change rate of the catalyst before and after the heat cycle durability test.
Furthermore, Table 2 shows the weight change rate when the catalyst was forcibly removed from the sample after the heat cycle test by ultrasonic cleaning.
表２
ヒートサイクル耐久試験後サンプルの触媒剥離量
尚、ヒートサイクル耐久試験により、フォイルタイプの
メタルハニカムは平板と波板の部分の接合部にクラック
か発生し、テレスコープ現象か起っていることか確認さ
れたか、実施例のサンプルは外観上旬等変化しなかった
。Table 2 Amount of catalyst peeled off from sample after heat cycle durability test Furthermore, as a result of the heat cycle durability test, cracks were found in the foil-type metal honeycomb at the joint between the flat plate and the corrugated plate, and a telescoping phenomenon occurred. Confirmed that, the appearance of the sample of Example did not change.
±２０°Ｃ範囲内であるのに対し、比較例ては±５０℃
てあった。While it is within ±20°C range, the comparative example is ±50°C.
There was.
（発熱特性確認テスト）
ヒートサイクル耐久試験後のサンプルに１．０ｍ３／ｓ
ｉｎの空気を流入し、１２Ｖのバッテリーを用いて３０
秒間通電しハニカム構造体の中心近傍の隔壁を５点測温
した。その隔壁温度か３５０’Ｃになるまての到達時間
を表３に示す。(Heating property confirmation test) 1.0m3/s on the sample after heat cycle durability test
in and using a 12V battery for 30
Electricity was applied for seconds and the temperature was measured at five points on the partition wall near the center of the honeycomb structure. Table 3 shows the time required for the partition wall temperature to reach 350'C.
表３
（自動車排ガス用プレヒーター性能の確認）エンジン始
動時の性能を確認するために、市販の三元触媒の前方に
プレヒーターとして本実施例のサンプルを設置した触媒
コンバーターを用いた。この触媒コンバーターにエンジ
ン排ガスを導入し、１００°Ｃから４２０°Ｃまて２分
間で定速昇温させ、４２０ ’Ｃて１分間キープし、排
ガスの浄化率を測定した。Table 3 (Confirmation of performance of preheater for automobile exhaust gas) In order to confirm performance at engine startup, a catalytic converter in which the sample of this example was installed as a preheater in front of a commercially available three-way catalyst was used. Engine exhaust gas was introduced into this catalytic converter, the temperature was raised at a constant rate from 100°C to 420°C over 2 minutes, and the temperature was maintained at 420'C for 1 minute to measure the purification rate of the exhaust gas.
尚、ヒーターはヒートサイクル試験後のサンフルを用い
、１２Ｖのバッテリーて１分間通゛セした状態とした。The heater used was Sunflu after the heat cycle test, and the heater was turned off for 1 minute using a 12V battery.
Ｏから３分間の各ガスの平均浄化率を表４に示す。Table 4 shows the average purification rate of each gas for 3 minutes from O.
尚、サンプルの温度分布は、実施例１〜４ては表４
平均転化率
（％）
［発明の効果］
以上説明したように、本発明によれば、耐久性および触
媒担持性に優れるとともに、優れた昇温特性と均一な発
熱特性を有するハニカムヒーターを提供てき、さらに上
記特性を有し、排ガス浄化性能の向上した触媒コンバー
ターを提供することかてきる。In addition, the temperature distribution of the samples is shown in Table 4 for Examples 1 to 4. Average conversion rate (%) It is possible to provide a honeycomb heater having excellent temperature increase characteristics and uniform heat generation characteristics, and furthermore to provide a catalytic converter having the above characteristics and improved exhaust gas purification performance.
Claims (7)
金属質ハニカム構造体に、通電のための少なくとも２つ
の電極を設け、該金属質ハニカム構造体における貫通孔
内のガス流体を加熱することを特徴とするハニカムヒー
ター。(1) A metallic honeycomb structure made by extruding metal powder into a honeycomb shape and sintering is provided with at least two electrodes for electricity supply, and the gas fluid in the through holes in the metallic honeycomb structure is heated. A honeycomb heater that is characterized by:
熱性金属酸化物で被覆した請求項１記載のハニカムヒー
ター。(2) The honeycomb heater according to claim 1, wherein the surfaces of the partition walls and pores of the metallic honeycomb structure are coated with a heat-resistant metal oxide.
または２記載のハニカムヒーターを配設したことを特徴
とする触媒コンバーター。(3) Close to the upstream side of the main monolith catalyst, as claimed in claim 1.
Or a catalytic converter characterized by having arranged the honeycomb heater according to 2.
金属質ハニカム構造体に触媒を担持させるとともに、通
電のための少なくとも２つの電極を設けたことを特徴と
する触媒コンバーター。(4) A catalytic converter characterized in that a metal honeycomb structure is formed by extruding metal powder into a honeycomb shape and sintered to support a catalyst, and at least two electrodes for conducting electricity are provided.
熱性金属酸化物で被覆した請求項４記載の触媒コンバー
ター。(5) The catalytic converter according to claim 4, wherein the surfaces of the partition walls and pores of the metallic honeycomb structure are coated with a heat-resistant metal oxide.
をハニカム状に押出成形し焼結させた金属質ハニカム構
造体に触媒を担持させ且つ通電のための少なくとも２つ
の電極を設けてなるハニカムヒーターを配設したことを
特徴とする触媒コンバーター。(6) A metallic honeycomb structure formed by extruding metal powder into a honeycomb shape and sintering the metal powder in close proximity to the upstream side of the main monolithic catalyst supports the catalyst and is provided with at least two electrodes for conducting electricity. A catalytic converter featuring a honeycomb heater.
熱性金属酸化物で被覆した請求項６記載の触媒コンバー
ター。(7) The catalytic converter according to claim 6, wherein the surfaces of the partition walls and pores of the metallic honeycomb structure are coated with a heat-resistant metal oxide.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2088956A JP2898337B2 (en) | 1990-04-03 | 1990-04-03 | Honeycomb heater and catalytic converter |
| ES91302855T ES2119761T3 (en) | 1990-04-03 | 1991-04-02 | HEAT RESISTANT METALLIC MONOLITH AND PROCEDURE FOR ITS MANUFACTURE. |
| DE69129644T DE69129644T2 (en) | 1990-04-03 | 1991-04-02 | Highly heat-resistant metallic monolith and process for its manufacture |
| KR1019910005295A KR0134368B1 (en) | 1990-04-03 | 1991-04-02 | Heat-resistant metal monolith and manufacturing method therefor |
| EP91302855A EP0450897B1 (en) | 1990-04-03 | 1991-04-02 | Heat-resistant metal monolith and manufacturing method therefor |
| CA002039509A CA2039509C (en) | 1990-04-03 | 1991-04-02 | Heat-resistant metal monolith and manufacturing method therefor |
| AU74060/91A AU653713B2 (en) | 1990-04-03 | 1991-04-03 | Heat-resistant metal monolith and manufacturing method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2088956A JP2898337B2 (en) | 1990-04-03 | 1990-04-03 | Honeycomb heater and catalytic converter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03288525A true JPH03288525A (en) | 1991-12-18 |
| JP2898337B2 JP2898337B2 (en) | 1999-05-31 |
Family
ID=13957305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2088956A Expired - Fee Related JP2898337B2 (en) | 1990-04-03 | 1990-04-03 | Honeycomb heater and catalytic converter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2898337B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009279482A (en) * | 2008-05-20 | 2009-12-03 | Gifu Univ | Apparatus for treating volatile organic compound |
| JP2011230115A (en) * | 2010-04-09 | 2011-11-17 | Ibiden Co Ltd | Honeycomb structure |
-
1990
- 1990-04-03 JP JP2088956A patent/JP2898337B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009279482A (en) * | 2008-05-20 | 2009-12-03 | Gifu Univ | Apparatus for treating volatile organic compound |
| JP2011230115A (en) * | 2010-04-09 | 2011-11-17 | Ibiden Co Ltd | Honeycomb structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2898337B2 (en) | 1999-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2931362B2 (en) | Resistance control type heater and catalytic converter | |
| JP2919987B2 (en) | Resistance adjustment type heater | |
| JP3001281B2 (en) | Honeycomb monolith heater | |
| US5288975A (en) | Resistance adjusting type heater | |
| US5200154A (en) | Honeycomb heater having integrally formed electrodes and/or integrally sintered electrodes and method of manufacturing such honeycomb heater | |
| JP3040510B2 (en) | Honeycomb heater | |
| AU651814B2 (en) | Resistance adjusting type heater and catalytic converter | |
| US5264186A (en) | Catalytic converter for use in controlling automotive exhaust emissions | |
| US5266278A (en) | Honeycomb heater having integrally formed electrodes and/or integrally sintered electrodes and method of manufacturing such honeycomb heater | |
| US5229080A (en) | Resistance adjusting type heater and catalytic converter | |
| US5202548A (en) | Resistance adjusting type heater | |
| KR0134368B1 (en) | Heat-resistant metal monolith and manufacturing method therefor | |
| JP3058995B2 (en) | Honeycomb heater | |
| JP3091246B2 (en) | Heat-resistant metallic monolith and method for producing the same | |
| JP3953944B2 (en) | Metal foil and honeycomb structure | |
| JPH0466714A (en) | Resistance regulation type heater and catalyst converter and operation method of catalyst converter | |
| JPH03288525A (en) | Honeycomb heater and catalyst converter | |
| JPH04366584A (en) | Resistance regulating type heater and heater unit | |
| JP3145166B2 (en) | Resistance adjustment type heater | |
| JP2818477B2 (en) | Catalytic converter for automotive exhaust gas purification | |
| JP3058991B2 (en) | Multi-stage honeycomb heater and method of operating the same | |
| JP2863330B2 (en) | Resistance adjustment type heater | |
| JP3091201B2 (en) | Catalytic converter for automotive exhaust gas purification | |
| JP2821006B2 (en) | Resistance control type heater and catalytic converter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |