JPH05293388A - Production of metal honeycomb catalyst carrier for purification of exhaust gas - Google Patents
Production of metal honeycomb catalyst carrier for purification of exhaust gasInfo
- Publication number
- JPH05293388A JPH05293388A JP4098200A JP9820092A JPH05293388A JP H05293388 A JPH05293388 A JP H05293388A JP 4098200 A JP4098200 A JP 4098200A JP 9820092 A JP9820092 A JP 9820092A JP H05293388 A JPH05293388 A JP H05293388A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- honeycomb structure
- aluminum
- catalyst
- lanthanum
- 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.)
- Pending
Links
- 238000000746 purification Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 title claims description 80
- 229910052751 metal Inorganic materials 0.000 title claims description 51
- 239000002184 metal Substances 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 33
- 229910052782 aluminium Inorganic materials 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 229910052746 lanthanum Inorganic materials 0.000 claims description 16
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 9
- 239000010954 inorganic particle Substances 0.000 claims description 8
- -1 lanthanum aluminate Chemical class 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002604 lanthanum compounds Chemical class 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000007751 thermal spraying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 28
- 238000005507 spraying Methods 0.000 abstract description 10
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 239000000567 combustion gas Substances 0.000 abstract description 4
- 239000010935 stainless steel Substances 0.000 abstract description 4
- 229910000859 α-Fe Inorganic materials 0.000 abstract 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 241000264877 Hippospongia communis Species 0.000 description 60
- 230000000694 effects Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000007084 catalytic combustion reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000005219 brazing Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 206010040844 Skin exfoliation Diseases 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、排ガス浄化用金属ハニ
カム触媒担体の製法に関し、特に自動車エンジンの排気
を初め、各種産業・化学プラントから発生する廃（排）
ガス中の各種炭化水素（以下、ＨＣと記すことがあ
る）、一酸化炭素（ＣＯ）等、燃焼可能な有害物質を除
去するための触媒担体の製法および該担体を用いた触媒
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a metal honeycomb catalyst carrier for purifying exhaust gas, and particularly waste (exhaust gas) generated from various industrial and chemical plants including exhaust gas from automobile engines.
The present invention relates to a method for producing a catalyst carrier for removing harmful substances combustible such as various hydrocarbons (hereinafter sometimes referred to as HC) and carbon monoxide (CO) in a gas, and a catalyst using the carrier.
【０００２】[0002]
【従来の技術】排ガス浄化技術の分野においては、近
年、単位体積当たりの表面積が大きくとれ、しかも圧力
損失を低く抑えることのできる、いわゆるハニカム触媒
が広く利用されている。ハニカム触媒の基材としては、
押出し成形法で製造されるセラミックスハニカムが一般
的に用いられており、その断面形状は蜂の巣状、正方形
等各種のものがある。セラミック繊維を紙状素材に抄造
した、いわゆるセラミックペーパーをコルゲート（波
状）加工し、これらを平板とともに巻き込んでハニカム
構造とする基材も利用されるようになっている。2. Description of the Related Art In the field of exhaust gas purification technology, so-called honeycomb catalysts have been widely used in recent years because they have a large surface area per unit volume and can suppress pressure loss to a low level. As the base material of the honeycomb catalyst,
A ceramic honeycomb manufactured by an extrusion molding method is generally used, and various sectional shapes such as a honeycomb shape and a square shape are available. A base material having a honeycomb structure is also used in which corrugated (corrugated) processing is performed on so-called ceramic paper obtained by making ceramic fibers into a paper-like material, and these are wound together with a flat plate.
【０００３】セラミックハニカムとは別に、最近はアル
ミニウムを数％含有し、耐酸化性向上のためにイットリ
ウムやセリウムを微量添加したフェライト系ステンレス
鋼薄板（通常５０μｍ前後）を用いた、目の細かい金属
ハニカム構造体が適用されつつある。上記のセラミック
または金属ハニカム構造体を排ガス浄化用触媒体とする
ことに対しては、通常、活性アルミナに代表される高比
表面積無機粒子（比表面積：数十〜百数十ｍ2 ／ｇが一
般的）をウォッシュコートして、これを触媒担体とし、
この触媒担体に触媒活性のある金属（Ｐｄ、Ｐｔ等）を
分散担持させる方法がとられる。Apart from the ceramic honeycomb, recently, a fine-grained metal using a ferritic stainless steel thin plate (usually around 50 μm) containing a few% of aluminum and a slight amount of yttrium or cerium added to improve oxidation resistance is used. Honeycomb structures are being applied. In order to use the above ceramic or metal honeycomb structure as an exhaust gas purifying catalyst, high specific surface area inorganic particles typified by activated alumina (specific surface area: tens to hundreds of tens m 2 / g (Generally) is washcoated, and this is used as a catalyst carrier,
A method of dispersing and supporting a metal having catalytic activity (Pd, Pt, etc.) on this catalyst carrier is adopted.
【０００４】[0004]
【発明が解決しようとする課題】接触燃焼によって排ガ
スを浄化する触媒は、通常２００〜３００℃で着火し、
５００℃前後またはこれを超える温度で燃え切るような
仕様とされており、これに対応した装置設計条件や運転
条件が適用される。一般の産業プラントの排ガスの浄化
に対して触媒燃焼法を適用する場合、こうした条件設定
は通常手段であり、運転開始時または運転中に触媒の温
度が着火温度以下となる場合は、通常、助燃手段がとら
れ、これについては装置運用または環境汚染の問題は特
に見当たらない。A catalyst for purifying exhaust gas by catalytic combustion normally ignites at 200 to 300 ° C.
It is designed to burn out at temperatures around 500 ° C or higher, and device design conditions and operating conditions corresponding to this are applied. When applying the catalytic combustion method for purification of exhaust gas from general industrial plants, such condition setting is usually a means, and when the temperature of the catalyst is below the ignition temperature at the start of operation or during operation, it is usually the auxiliary combustion. Measures have been taken, for which no particular problems with equipment operation or environmental pollution have been found.
【０００５】しかしながら燃焼エネルギーを動力源とす
る自動車や発電機のように、コールドスタートを避け得
ないものにおいては、運転開始後から触媒が着火温度に
達するまでの時間内に触媒を通過する排ガスは、実質的
に処理されずに大気中に放出されることになる。特にコ
ールドスタート時は完全燃焼が起きにくいので、多量の
有害ガスが排出される。この問題は特に熱伝導率が低い
セラミックハニカム触媒の場合に重大となる。However, in vehicles such as automobiles and generators that use combustion energy as a power source, in which cold start is unavoidable, the exhaust gas that passes through the catalyst within the time from the start of operation until the catalyst reaches the ignition temperature is , Will be released into the atmosphere substantially untreated. Especially at cold start, a large amount of harmful gas is emitted because complete combustion is difficult to occur. This problem becomes serious especially in the case of a ceramic honeycomb catalyst having a low thermal conductivity.
【０００６】こうした問題を解決する１つの手段は、熱
伝導率が高く、運転開始初期に温度が容易に上昇する金
属ハニカム触媒を用いることである。金属ハニカム触媒
用の金属材料としては、アルミニウムを含有した耐酸化
性の良好なフェライト系ステンレス鋼薄板が好適である
が、本材料は、従来、薄板製造が困難なため高価であっ
た。最近は製造技術の進歩により、安価に製造されるよ
うになっているが、通常の汎用ステンレス鋼と較べる
と、価格にはまだ大きな差があり、さらにコルゲート加
工後に基材を一体化するためのろう付け加工や、触媒と
する上で前提条件となる高比表面積無機粒子（触媒担
体）のウォッシュコートのため、一旦高温加熱によりア
ルミナのウィスカを析出させるなどの処理が必要であ
り、種々の面で従来のセラミックハニカム基材と較べ、
製造コストが高くなるという欠点がある。One means for solving such a problem is to use a metal honeycomb catalyst which has a high thermal conductivity and whose temperature easily rises in the initial stage of operation. As a metal material for the metal honeycomb catalyst, a ferritic stainless steel thin plate containing aluminum and having good oxidation resistance is suitable, but this material has been expensive since it is difficult to manufacture a thin plate. Recently, due to the progress of manufacturing technology, it is manufactured at low cost, but there is still a big difference in price compared to ordinary general-purpose stainless steel, and further, it is necessary to integrate the base material after corrugating. Since it is a brazing process or a washcoat of high specific surface area inorganic particles (catalyst carrier), which is a prerequisite for using as a catalyst, it is necessary to perform treatment such as precipitation of alumina whiskers once by heating at high temperature. Compared with the conventional ceramic honeycomb substrate,
It has the drawback of high manufacturing costs.
【０００７】また金属基材と高比表面積無機粒子との熱
膨脹係数が大きく異なるため、昇温冷却の繰返しに伴う
ウォッシュコート層の剥離や、機械的振動による剥離の
恐れがある。従来の金属ハニカム触媒におけるもう１つ
の問題は、昇温時に基材が熱膨脹する結果、ハニカムの
中心部が外部にせり出す現象（フィルムアウト現象）を
生じることである。これは波板と平板を強固にろう付け
または溶接することなどで解決できる問題であるが、よ
り信頼性の高いものをつくろうとすると製造コストが著
しく増大するといった問題を引き起こす。Further, since the thermal expansion coefficient of the metal base material and that of the high specific surface area inorganic particles are largely different, there is a risk of peeling of the washcoat layer due to repeated heating and cooling, and peeling due to mechanical vibration. Another problem in the conventional metal honeycomb catalyst is that the base material thermally expands when the temperature rises, resulting in a phenomenon (film-out phenomenon) in which the central portion of the honeycomb protrudes to the outside. This is a problem that can be solved by firmly brazing or welding the corrugated plate and the flat plate, but when trying to make a more reliable one, the manufacturing cost increases significantly.
【０００８】このように金属ハニカム触媒は、運転開始
直後の排ガス浄化性能の改善には効果が期待されるもの
の、製造コストや信頼性の点でまだ多くの問題がある。
触媒活性を短時間のうちに発現させる別の方法は、金属
ハニカム触媒に電極を配置し、通電により自己発熱させ
ることである。しかし上記の金属薄板を使う場合は、抵
抗値が数ｍΩ〜数十ｍΩにしかならないので、通電する
と大電流が流れ、電力消費量がきわめて大きくなり、電
源が特殊なものになったり、使用方法が限定されること
になるという問題がある。As described above, the metal honeycomb catalyst is expected to be effective in improving the exhaust gas purification performance immediately after the start of operation, but still has many problems in terms of manufacturing cost and reliability.
Another method of exhibiting the catalytic activity in a short time is to dispose electrodes on the metal honeycomb catalyst and to self-heat by energization. However, when using the above thin metal plates, the resistance value is only a few mΩ to several tens of mΩ, so a large current flows when energized, the power consumption becomes extremely large, the power supply becomes a special one, and the usage method There is a problem that will be limited.
【０００９】[0009]
【課題を解決するための手段】上記した金属ハニカム触
媒の種々の課題は、金属ハニカム触媒の基材を、アルミ
ニウムを主要合金成分として含有しない安価なフェライ
ト系ステンレス鋼とし、これをエキスパンド加工した
後、アルミニウムを溶射したものを出発原料とし、次い
でコルゲート加工、プレス加工等により、波状の凹凸を
つけ、凹凸をつけない薄板と重ね合わせるなどの方法に
よりハニカム構造体とし、その後に耐酸化性向上の手段
として、ランタン、イットリウム、セリウムのいずれか
の元素を単独または複合してアルミニウム溶射層に含浸
し、適当な熱処理を施し、必要に応じ高比表面積の無機
粒子をウォッシュコートすることによって解決される。
このようにして製造されたハニカム触媒担体に対し、排
ガス中の可燃成分の接触燃焼を可能とする触媒成分を担
持させて本発明の排ガス浄化触媒が得られる。[Means for Solving the Problems] Various problems of the above-mentioned metal honeycomb catalyst are as follows. The base material of the metal honeycomb catalyst is an inexpensive ferritic stainless steel which does not contain aluminum as a main alloying component, and it is expanded after being expanded. , Aluminum sprayed as a starting material, and then corrugated, pressed, etc. to make corrugated unevenness, and to form a honeycomb structure by a method such as stacking with a thin plate that does not have unevenness, and then improve the oxidation resistance. As a means, any one of lanthanum, yttrium, and cerium elements may be used alone or in combination to impregnate an aluminum sprayed layer, appropriate heat treatment may be performed, and a high specific surface area inorganic particles may be wash-coated as necessary. ..
An exhaust gas purifying catalyst of the present invention is obtained by supporting a catalyst component that enables catalytic combustion of combustible components in exhaust gas on the honeycomb catalyst support manufactured in this manner.
【００１０】すなわち、本発明の第１は、主要合金成分
としてアルミニウム（Ａｌ）を含まないフェライト系ス
テンレス鋼薄板をエキスパンド加工したものにアルミニ
ウムを溶射し、さらにこれを加工してハニカム構造体と
したものをランタン（Ｌａ）化合物を含む溶液に浸漬し
た後、５００〜１２００℃で熱処理することを特徴とす
る排ガス浄化用金属ハニカム触媒担体の製法である。That is, according to the first aspect of the present invention, a ferritic stainless steel thin plate which does not contain aluminum (Al) as a main alloy component is expanded, and then aluminum is sprayed and further processed to obtain a honeycomb structure. This is a method for producing a metal honeycomb catalyst carrier for exhaust gas purification, which comprises immersing an object in a solution containing a lanthanum (La) compound and then heat-treating at 500 to 1200 ° C.
【００１１】本発明の第２は、ハニカム構造体をランタ
ン化合物を含む溶液に浸漬する代わりに、該ハニカム構
造体にランタンアルミネート（ＬａＡｌＯ3 ）を含有す
るランタン−アルミナ焼成物をウォッシュコートするこ
とを特徴とする前記第１記載の金属ハニカム触媒担体の
製法である。本発明の第３は、主要合金成分としてアル
ミニウム（Ａｌ）を含まないフェライト系ステンレス鋼
薄板をエキスパンド加工したものにアルミニウムを溶射
し、さらにこれを加工してハニカム構造体としたもの
を、イットリウム（Ｙ）またはセリウム（Ｃｅ）を含有
する溶液に浸漬した後、５００〜１２００℃で熱処理
し、次いで高比表面積の無機粒子をウォッシュコートす
ることを特徴とする排ガス浄化用金属ハニカム触媒担体
の製法である。In a second aspect of the present invention, instead of immersing the honeycomb structure in a solution containing a lanthanum compound, the honeycomb structure is wash-coated with a lanthanum-alumina fired product containing lanthanum aluminate (LaAlO 3 ). The method for producing a metal honeycomb catalyst carrier according to the first aspect is characterized in that. In a third aspect of the present invention, a ferritic stainless steel thin plate that does not contain aluminum (Al) as a main alloy component is subjected to an expanding process, aluminum is sprayed, and this is further processed into a honeycomb structure. Y) or a solution containing cerium (Ce), and then heat treated at 500 to 1200 ° C., and then wash-coating with inorganic particles having a high specific surface area. is there.
【００１２】本発明の第４は、ハニカム構造体に電極を
配置し、通電可能としたことを特徴とする前記第１ない
し第３のいずれかに記載の排ガス浄化用金属ハニカム触
媒担体の製法である。本発明の第５は、前記第１ないし
第４のいずれかで製造された金属ハニカム触媒担体に触
媒成分を担持したことを特徴とする排ガス浄化用金属ハ
ニカム触媒である。A fourth aspect of the present invention is the method for producing a metal honeycomb catalyst carrier for exhaust gas purification according to any one of the first to third aspects, characterized in that electrodes are arranged in the honeycomb structure so that electricity can be applied. is there. A fifth aspect of the present invention is an exhaust gas-purifying metal honeycomb catalyst characterized in that a catalyst component is carried on the metal honeycomb catalyst carrier produced in any of the first to fourth aspects.
【００１３】[0013]
【作用】本発明においてエキスパンド加工した薄板を用
いる理由は次のようなものである。なお、ここではエキ
スパンド加工しない薄板を用いる、従来の金属ハニカム
構造体／触媒をバルクメタル型、エキスパンド加工薄板
を用いるものをラスメタル型と称する。 （ａ）ハニカムの通路方向だけでなぐ、横方向に対して
もガスが流通できるようになり、触媒と排ガスの接触効
率がきわめて高くなる。 （ｂ）構造的に三次元状態ができているので、薄板同士
が機械的に拘束された形となり、通常の金属ハニカム触
媒でしばしば問題となるフィルムアウト現象が本質的に
起きにくいので、特にろう付けを必要としない。 （ｃ）バルクメタル型と同じ見掛け容積の場合は材料量
が少なく、したがって軽くできるとともに、熱容量が小
さくなる結果、運転初期の昇温がさらに容易になる。 （ｄ）通電可能構造とする際に、抵抗値を大きくでき、
また加工条件を適当にコントロールすることにより、抵
抗値をある程度選ぶことができる。The reason for using the expanded thin plate in the present invention is as follows. The conventional metal honeycomb structure / catalyst using a thin plate that is not expanded is referred to as a bulk metal type, and the one using an expanded thin plate is referred to as a lath metal type. (A) The gas can flow in the lateral direction as well as only in the passage direction of the honeycomb, and the contact efficiency between the catalyst and the exhaust gas becomes extremely high. (B) Since the three-dimensional state is structurally formed, the thin plates are mechanically constrained, and the film-out phenomenon, which is often a problem with ordinary metal honeycomb catalysts, is essentially unlikely to occur. No need to attach. (C) When the apparent volume is the same as that of the bulk metal type, the amount of material is small and therefore the weight can be reduced, and the heat capacity is reduced. (D) The resistance value can be increased when the structure can be energized,
Further, the resistance value can be selected to some extent by appropriately controlling the processing conditions.
【００１４】従来のバルクメタル型の場合は、排ガスと
の接触が平面的にしか行われないので、接触面積を大き
くとるためにはハニカムの目数を多くする必要がある
が、ラスメタル型は針金の織物に近いので、排ガスとの
接触は３次元的となり、上記した熱容量の点に加え、排
ガスから基材への熱の伝達が容易になり、昇温が効果的
に行われる。排ガスとの接触効率、ひいては触媒の排ガ
ス浄化効果はバルクメタル型の場合よりも顕著になる。
なお、腐食法により金属薄板に開口部を設ける方法も考
えられるが、この方法の場合は、単に平面的な開口部が
存在するだけであり、エキスパンド加工の場合ほど接触
効率は向上しない。これはエキスパンド加工薄板の場合
は、３次元の状態ができているためである。すなわちエ
キスパンド加工した薄板は３次元構造が一体的に形成さ
れているので、互いに接触したときに拘束力が大きく、
金網等の場合のように滑りを生じにくい。In the case of the conventional bulk metal type, since the contact with the exhaust gas is made only in a plane, it is necessary to increase the number of honeycombs in order to increase the contact area. Since it is close to the woven fabric, the contact with the exhaust gas becomes three-dimensional, and in addition to the above-mentioned heat capacity, heat can be easily transferred from the exhaust gas to the substrate, and the temperature can be effectively raised. The contact efficiency with the exhaust gas, and consequently the exhaust gas purification effect of the catalyst, becomes more remarkable than in the case of the bulk metal type.
A method of providing an opening in a thin metal plate by a corrosion method is also conceivable, but in the case of this method, only a flat opening is present and the contact efficiency is not improved as much as in the expanding process. This is because the expanded thin plate has a three-dimensional state. That is, since the expanded thin plate has a three-dimensional structure integrally formed, it has a large binding force when contacting each other.
Less likely to slip as in the case of wire mesh.
【００１５】エキスパンド加工の条件は、触媒活性が効
率よく発現されるものを選べばよく、その選び方は上記
したことのいずれに重点を置くかで決まるものであるの
で、本発明では加工条件を特に規定しない。次にアルミ
ニウムを基材に溶射するのは次のような理由による。１
つは表面に幾何学的な凹凸を設けるためであり、他の理
由は耐酸化性の乏しいフェライト系ステンレス鋼の耐酸
化性を向上させるためである。さらに適当な熱処理や陽
極酸化法などによってアルミニウム溶射層をアルミナ酸
化物層とすることにより、エキスパンド加工薄板同士が
接触しても電気的絶縁が維持されるという特徴も有す
る。溶射量と熱処理条件を適切に選べば、薄板同士が固
着するようになるので、ろう付けすることと同様の効果
を持たせることもできる。The conditions for the expanding process may be selected so that the catalytic activity can be efficiently expressed, and the method of selection depends on which of the above points is emphasized. Not specified. Next, the reason why the aluminum is sprayed on the substrate is as follows. 1
One is to provide geometrical irregularities on the surface, and the other reason is to improve the oxidation resistance of ferritic stainless steel, which has poor oxidation resistance. Further, by forming the aluminum sprayed layer into an alumina oxide layer by an appropriate heat treatment or anodic oxidation method, electrical insulation is maintained even if the expanded thin plates come into contact with each other. By appropriately selecting the thermal spraying amount and the heat treatment conditions, the thin plates will adhere to each other, so that the same effect as brazing can be provided.
【００１６】またアルミニウムの溶射にはアーク溶射
法、ガス溶射法、その他の溶射法を適用することがで
き、本発明ではその種類を限定するものではない。しか
し通常、大気中または燃焼ガス中で溶射されたアルミニ
ウムは部分的に酸化物や窒化物になっており、アーク溶
射法では特に酸化物と窒化物への変換が多く、触媒活性
向上の点からは、アーク溶射法が好ましい結果を与える
こともある。Further, an arc spraying method, a gas spraying method, or another spraying method can be applied to the spraying of aluminum, and the type thereof is not limited in the present invention. However, aluminum that has been sprayed in the atmosphere or in combustion gas is usually partially oxidized or nitrided. In the arc spraying method, there are many conversions to oxides and nitrides. In some cases, arc spraying may give desirable results.
【００１７】アルミニウムの溶射量は３０〜１００ｇ／
ｍ2 であれば、基材のほぼ全面を溶射することができ
る。溶射量は最終的な触媒の活性との関連で決定すれば
よく、本発明はアルミニウムの溶射量を規定するもので
はない。次にエキスパンド加工後アルミニウム溶射した
薄板からハニカム構造体を形成するには、例えば前記の
アルミニウム溶射した薄板に波状の凹凸加工した後、こ
れと凹凸をつけない薄板を重ねて略円柱状に巻き込む
か、または単に重ね合わせる方法が挙げられるが、これ
らに限定されるものではない。The amount of aluminum sprayed is 30 to 100 g /
With m 2 , almost the entire surface of the base material can be sprayed. The sprayed amount may be determined in relation to the final activity of the catalyst, and the present invention does not specify the sprayed amount of aluminum. Next, in order to form a honeycomb structure from an aluminum-sprayed thin plate after the expanding process, for example, after corrugating the aluminum-sprayed thin plate described above and corrugating it, a thin plate that does not have unevenness is stacked and rolled into a substantially cylindrical shape. However, the method is not limited to these.
【００１８】次に前記ハニカム構造体をランタン、イッ
トリウム、またはセリウムを含有する溶液に浸漬して、
これらをアルミニウム溶射層に含浸させるのであるが、
これは耐酸化性を一層向上させることを目的とするもの
である。すなわちアルミニウムを主要成分として含有し
ないフェライト系ステンレス鋼であってもアルミニウム
溶射を行うことで、耐酸化性は向上するが、加熱冷却が
繰返されるような使用条件下では、アルミニウム溶射層
が母材から剥離し、耐酸化性が維持できなくなる。これ
は５００〜７００℃の高温にさらされた時点で溶射され
たアルミニウムはアルミナまたはアルミナとアルミニウ
ム−鉄合金の混合相に変化しており、耐酸化性はアルミ
ナに依存しているからである。ところがランタン、イッ
トリウムまたはセリウムが存在するとアルミナ層または
膜が母材に強固に接着し、加熱冷却の繰返しに対しても
高い耐酸化性を保持することができる。なお、前述した
ように、バルクメタル型ハニカム触媒では、原料として
イットリウムまたはセリウムを微量含有した高耐酸化性
フェライト系ステンレス鋼が知られているが、本発明で
は気孔率が数％〜十数％あるアルミニウム溶射層にラン
タン、イットリウム、またはセリウムを含む溶液、例え
ば硝酸ランタン水溶液を滲み込ませて、上記の高耐酸化
性ステンレス鋼と同等の性能を発揮させるようにした点
に特徴を有する。Next, the honeycomb structure is immersed in a solution containing lanthanum, yttrium, or cerium,
Although these are impregnated into the aluminum sprayed layer,
This is intended to further improve the oxidation resistance. That is, even if it is a ferritic stainless steel that does not contain aluminum as a main component, by performing aluminum spraying, the oxidation resistance is improved, but under the use conditions in which heating and cooling are repeated, the aluminum sprayed layer is formed from the base material. It peels off and the oxidation resistance cannot be maintained. This is because the aluminum sprayed at the time of being exposed to a high temperature of 500 to 700 ° C. has changed to alumina or a mixed phase of alumina and an aluminum-iron alloy, and the oxidation resistance depends on alumina. However, when lanthanum, yttrium, or cerium is present, the alumina layer or film is firmly adhered to the base material, and high oxidation resistance can be maintained even with repeated heating and cooling. As described above, in the bulk metal type honeycomb catalyst, high oxidation resistance ferritic stainless steel containing a small amount of yttrium or cerium as a raw material is known, but in the present invention, the porosity is several percent to several tens percent. It is characterized in that a solution containing lanthanum, yttrium, or cerium, for example, an aqueous solution of lanthanum nitrate is soaked into a certain aluminum sprayed layer so as to exhibit the same performance as that of the above-mentioned high oxidation resistant stainless steel.
【００１９】本発明において、前記アルミニウム溶射層
にランタン化合物を含浸して５００〜１２００℃で焼成
すると、ランタンは上記の酸化物固着効果を示すととも
に、アルミニウム溶射層中のアルミナ（溶射のままでは
γアルミナになっている）と反応して、ランタン−アル
ミナを形成するが、このランタン−アルミナは、通常比
表面積が３０〜１２０ｍ2 ／ｇ程度であり、かつα化し
にくい特徴を持っており、そのまま触媒担体として利用
することができる。In the present invention, when the aluminum sprayed layer is impregnated with a lanthanum compound and calcined at 500 to 1200 ° C., lanthanum exhibits the above oxide fixing effect, and the alumina in the aluminum sprayed layer (γ in the as-sprayed state) Lanthanum-alumina is formed by reacting with (alumina), and this lanthanum-alumina usually has a specific surface area of about 30 to 120 m 2 / g and has a characteristic that it is difficult to form α, It can be used as a catalyst carrier.
【００２０】本発明でランタン化合物を含有する溶液に
浸漬した後の焼成温度を５００〜１２００℃に規定して
いるのは、上記の２つの効果をねらったものである。す
なわち５００℃未満の温度で焼成した場合は、反応が充
分起こらず、金属アルミニウムの含有量が高いままとな
って、触媒担体として適さないし、一方焼成温度が１２
００℃を超えると、アルミナのα化が進み、比表面積が
低下して、やはり触媒担体としては性能が低下するから
である。In the present invention, the firing temperature after immersion in the solution containing the lanthanum compound is regulated to 500 to 1200 ° C. for the above two effects. That is, when calcined at a temperature of less than 500 ° C., the reaction does not sufficiently occur and the content of metallic aluminum remains high, which makes it unsuitable as a catalyst carrier.
This is because if the temperature exceeds 00 ° C., the α-formation of alumina proceeds, the specific surface area decreases, and the performance as a catalyst carrier also decreases.
【００２１】本発明者らの研究の結果によると、ランタ
ン化合物の代わりにイットリウムまたはセリウムの化合
物をアルミニウム溶射層に含浸したものでは、ランタン
化合物を含浸した場合ほど比表面積が上がらず、かつア
ルミナのα化遅延効果が見られなかった。したがって、
イットリウムまたはセリウムを利用する場合は、含浸後
５００〜１２００℃で焼成して一旦溶射アルミニウム層
と適度に反応させ、その後、比表面積の大きい無機粒子
をウォッシュコートする方法が適している。According to the results of the research conducted by the present inventors, in the case where the aluminum sprayed layer is impregnated with a compound of yttrium or cerium instead of the lanthanum compound, the specific surface area is not increased as much as when the lanthanum compound is impregnated, and No alpha-delaying effect was observed. Therefore,
When yttrium or cerium is used, a method is suitable in which after impregnation, firing is performed at 500 to 1200 ° C. to once react appropriately with the sprayed aluminum layer, and then the inorganic particles having a large specific surface area are wash-coated.
【００２２】ウォッシュコートに用いる高比表面積の無
機粒子としては、活性アルミナが代表的なものである
が、ゼオライト、チタニア（アナターゼ）ほか各種のも
のが適用できる。要は触媒活性を発揮できるように、触
媒成分を充分に分散担持できるものであればよい。ラン
タンアルミネート（ＬａＡｌＯ3 ）を含有するランタン
−アルミナ焼成物をウォッシュコートすると、上記と同
等およびさらにこれに付随する効果が得られることを次
に説明する。As the inorganic particles having a high specific surface area used for the wash coat, activated alumina is representative, but various kinds such as zeolite, titania (anatase) and the like can be applied. What is essential is that the catalyst component can be sufficiently dispersed and supported so that the catalyst activity can be exhibited. It will be explained below that wash-coating a lanthanum-alumina calcined product containing lanthanum aluminate (LaAlO 3 ) produces effects equivalent to or above the above effects.
【００２３】ランタンアルミネートは水可溶であり、こ
れを含有するランタン−アルミナ焼成物をウォッシュコ
ートするため、該焼成物と水のスラリをつくると、スラ
リ中にランタンイオン（Ｌａ3+）が生成し、これがアル
ミニウム溶射層に浸透して、ランタン化合物のみ含有す
る溶液に浸漬した場合と同等の効果が生じる。こうした
ランタンアルミネートを含有するランタン−アルミナ焼
成物は、例えば硝酸ランタンとベーマイトを混合し、焼
成温度を１２００℃未満とすることで得られる。焼成温
度が１２００℃を超えるとランタンアルミネートが形成
されず、安定な酸化物が生成する。さらにこのランタン
−アルミナ焼成物はα化していないので、通常５０〜１
５０ｍ2 ／ｇ程度の高い比表面積を持っており、触媒担
体として好適なものとなる。本発明におけるランタン−
アルミナ焼成物は触媒担体として使用できる限りその組
成、焼成温度は特に規定されない。Lanthanum aluminate is water-soluble, and a lanthanum-alumina calcined product containing the lanthanum aluminate is wash-coated. Therefore, when a slurry of the calcined product and water is prepared, lanthanum ions (La 3+ ) are generated in the slurry. It is produced, and this penetrates into the aluminum sprayed layer, and the same effect as when it is immersed in the solution containing only the lanthanum compound is produced. The lanthanum-alumina calcined product containing such a lanthanum aluminate can be obtained, for example, by mixing lanthanum nitrate and boehmite and setting the calcining temperature to less than 1200 ° C. When the firing temperature exceeds 1200 ° C., lanthanum aluminate is not formed and a stable oxide is formed. Furthermore, since this lanthanum-alumina fired product is not alpha-converted, it is usually 50 to 1
It has a high specific surface area of about 50 m 2 / g and is suitable as a catalyst carrier. Lantern in the present invention
The composition and calcination temperature of the calcined alumina product are not particularly limited as long as it can be used as a catalyst carrier.
【００２４】本発明においては、触媒体または触媒担体
に電極を配置して通電可能とすることも含まれるが、電
極を配置して通電可能とする自体は、バルクメタル型ハ
ニカム触媒ですでに多くの公知例がある。しかしバルク
メタル型ハニカムの場合は、本質的に抵抗値が小さく、
結果的に通電すると大電流が流れることになる。充分容
量の大きい電源がある場合には、この大電流、大電力発
生は問題にならないが、自動車等の電源が制限されるも
のに対しては、実際問題として実用化できるものではな
い。これに対して、本発明のラスメタル型ハニカム触媒
担体／触媒は、アルミニウム溶射層の絶縁効果と相まっ
て、バルクメタル型ハニカム触媒担体／触媒と同等の容
積の場合で、略５〜２０倍大きい抵抗値となるので、同
じ電圧を負荷したときの電流は１／５〜１／２０小さく
なる。電流が充分小さくなると、配線容量、電源容量を
小さくでき、通電可能とすることが実用上可能になる。
逆に通電による発熱量は小さくなるが、これは必要に応
じ通電時間を長くする、発熱部分を小さくし、熱容量を
小さくする等で補える事柄である。以上のことから本発
明のラスメタル型ハニカム触媒を通電可能とすると、公
知例では予想されなかった効果が得られることになる。In the present invention, the arrangement of electrodes on the catalyst body or the catalyst carrier to make them electrically conductive is included. However, the arrangement of electrodes to make them electrically conductive is already common in bulk metal type honeycomb catalysts. There are known examples of. However, in the case of a bulk metal type honeycomb, the resistance value is essentially small,
As a result, when energized, a large current flows. If there is a power supply with a sufficiently large capacity, this large current and large power generation will not be a problem, but it cannot be practically put to practical use for power supplies such as automobiles that are limited. On the other hand, the lath metal type honeycomb catalyst carrier / catalyst of the present invention, combined with the insulating effect of the aluminum sprayed layer, has a resistance value approximately 5 to 20 times larger in the case of a volume equivalent to that of the bulk metal type honeycomb catalyst carrier / catalyst. Therefore, the current when the same voltage is loaded becomes 1/5 to 1/20 smaller. When the current is sufficiently small, the wiring capacity and the power supply capacity can be reduced, and it becomes practically possible to energize.
On the contrary, the amount of heat generated by energization is small, but this is a matter that can be compensated for by increasing the energization time, reducing the heat generating portion, and reducing the heat capacity as necessary. From the above, when the lath metal type honeycomb catalyst of the present invention can be energized, an effect which has not been expected in the known example can be obtained.
【００２５】最終的には、このようにして製造されたハ
ニカム構造体に対し、排ガス中の可燃成分の接触燃焼を
可能とする触媒成分を担持して排ガス浄化触媒を得る。Finally, the honeycomb structure manufactured in this manner is loaded with a catalyst component that enables catalytic combustion of combustible components in the exhaust gas to obtain an exhaust gas purification catalyst.
【００２６】[0026]
実施例１ 厚さ０．２mm、幅５００mmのＳＵＳ４３０をエキスパン
ド加工し、これにアーク溶射法でアルミニウムを溶射し
た（溶射量：約５０ｇ／ｍ2 ）。エキスパンド加工にお
ける切り込み幅は３mmで、エキスパンド前後の長さの比
は１８０％である。次にこの原料を幅１００mmに切断
し、公称高さ５mm、ピッチ５mmのコルゲートロールに通
して、山谷高さが約３mmの波板を得た。この波板とコル
ゲート加工しないエキスパンド薄板を直径８mm、肉厚
０．５mmのＳＵＳ３０４製パイプを芯金として巻き込
み、直径約６５mm、長さ１００mmのハニカム構造体を得
た（見掛け容積：３３０cc）。次にこの金属ハニカム構
造体を５０％硝酸ランタン水溶液に浸漬し、溶液より取
出して充分液切りした後、１３０℃で乾燥した。乾燥後
９００℃の大気中で焼成した。この金属ハニカム構造体
を０．２％のＰｄを含む硝酸パラジウム水溶液に１０〜
２０秒浸漬し、１００℃で充分に乾燥後、最終的に５５
０℃で焼成し、Ｐｄの含有量がほぼ１ｇ／Ｌ（触媒の見
掛け体積、以下同じ）である触媒を得た。Example 1 SUS430 having a thickness of 0.2 mm and a width of 500 mm was expanded, and aluminum was sprayed on this by an arc spraying method (spraying amount: about 50 g / m 2 ). The cut width in the expanding process is 3 mm, and the length ratio before and after the expansion is 180%. Next, this raw material was cut into a width of 100 mm and passed through a corrugated roll having a nominal height of 5 mm and a pitch of 5 mm to obtain a corrugated plate having a peak and valley height of about 3 mm. The corrugated plate and the expanded thin plate not subjected to corrugation were wound by using a SUS304 pipe having a diameter of 8 mm and a wall thickness of 0.5 mm as a core metal to obtain a honeycomb structure having a diameter of about 65 mm and a length of 100 mm (apparent volume: 330 cc). Next, this metal honeycomb structure was immersed in a 50% lanthanum nitrate aqueous solution, taken out from the solution, sufficiently drained, and then dried at 130 ° C. After drying, it was baked in the air at 900 ° C. This metal honeycomb structure was immersed in a palladium nitrate aqueous solution containing 0.2% Pd in an amount of 10 to 10.
Immerse for 20 seconds, fully dry at 100 ℃, and finally 55
It was calcined at 0 ° C. to obtain a catalyst having a Pd content of about 1 g / L (apparent volume of catalyst, the same applies hereinafter).
【００２７】実施例２ 実施例１のハニカム構造体を、ランタンアルミナを約２
０％含有するランタン−アルミナ焼成物−水スラリ（濃
度２０％）に浸漬し、余剰液を除去して乾燥し、５５０
℃で焼成した。次いでこの金属ハニカム構造体を０．２
％のＰｄを含む硝酸パラジウム水溶液に１０〜２０秒浸
漬し、１００℃で充分に乾燥後、最終的に５５０℃で焼
成して、Ｐｄの含有量がほぼ１ｇ／Ｌである触媒を得
た。Example 2 The honeycomb structure of Example 1 was prepared by adding about 2 lanthanum alumina.
It was dipped in a lanthanum-alumina calcined product-water slurry (concentration 20%) containing 0% to remove excess liquid and dried.
Baked at ° C. Next, this metal honeycomb structure is 0.2
% Pd in a palladium nitrate aqueous solution for 10 to 20 seconds, sufficiently dried at 100 ° C., and finally calcined at 550 ° C. to obtain a catalyst having a Pd content of about 1 g / L.
【００２８】実施例３ 実施例１のハニカム構造体を５０％硝酸イットリウム水
溶液に浸漬し、溶液より取出して充分液切りした後、１
３０℃で乾燥した。乾燥後９００℃の大気中で焼成し
た。次いでこの金属ハニカムを活性アルミナスラリ（濃
度１５％）に浸漬し、余剰液を除去した後、乾燥し、５
５０℃で焼成した。その後０．２％のＰｄを含む硝酸パ
ラジウム水溶液に１０〜２０秒浸漬し、１００℃で充分
に乾燥後、最終的に５５０℃で焼成したＰｄの含有量が
ほぼ１ｇ／Ｌである触媒を得た。Example 3 The honeycomb structure of Example 1 was dipped in a 50% yttrium nitrate aqueous solution, taken out from the solution and sufficiently drained, and then 1
It was dried at 30 ° C. After drying, it was baked in the air at 900 ° C. Next, this metal honeycomb is immersed in an activated alumina slurry (concentration 15%) to remove excess liquid, and then dried.
It was baked at 50 ° C. Then, it was immersed in an aqueous palladium nitrate solution containing 0.2% Pd for 10 to 20 seconds, sufficiently dried at 100 ° C., and finally calcined at 550 ° C. to obtain a catalyst having a Pd content of about 1 g / L. It was
【００２９】実施例４ 実施例１のハニカム構造体を５０％硝酸セリウム水溶液
に浸漬し、溶液より取出して充分液切りした後、乾燥し
た。乾燥後９００℃の大気中で焼成した。次いでこの金
属ハニカムを活性アルミナスラリ（濃度１５％）に浸漬
し、余剰液を除去した後、乾燥し５５０℃で焼成した。
この金属ハニカムを０．２％のＰｄを含む硝酸パラジウ
ム水溶液に１０〜２０秒浸漬し、１００℃で充分に乾燥
後、最終的に５５０℃で焼成したＰｄの含有量がほぼ１
ｇ／Ｌである触媒を得た。Example 4 The honeycomb structure of Example 1 was immersed in a 50% cerium nitrate aqueous solution, taken out from the solution, sufficiently drained, and then dried. After drying, it was baked in the air at 900 ° C. Next, this metal honeycomb was immersed in an activated alumina slurry (concentration: 15%) to remove excess liquid, dried, and fired at 550 ° C.
This metal honeycomb was dipped in a palladium nitrate aqueous solution containing 0.2% Pd for 10 to 20 seconds, sufficiently dried at 100 ° C., and finally calcined at 550 ° C. so that the content of Pd was about 1.
A catalyst was obtained which was g / L.
【００３０】実施例５ 実施例１の金属ハニカム構造体の最外周部に電極をろう
付けし、中心部の芯金との間で通電できるようにしたの
ち、実施例２と同様の方法で触媒化し、金属ハニカム触
媒を得た。この触媒の両電極間の抵抗値は約０．２Ωで
あった。 比較例１ ４００セル／ｉｎ2 のコーディエライト製ハニカム基材
（実施例１とほぼ同じ寸法）に活性アルミナを通常の方
法でウォッシュコーティングし、実施例１と同様の方法
で、Ｐｄ担持量が約１ｇ／Ｌである触媒を得た。Example 5 An electrode was brazed to the outermost peripheral portion of the metal honeycomb structure of Example 1 so that electric current could be passed between the electrode and the cored bar in the central portion, and then a catalyst was prepared in the same manner as in Example 2. To obtain a metal honeycomb catalyst. The resistance value between both electrodes of this catalyst was about 0.2Ω. Comparative Example 1 A cordierite honeycomb substrate of 400 cells / in 2 (having substantially the same dimensions as in Example 1) was wash-coated with activated alumina by a conventional method, and the amount of Pd supported was changed by the same method as in Example 1. A catalyst of about 1 g / L was obtained.
【００３１】比較例２ ８００セル／ｉｎ2 の金属ハニカム構造体（実施例１と
ほぼ同じ寸法。基材組成：１３Ｃｒ−６Ａｌ−Ｙ、表面
処理として真空中１１００℃で熱処理）に活性アルミナ
を通常の方法でウォッシュコーティングし、実施例１と
同様の方法で、Ｐｄ担持量が約１ｇ／Ｌである触媒を得
た。Comparative Example 2 A metal honeycomb structure of 800 cells / in 2 (having substantially the same dimensions as in Example 1; base material composition: 13Cr-6Al-Y; heat treatment at 1100 ° C. in vacuum for surface treatment) was usually treated with activated alumina. Wash-coating was carried out by the same method as in Example 1 to obtain a catalyst having a Pd supported amount of about 1 g / L in the same manner as in Example 1.
【００３２】実施例１〜４の触媒と比較例１〜２の触媒
について、エンジン始動開始時における、両者の初期性
能を調べた。エンジン始動後の経過時間と触媒出口温
度、ＨＣ、およびＣＯ除去率の関係を表１に示す。本結
果から明らかなように、本発明の実施例１〜４の金属ハ
ニカム触媒は、エンジン始動直後から温度が上昇し始
め、触媒の活性が発現する温度に短時間のうちに到達
し、運転初期におけるＨＣ、ＣＯの浄化性能は、比較例
に較べ明らかに高い。The initial performances of the catalysts of Examples 1 to 4 and the catalysts of Comparative Examples 1 and 2 at the start of engine start were examined. Table 1 shows the relationship between the elapsed time after engine startup and the catalyst outlet temperature, HC, and CO removal rate. As is clear from the present results, in the metal honeycomb catalysts of Examples 1 to 4 of the present invention, the temperature starts to rise immediately after the engine is started, the temperature at which the activity of the catalyst is expressed is reached in a short time, and the operation is started. The purification performance of HC and CO in the above is clearly higher than that of the comparative example.
【００３３】[0033]
【表１】 [Table 1]
【００３４】実施例５についての実験結果を表２に示
す。実験における負荷電圧は１２Ｖで、このときの電流
は２０Ａであった。電圧負荷後約１２０秒経過した時点
で、触媒温度は約１５０℃に達しており、このあたりか
らＨＣの着火が生じている。The experimental results for Example 5 are shown in Table 2. The load voltage in the experiment was 12V, and the current at this time was 20A. At about 120 seconds after the voltage was loaded, the catalyst temperature reached about 150 ° C., and HC ignition occurred around this point.
【００３５】[0035]
【表２】 [Table 2]
【００３６】[0036]
【発明の効果】請求項１ないし３および５記載の発明に
よれば、従来のバルクメタル型ハニカム触媒において問
題となっていた数々の技術的課題が、きわめて実用的な
方法で解決されるうえ、特に自動車等燃焼ガスを動力源
とするものにあっては、運転初期の排ガスの浄化を確実
に行わせることが可能となり、環境保全に対して大きな
寄与が期待できる。According to the inventions described in claims 1 to 3 and 5, various technical problems which have been problems in the conventional bulk metal type honeycomb catalyst can be solved by a very practical method. In particular, in the case of a vehicle such as an automobile that uses combustion gas as a power source, it becomes possible to reliably purify the exhaust gas in the initial stage of operation, and it can be expected to make a great contribution to environmental conservation.
【００３７】また請求項４記載の発明によれば、効果的
に触媒の温度を上げることが可能であり、自動車等の燃
焼ガスを動力源とするものにあっては、運転初期の排ガ
スの浄化をさらに確実に行わせることができる。Further, according to the invention of claim 4, it is possible to effectively raise the temperature of the catalyst, and in the case where the combustion gas of an automobile or the like is used as the power source, purification of exhaust gas at the initial stage of operation Can be performed more reliably.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 37/02 ３０１ Ｇ 7821−4Ｇ (72)発明者 山下 寿生 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical indication location B01J 37/02 301 G 7821-4G (72) Inventor Toshio Yamashita 4026 Kuji Town, Hitachi City, Ibaraki Stock Hitachi R & D Co., Ltd.
Claims (5)
ｌ）を含まないフェライト系ステンレス鋼薄板をエキス
パンド加工したものにアルミニウムを溶射し、さらにこ
れを加工してハニカム構造体としたものをランタン（Ｌ
ａ）成分を含む溶液に浸漬した後、５００〜１２００℃
で熱処理することを特徴とする排ガス浄化用金属ハニカ
ム触媒担体の製法。1. Aluminum (A) as a main alloying component
The lanthanum (L) is obtained by subjecting a ferritic stainless steel thin plate not containing l) to an expanded process to which aluminum is sprayed and then processed to form a honeycomb structure.
After immersion in a solution containing the component a), 500 to 1200 ° C
A method for producing a metal honeycomb catalyst carrier for exhaust gas purification, which is characterized in that it is heat-treated at room temperature.
溶液に浸漬する代わりに、該ハニカム構造体にランタン
アルミネート（ＬａＡｌＯ3 ）を含有するランタン−ア
ルミナ焼成物をウォッシュコートすることを特徴とする
請求項１記載の金属ハニカム触媒担体の製法。2. The honeycomb structure is wash-coated with a lanthanum-alumina fired product containing lanthanum aluminate (LaAlO 3 ) instead of immersing the honeycomb structure in a solution containing a lanthanum compound. Item 2. A method for producing a metal honeycomb catalyst carrier according to Item 1.
ｌ）を含まないフェライト系ステンレス鋼薄板をエキス
パンド加工したものにアルミニウムを溶射し、さらにこ
れを加工してハニカム構造体としたものを、イットリウ
ム（Ｙ）成分またはセリウム（Ｃｅ）成分を含有する溶
液に浸漬した後、５００〜１２００℃で熱処理し、次い
で高比表面積の無機粒子をウォッシュコートすることを
特徴とする排ガス浄化用金属ハニカム触媒担体の製法。3. Aluminum (A) as a main alloying component
A solution containing an yttrium (Y) component or a cerium (Ce) component, which is obtained by subjecting an expanded-processed ferritic stainless steel thin plate not containing l) to thermal spraying of aluminum, and further processing this to form a honeycomb structure. A process for producing a metal honeycomb catalyst carrier for exhaust gas purification, which comprises subjecting the substrate to heat treatment at 500 to 1200 ° C. and then wash-coating with inorganic particles having a high specific surface area.
能としたことを特徴とする請求項１ないし３のいずれか
に記載の排ガス浄化用金属ハニカム触媒担体の製法。4. The method for producing a metal honeycomb catalyst carrier for exhaust gas purification according to claim 1, wherein electrodes are arranged on the honeycomb structure so that electricity can be applied.
た金属ハニカム触媒担体に触媒成分を担持したことを特
徴とする排ガス浄化用金属ハニカム触媒。5. An exhaust gas-purifying metal honeycomb catalyst comprising a metal honeycomb catalyst carrier manufactured by any one of claims 1 to 4, which carries a catalyst component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4098200A JPH05293388A (en) | 1992-04-17 | 1992-04-17 | Production of metal honeycomb catalyst carrier for purification of exhaust gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4098200A JPH05293388A (en) | 1992-04-17 | 1992-04-17 | Production of metal honeycomb catalyst carrier for purification of exhaust gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05293388A true JPH05293388A (en) | 1993-11-09 |
Family
ID=14213366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4098200A Pending JPH05293388A (en) | 1992-04-17 | 1992-04-17 | Production of metal honeycomb catalyst carrier for purification of exhaust gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05293388A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08103661A (en) * | 1994-06-01 | 1996-04-23 | Hideo Kameyama | Self-regenerable catalytic body and treatment of organic halogen-containing gas using the same |
| JP2011147855A (en) * | 2010-01-20 | 2011-08-04 | Calsonic Kansei Corp | Electrically heating catalyst device and method for producing the same |
| WO2015115011A1 (en) * | 2014-01-28 | 2015-08-06 | カルソニックカンセイ株式会社 | Honeycomb structure |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS644255A (en) * | 1987-06-27 | 1989-01-09 | Toyota Motor Corp | Production of exhaust gas cleaning catalyst |
| JPS6415139A (en) * | 1987-07-09 | 1989-01-19 | Toyota Motor Corp | Catalyst for purifying exhaust gas |
| JPH0268145A (en) * | 1988-09-02 | 1990-03-07 | Babcock Hitachi Kk | Preparation of plate-shaped catalyst for removing nitrogen oxide |
| JPH0352642A (en) * | 1989-07-17 | 1991-03-06 | Babcock Hitachi Kk | Production of catalyst for combustion |
| JPH03193141A (en) * | 1989-12-21 | 1991-08-22 | Cataler Kogyo Kk | Preparation of self-heating type catalyst |
| JPH04104839A (en) * | 1990-08-24 | 1992-04-07 | Matsumoto Kokan Kk | Metal support for catalyst and its production |
| JPH05285387A (en) * | 1992-04-13 | 1993-11-02 | Hitachi Ltd | Catalyst for purification of exhaust gas and purification method |
-
1992
- 1992-04-17 JP JP4098200A patent/JPH05293388A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS644255A (en) * | 1987-06-27 | 1989-01-09 | Toyota Motor Corp | Production of exhaust gas cleaning catalyst |
| JPS6415139A (en) * | 1987-07-09 | 1989-01-19 | Toyota Motor Corp | Catalyst for purifying exhaust gas |
| JPH0268145A (en) * | 1988-09-02 | 1990-03-07 | Babcock Hitachi Kk | Preparation of plate-shaped catalyst for removing nitrogen oxide |
| JPH0352642A (en) * | 1989-07-17 | 1991-03-06 | Babcock Hitachi Kk | Production of catalyst for combustion |
| JPH03193141A (en) * | 1989-12-21 | 1991-08-22 | Cataler Kogyo Kk | Preparation of self-heating type catalyst |
| JPH04104839A (en) * | 1990-08-24 | 1992-04-07 | Matsumoto Kokan Kk | Metal support for catalyst and its production |
| JPH05285387A (en) * | 1992-04-13 | 1993-11-02 | Hitachi Ltd | Catalyst for purification of exhaust gas and purification method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08103661A (en) * | 1994-06-01 | 1996-04-23 | Hideo Kameyama | Self-regenerable catalytic body and treatment of organic halogen-containing gas using the same |
| JP2011147855A (en) * | 2010-01-20 | 2011-08-04 | Calsonic Kansei Corp | Electrically heating catalyst device and method for producing the same |
| WO2015115011A1 (en) * | 2014-01-28 | 2015-08-06 | カルソニックカンセイ株式会社 | Honeycomb structure |
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