EP0431405A1 - Device for catalytic purification of exhaust gases of internal combustion two-stroke engines - Google Patents

Device for catalytic purification of exhaust gases of internal combustion two-stroke engines Download PDF

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Publication number
EP0431405A1
EP0431405A1 EP90122290A EP90122290A EP0431405A1 EP 0431405 A1 EP0431405 A1 EP 0431405A1 EP 90122290 A EP90122290 A EP 90122290A EP 90122290 A EP90122290 A EP 90122290A EP 0431405 A1 EP0431405 A1 EP 0431405A1
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EP
European Patent Office
Prior art keywords
inner tube
arrangement according
catalyst
tube
exhaust
Prior art date
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Application number
EP90122290A
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German (de)
French (fr)
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EP0431405B1 (en
Inventor
Rainer Dr. Domesle
Bernd Dr. Engler
Edgar Dr. Koberstein
Ulrich Plotzke
Herbert Völker
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Evonik Operations GmbH
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Degussa GmbH
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Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28Construction of catalytic reactors
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/009Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28Construction of catalytic reactors
    • F01N3/2803Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2807Metal other than sintered metal
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N1/00Silencing apparatus characterised by method of silencing
    • F01N1/08Silencing apparatus characterised by method of silencing by reducing exhaust energy by throttling or whirling
    • F01N1/089Silencing apparatus characterised by method of silencing by reducing exhaust energy by throttling or whirling using two or more expansion chambers in series
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2470/00Structure or shape of gas passages, pipes or tubes
    • F01N2470/02Tubes being perforated
    • F01N2470/04Tubes being perforated characterised by shape, disposition or dimensions of apertures
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2490/00Structure, disposition or shape of gas-chambers
    • F01N2490/02Two or more expansion chambers in series connected by means of tubes
    • F01N2490/04Two or more expansion chambers in series connected by means of tubes the gases flowing longitudinally from inlet to outlet only in one direction
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00Surface coverings
    • F01N2510/06Surface coverings for exhaust purification, e.g. catalytic reaction
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02BINTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B75/00Other engines
    • F02B75/02Engines characterised by their cycles, e.g. six-stroke
    • F02B2075/022Engines characterised by their cycles, e.g. six-stroke having less than six strokes per cycle
    • F02B2075/025Engines characterised by their cycles, e.g. six-stroke having less than six strokes per cycle two
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02BINTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B75/00Other engines
    • F02B75/02Engines characterised by their cycles, e.g. six-stroke
    • F02B2075/022Engines characterised by their cycles, e.g. six-stroke having less than six strokes per cycle
    • F02B2075/027Engines characterised by their cycles, e.g. six-stroke having less than six strokes per cycle four

Definitions

  • the invention relates to an arrangement for the catalytic cleaning of the exhaust gases of internal combustion engines, in particular of two-stroke engines.
  • the invention has for its object to provide a catalytic exhaust gas purification system which is more suitable for such engines. This object is achieved by the arrangement described in the claims.
  • the arrangement according to the invention is also suitable for four-stroke engines, since these also require fine tuning of the exhaust system.
  • the casing tube (1) can have any shape.
  • the inner tube (3) is shaped accordingly in order to obtain an annular space (5) of approximately constant cross section. Tapered annular spaces are also part of the invention.
  • annular space (5) takes up only a fraction of the volume of the casing tube (1) due to the dimensions provided.
  • Annulus (5) and perforation reinforce the in the catalyst area Turbulence and thus gas exchange. This effect is reinforced in the basic configuration of the arrangement according to the invention by the annular gap which is open on both sides and which ensures a backflow of the catalytically coated inner tube.
  • annular gap which is open on both sides and which ensures a backflow of the catalytically coated inner tube.
  • an at least one-sided closure of the annular space at any point is expedient (claim 2).
  • the hole diameters of the inner tube range from 0.75 to 10 mm, with a hole spacing of 1.0 to 15 mm. Hole diameters of 1.5 to 6 mm and hole spacing of 2.0 to 7.5 mm are preferred (claim 7).
  • the inner tube can have regularly arranged holes of different diameters over the entire jacket.
  • tubular body can also consist of expanded metal or coarse wire mesh.
  • the relative free hole area is in the different embodiments 5 to 80%, preferably 20-60% (claim 8).
  • the inner tube can, if appropriate, in particular for manufacturing reasons, be formed from two half-shells which are optionally connected to one another (claim 4). This can result in a division of the annular space into two halves.
  • the geometric surface can be increased by surrounding it with a wire mesh, expanded metal or another perforated tube in order to achieve increased conversion rates for the pollutants (claim 5).
  • the arrangement according to the invention is suitable both as a main catalyst and as a starting catalyst for a downstream main catalyst (6) of any type (claim 6).
  • a starting catalytic converter When used as a starting catalytic converter, partial conversion of pollutants results in an increase in temperature, which makes it easier or even possible to start a main catalytic converter which may be connected in a cooler part of the exhaust system. If high concentrations of pollutants occur and at the same time high exhaust gas temperatures, a partial conversion has a favorable effect in that it reduces the temperature load due to the exhaust gas cooling between the start and main catalytic converter and protects the main catalytic converter from premature destruction or thermal deactivation.
  • the conversion rates of the arrangement according to the invention are surprisingly high when used as the main catalyst. Also at When used on two-wheelers, the main catalyst can be used to meet current and future limit values.
  • Pt, Pd and / or Rh-containing noble metal catalysts on a heat-resistant, oxidic support material are particularly suitable.
  • the carrier material can be provided with oxidic additives such as CeO2, ZrO2, alkaline earth metal oxide and / or rare earth oxides.
  • a pre-treatment by sandblasting, flame spraying, aluminizing is carried out before the application of the oxidic carrier material in order to improve the temperature resistance of the perforated tubular body and the adhesion of the coating.
  • a perforated, tapered pipe bend with diameters of 30 mm or 55 mm, an elongated pipe length of 345 mm, 2 mm hole diameter and 3.15 mm hole spacing made of high-temperature resistant steel 1.4841 is first tempered in air at 900 ° C for 3 h.
  • the tube bend is then coated with an approximately 40% dispersion of ⁇ -Al2O3, (150 m2 / g), cerium acetate and zirconium acetate, dried at 120 ° C. and calcined at 600 ° C. for 2 hours.
  • the coating amount was 7.5 g Al2O3, 2 g CeO2, 0.5 g ZrO2 per part.
  • the amount of precious metal loaded is 0.24 g / part.
  • the catalyst according to Example 1 was tested in accordance with the experimental arrangement in FIG. 1.
  • the annular gap between the inner tube outer diameter and the inner tube diameter was 1 mm.
  • a two-wheel motorcycle with an air-cooled two-stroke single-cylinder engine with a displacement of 148 cm3 served as the test vehicle.
  • the performance of the two-wheeler was 14 KW at a nominal speed of 8100 min ⁇ 1.
  • An oil / petrol mixture of 1:50 was used.
  • the vehicle was measured on a roller test bench in accordance with test specification ECE R40.
  • the exhaust gas temperatures at the catalyst inlet varied in the test cycle from 250-650 ° C.
  • the exhaust gas analysis was carried out according to the CVS principle.
  • the metal tube pretreated in this way is immersed in a 42% suspension of La2O3-stabilized ⁇ -Al2O3 (130 m2 / g) and cerium oxide, excess coating material is removed by blowing, dried and tempered at 500 ° C. for 2 hours.
  • the amount of noble metal was 125 mg / part.
  • the catalyst according to Example 3 was tested in accordance with the experimental arrangement in FIG. 2.
  • the annular gap between the inner tube outer diameter and the inner tube diameter was 1.5 mm on average.
  • a two-wheel motorcycle with an air-cooled two-stroke single-cylinder engine with a displacement of 134 cm3 served as the test vehicle.
  • the engine output was 12 KW at a rated speed of 8100 min ⁇ 1.
  • An oil / petrol mixture of 1:30 was used.
  • the vehicle was measured on a roller test bench in accordance with test specification ECE R40.
  • the exhaust gas temperature at the catalyst inlet was 150-420 ° C.
  • the exhaust gas analysis was carried out according to the CVS principle. The following emission values were determined: The conversion types were therefore 53% for CO, 41% for HC and 13% for NO x .
  • a monolithic metal support with a diameter of 60 mm, a length of 75 mm and a cell density of 31 cells / cm2 is coated by immersion in an aqueous suspension of ⁇ -Al2O3, cerium acetate and zirconium acetate and excess coating material is removed by blowing out. After drying at 120 ° C and calcining for one hour at 700 ° C there are 25 g Al2O3, 5 g CeO2, and 1g ZrO2 on the support.
  • Example 4 are integrated into the exhaust of a two-stroke motorcycle. The tests are carried out in accordance with Example 4.
  • Example 4 Compared to Example 4, there were significantly increased conversion types of 84% for CO and 86% for HC, with almost the same nitrogen oxide emissions. Such a concept is therefore particularly suitable when future, stricter limit values have to be met.

Abstract

The invention relates to an arrangement for catalytic purification of the exhaust gases of internal combustion engines, especially two-stroke engines, consisting of a jacket tube (1) which is arranged in the exhaust path and in which there is installed a perforated inner tube (3) to form a narrow annular space (5) between the jacket tube and the inner tube. The inner tube (3) is occupied by a catalyst. <IMAGE>

Description

Die Erfindung betrifft eine Anordnung zur katalytischen Reinigung der Auspuffgase von Verbrennungsmotoren, insbesondere von Zweitaktmotoren.The invention relates to an arrangement for the catalytic cleaning of the exhaust gases of internal combustion engines, in particular of two-stroke engines.

Verbrennungsmotoren, insbesondere nach dem Zweitaktprinzip, erfordern zum Zwecke eines günstigen Ablaufs der Gaswechselvorgänge (Frischgasfüllungs- Spülungs-und Abgasausstoßvorgang) eine bestimmte Ausbildung der Abgasführung. Dafür spielen neben einer passenden Abstimmung des Schalldämpfers bestimmte konstruktive Maßnahmen im Bereich zwischen Abgasauslaß des Motors und dem Schalldämpfer eine leistungsrelevante Rolle. So werden z. B. im oder unmittelbar nach dem Auspuffkrümmer Reflexionsflächen und/oder Expansionsräume (sog. Auspuffbirnen) vorgesehen, um die Gasdynamik positiv zu beeinflussen.Internal combustion engines, in particular according to the two-stroke principle, require a certain design of the exhaust gas routing for the purpose of a favorable sequence of the gas exchange processes (fresh gas filling, purging and exhaust gas discharge process). In addition to a suitable tuning of the muffler, certain design measures in the area between the exhaust gas outlet of the engine and the muffler play a role relevant to performance. So z. B. in or immediately after the exhaust manifold reflection surfaces and / or expansion spaces (so-called. Exhaust bulbs) provided to positively influence the gas dynamics.

Herkömmliche katalytische Abgasreinigungsanlagen, wie Schüttbett- oder Monolithkatalysatoren, welche meist im motornahen Bereich der Auspuffanlage angeordnet werden müssen, haben sich bei Fahrzeugen mit Zweitaktmotoren auf Grund des durch sie bedingten Abgasgegendrucks und der Störung der gasdynamischen Schwingungen als leistungsmindern erwiesen.Conventional catalytic exhaust gas cleaning systems, such as loose bed or monolith catalysts, which usually have to be arranged in the area of the exhaust system near the engine, have proven to be less efficient in vehicles with two-stroke engines due to the exhaust gas back pressure caused by them and the disturbance of the gas dynamic vibrations.

Weiterhin können Verstopfungen durch Ölkohle auftreten; dies geschieht z. B. manchmal bei Monolithkatalysatoren unter bestimmten Betriebsbedingungen des Motors. Herkömmliche Monolithkatalysatoren erweisen sich überhaupt als nachteilig, da solche Katalysatoren bei Motoren mit hohen Emissionen aufgrund ihres sehr hohen Konvertierungspotentials auf kleinen Volumen hohen Exothermen ausgesetzt sind und daher die Gefahr einer thermischen Schädigung bis hin zum Verschmelzen des Katalysators besteht. Der Erfindung liegt die Aufgabe zugrunde, ein für solche Motoren besser geeignetes katalytisches Abgasreinigungssystem zu schaffen. Diese Aufgabe wird durch die in den Ansprüchen beschriebene Anordnung gelöst.Oil coal blockages can also occur; this happens e.g. B. sometimes with monolith catalysts under certain engine operating conditions. Conventional monolith catalysts prove to be disadvantageous at all, since such catalysts in engines with high emissions are exposed to high exotherms due to their very high conversion potential on small volumes and therefore there is a risk of thermal damage up to the melting of the catalyst. The invention has for its object to provide a catalytic exhaust gas purification system which is more suitable for such engines. This object is achieved by the arrangement described in the claims.

Die erfindungsgemäße Anordnung nach den Ansprüchen ist auch für Viertaktmotoren geeignet, da auch bei diesen eine Feinabstimmung der Auspuffanlage erforderlich ist.The arrangement according to the invention is also suitable for four-stroke engines, since these also require fine tuning of the exhaust system.

Bei der erfindungsgemäßen Anordnung zur Abgasreinigung kann das Mantelrohr (1) beliebig geformt sein. Das Innenrohr (3) ist entsprechend geformt, um einen Ringraum (5) annähernd gleichbleibenden Querschnitts zu erhalten. Auch konisch zulaufende Ringräume sind Bestandteil der Erfindung.In the arrangement for exhaust gas purification according to the invention, the casing tube (1) can have any shape. The inner tube (3) is shaped accordingly in order to obtain an annular space (5) of approximately constant cross section. Tapered annular spaces are also part of the invention.

Der Ringraum (5) nimmt aufgrund der vorgesehenen Dimensionierung nur einen Bruchteil des Volumens des Mantelrohrs (1) in Anspruch. Ringraum (5) und Perforation verstärken im Katalysatorbereich die Turbulenzen und damit den Gasaustausch. Dieser Effekt wird bei der Grundausführung der erfindungsgemäßen Anordnung durch den beidseitig offenen Ringspalt verstärkt, der eine Hinterströmung des katalytisch beschichteten Innenrohrs gewährleistet. Bei manchen Motorkonstruktionen ist eine zumindest einseitige Schließung des Ringraums an beliebiger Stelle zweckmäßig (Anspruch 2).The annular space (5) takes up only a fraction of the volume of the casing tube (1) due to the dimensions provided. Annulus (5) and perforation reinforce the in the catalyst area Turbulence and thus gas exchange. This effect is reinforced in the basic configuration of the arrangement according to the invention by the annular gap which is open on both sides and which ensures a backflow of the catalytically coated inner tube. In some motor designs, an at least one-sided closure of the annular space at any point is expedient (claim 2).

Bei Rundlöchern als Perforationen bewegen sich die Lochdurchmesser des Innenrohrs von 0.75 bis 10 mm, bei einem Lochabstand von 1.0 bis 15 mm. Bevorzugt sind Lochdurchmesser von 1.5 bis 6 mm und Lochabstände von 2.0 bis 7.5 mm (Anspruch 7). Das Innenrohr kann über den gesamten Mantel regelmäßig angeordnete Löcher unterschiedlichen Durchmessers aufweisen.With round holes as perforations, the hole diameters of the inner tube range from 0.75 to 10 mm, with a hole spacing of 1.0 to 15 mm. Hole diameters of 1.5 to 6 mm and hole spacing of 2.0 to 7.5 mm are preferred (claim 7). The inner tube can have regularly arranged holes of different diameters over the entire jacket.

Neben den Rundlochungen können auch Rechteck- und Schlitzlochungen und solche beliebiger Form Anwendung finden sowie deren Kombination. Ebenso kann die Perforationsgröße oder -anzahl über die Länge des Innenrohrs variiert werden. Gegebenenfalls kann der Rohrkörper auch aus Streckmetall oder grobem Drahtgewebe bestehen.In addition to the round perforations, rectangular and slot perforations and any shape can be used and their combination. Likewise, the size or number of perforations can be varied over the length of the inner tube. If necessary, the tubular body can also consist of expanded metal or coarse wire mesh.

Die relative freie Lochfläche (Gesamtlochfläche) beträgt bei den verschiedenen Ausführungsformen 5 bis 80%, bevorzugt 20-60% (Anspruch 8).The relative free hole area (total hole area) is in the different embodiments 5 to 80%, preferably 20-60% (claim 8).

Die als Turbulatoren wirkenden Perforationen im Innenrohr können gemäß Anspruch 3 in ihrer Wirkung verstärkt werden.The perforations in the inner tube which act as turbulators can be reinforced in their effect according to claim 3.

Das Innenrohr kann gegebenenfalls, insbesondere aus fertigungstechnischen Gründen, aus 2 gegebenenfalls miteinander verbundenen Halbschalen ausgebildet sein (Anspruch 4). Dadurch kann sich eine Teilung des Ringraumes in zwei Hälften ergeben.The inner tube can, if appropriate, in particular for manufacturing reasons, be formed from two half-shells which are optionally connected to one another (claim 4). This can result in a division of the annular space into two halves.

Die geometrische Oberfläche kann durch Umgeben mit einem Drahtnetz, Streckmetall oder einem weiteren perforierten Rohr erhöht werden, um erhöhte Konvertierungsraten für die Schadstoffe zu erzielen (Anspruch 5).The geometric surface can be increased by surrounding it with a wire mesh, expanded metal or another perforated tube in order to achieve increased conversion rates for the pollutants (claim 5).

Die erfindungsgemäße Anordnung eignet sich sowohl als Hauptkatalysator wie als Startkatalysator für einen nachgeschalteten Hauptkatalysator (6) beliebiger Bauart (Anspruch 6). Durch Verwendung als Startkatalysator ergibt sich durch Teilumsatz von Schadstoffen eine Temperaturerhöhung, welcher das Anspringen eines gegebenenfalls in einem kühleren Teil der Abgasanlage nachgeschalteten Hauptkatalysators erleichtert oder erst ermöglicht. Bei Auftreten hoher Schadstoffkonzentrationen und gleichzeitig hohen Abgastemperaturen wirkt sich ein Teilumsatz insofern günstig aus, als er die Temperaturbelastung wegen der zwischen Start- und Hauptkatalysator erfolgenden Abgaskühlung vermindert und den Hauptkatalysator vor vorzeitiger Zerstörung oder thermischer Deaktivierung bewahrt. Die Umsatzraten der erfindungsgemäßen Anordnung liegen, wie die nachfolgenden Ausführungsbeispiele zeigen, bei Verwendung als Hauptkatalysator überraschend hoch. Auch bei Verwendung als Hauptkatalysator lassen sich bei Einsatz an Zweirädern heute bereits gültige und zukünftige Grenzwerte erfüllen.The arrangement according to the invention is suitable both as a main catalyst and as a starting catalyst for a downstream main catalyst (6) of any type (claim 6). When used as a starting catalytic converter, partial conversion of pollutants results in an increase in temperature, which makes it easier or even possible to start a main catalytic converter which may be connected in a cooler part of the exhaust system. If high concentrations of pollutants occur and at the same time high exhaust gas temperatures, a partial conversion has a favorable effect in that it reduces the temperature load due to the exhaust gas cooling between the start and main catalytic converter and protects the main catalytic converter from premature destruction or thermal deactivation. As the following exemplary embodiments show, the conversion rates of the arrangement according to the invention are surprisingly high when used as the main catalyst. Also at When used on two-wheelers, the main catalyst can be used to meet current and future limit values.

Als Katalysator können alle üblichen von der Abgasreinigung von Ottomotoren her bekannten edelmetall- und/oder nichtedelmetallhaltigen Formulierungen zum Einsatz gelangen.All of the formulations containing noble metals and / or non-noble metals known from exhaust gas cleaning of gasoline engines can be used as the catalyst.

Besonders geeignet sind Pt, Pd und/oder Rh-haltige Edelmetallkatalysatoren auf hitzebeständigem, oxidischen Trägermaterial (Al₂O₃, SiO₂, Aluminiumsilikaten). Zur Aktivierung und Verbesserung der thermischen Stabilität kann das Trägermaterial mit oxidischen Zusätzen wie CeO₂, ZrO₂, Erdalkalimetalloxid und/oder Seltenerdoxiden versehen sein.Pt, Pd and / or Rh-containing noble metal catalysts on a heat-resistant, oxidic support material (Al₂O₃, SiO₂, aluminum silicates) are particularly suitable. To activate and improve the thermal stability, the carrier material can be provided with oxidic additives such as CeO₂, ZrO₂, alkaline earth metal oxide and / or rare earth oxides.

Gegebenenfalls wird vor der Aufbringung des oxidischen Trägermaterials eine Vorbehandlung durch Sandstrahlen, Flammspritzen, Aluminieren durchgeführt, um die Temperaturbeständigkeit des perforierten Rohrkörpers und die Haftung der Beschichtung zu verbessern.If necessary, a pre-treatment by sandblasting, flame spraying, aluminizing is carried out before the application of the oxidic carrier material in order to improve the temperature resistance of the perforated tubular body and the adhesion of the coating.

Beispiel 1example 1

Ein perforierter, konisch zulaufender Rohrbogen mit Durchmessern von 30 mm bzw. 55 mm, einer gestreckten Rohrlänge von 345 mm, 2 mm Lochdurchmesser und 3,15 mm Lochabstand aus hochtemperaturbeständigem Stahl 1.4841 wird zunächst 3 h bei 900°C an Luft getempert.A perforated, tapered pipe bend with diameters of 30 mm or 55 mm, an elongated pipe length of 345 mm, 2 mm hole diameter and 3.15 mm hole spacing made of high-temperature resistant steel 1.4841 is first tempered in air at 900 ° C for 3 h.

Anschließend wird der Rohrbogen mit einer ca. 40% Dispersion aus γ-Al₂O₃, (150 m²/g), Ceracetat und Zirkonylacetat belegt, bei 120°C getrocknet und bei 600°C 2 h calciniert. Die Beschichtungsmenge betrug 7,5 g Al₂O₃, 2 g CeO₂, 0,5 g ZrO₂ pro Teil. Anschließend wird der Rohrkörper mit einer Lösung von Pt(NH₃)₄(OH)₂ und Rh(NO₃)₃ (Gewichtsverhältnis Pt:Rh = 5:1 ) imprägniert, getrocknet und im Formiergas (N₂:H₂=95:5) bei 400°C reduziert. Die Edelmetallbeladungsmenge beträgt 0,24 g/Teil.The tube bend is then coated with an approximately 40% dispersion of γ-Al₂O₃, (150 m² / g), cerium acetate and zirconium acetate, dried at 120 ° C. and calcined at 600 ° C. for 2 hours. The coating amount was 7.5 g Al₂O₃, 2 g CeO₂, 0.5 g ZrO₂ per part. Then the tubular body is impregnated with a solution of Pt (NH₃) ₄ (OH) ₂ and Rh (NO₃) ₃ (weight ratio Pt: Rh = 5: 1), dried and in the forming gas (N₂: H₂ = 95: 5) at 400 ° C reduced. The amount of precious metal loaded is 0.24 g / part.

Beispiel 2Example 2

Der Katalysator nach Beispiel 1 wurde gemäß der Versuchsanordnung in Fig. 1 getestet. Der Ringspalt zwischen Innenrohr-Außendurchmesser und Mantelrohr-Innendurchmesser betrug 1 mm. Als Versuchsträger diente ein zweirädriges Motorrad mit einem luftgekühlten Zweitakt-Einzylindermotor mit einem Hubraum von 148 cm³. Die Leistung des Zweirades betrug 14 KW bei einer Nenndrehzahl von 8100 min⁻¹. Ein Öl/Benzin-Gemisch von 1:50 kam zum Einsatz.The catalyst according to Example 1 was tested in accordance with the experimental arrangement in FIG. 1. The annular gap between the inner tube outer diameter and the inner tube diameter was 1 mm. A two-wheel motorcycle with an air-cooled two-stroke single-cylinder engine with a displacement of 148 cm³ served as the test vehicle. The performance of the two-wheeler was 14 KW at a nominal speed of 8100 min⁻¹. An oil / petrol mixture of 1:50 was used.

Das Fahrzeug wurde auf einem Rollenprüfstand gemäß der Testvorschrift ECE R40 vermessen. Die Abgastemperaturen am Katalysatoreintritt variierten im Testzyklus von 250-650°C. Die Abgasanalyse erfolgte nach dem CVS-Prinzip.The vehicle was measured on a roller test bench in accordance with test specification ECE R40. The exhaust gas temperatures at the catalyst inlet varied in the test cycle from 250-650 ° C. The exhaust gas analysis was carried out according to the CVS principle.

Folgende Emissionswerte wurden ermittelt:

Figure imgb0001

Die Konvertierungsarten betrugen somit 68% für CO und 56% für (HC+NOx).The following emission values were determined:
Figure imgb0001

The conversion types were 68% for CO and 56% for (HC + NO x ).

Durch den Einsatz dieses speziell ausgebildeten Katalysators ist es möglich, die ab 01.10.1990 geltenden Schweizer Grenzwerte (CO = 8,0 g/km, HC+NOx =3,1 g/km zu unterschreiten, ohne daß es zu einer starken Beeinträchtigung der gasdynamischen Vorgänge kommt, die zu einem Leistungsabfall des Zweitaktmotors führen.By using this specially designed catalytic converter, it is possible to fall below the Swiss limit values applicable from October 1st, 1990 (CO = 8.0 g / km, HC + NO x = 3.1 g / km), without causing any severe impairment of the gas dynamic processes that lead to a drop in performance of the two-stroke engine.

Beispiel 3Example 3

Ein konisches Rohr aus hitzebeständigem Stahl 1.4828 mit der Blechstärke 1 mm mit Durchmessern von 39 mm bzw. 61 mm und einer Länge von 150 mm, das eine Schlitzlochung (1.5 mm Lochbreite x 6 mm Lochlänge, Stegbreite 1,3 mm) aufweist, wird durch Flammspritzen mit einer festhaftenden, rauhen Oxidschicht auf Al₂O₃-Basis belegt. Das so vorbehandelte Metallrohr wird in eine 42%ige Suspension aus La₂O₃-stabilisiertem γ-Al₂O₃ (130 m²/g) und Ceroxid getaucht, überschüssiges Beschichtungsmaterial durch Ausblasen entfernt, getrocknet und 2 h bei 500°C getempert. Nach der Beschichtung befanden sich auf dem Rohr 3,3 g Al₂O₃ , 0,2 g La₂O₃ und 1,0 g CeO₂. Anschließend wurde die Katalysatorvorstufe mit einer salpetersauren Lösung von Pt(NH₃)₂(NO₂)₂ und Pd(NO₃)₂ (Gewichtsverhältnis Pt:Pd = 2:1) imprägniert, getrocknet und bei 300°C in Luft calciniert. Die Edellmetallmenge betrug 125 mg/Teil.A conical tube made of heat-resistant steel 1.4828 with a sheet thickness of 1 mm with a diameter of 39 mm or 61 mm and a length of 150 mm, which has a slot perforation (1.5 mm hole width x 6 mm hole length, web width 1.3 mm), is through Flame spraying with a firmly adhering, rough oxide layer based on Al₂O₃. The metal tube pretreated in this way is immersed in a 42% suspension of La₂O₃-stabilized γ-Al₂O₃ (130 m² / g) and cerium oxide, excess coating material is removed by blowing, dried and tempered at 500 ° C. for 2 hours. After the coating was on the Tube 3.3 g Al₂O₃, 0.2 g La₂O₃ and 1.0 g CeO₂. The catalyst precursor was then impregnated with a nitric acid solution of Pt (NH₃) ₂ (NO₂) ₂ and Pd (NO₃) ₂ (Pt: Pd = 2: 1 weight ratio), dried and calcined at 300 ° C. in air. The amount of noble metal was 125 mg / part.

Beispiel 4Example 4

Der Katalysator nach Beispiel 3 wurde gemäß der Versuchsanordnung in Fig. 2 getestet. Der Ringspalt zwischen Innenrohr-Außendurchmesser und Mantelrohr-Innendurchmesser betrug im Durchschnitt 1,5 mm. Als Versuchsträger diente ein zweirädriges Motorrad mit einem luftgekühlten Zweitakt-Einzylindermotor mit einem Hubraum von 134 cm³. Die Leistung des Motors betrug 12 KW bei einer Nenndrehzahl von 8100 min⁻¹. Es kam eine Öl/Benzin-Gemisch von 1:30 zum Einsatz.The catalyst according to Example 3 was tested in accordance with the experimental arrangement in FIG. 2. The annular gap between the inner tube outer diameter and the inner tube diameter was 1.5 mm on average. A two-wheel motorcycle with an air-cooled two-stroke single-cylinder engine with a displacement of 134 cm³ served as the test vehicle. The engine output was 12 KW at a rated speed of 8100 min⁻¹. An oil / petrol mixture of 1:30 was used.

Das Fahrzeug wurde auf einem Rollenprüfstand gemäß der Testvorschrift ECE R40 vermessen. Die Abgastemperatur am Katalysatoreintritt betrug 150-420 °C. Die Abgasanalyse erfolgte nach dem CVS-Prinzip. Folgende Emissionswerte wurden ermittelt:

Figure imgb0002
Die Konvertierungsarten betrugen somit 53 % für CO, 41% für HC und 13 % für NOx.The vehicle was measured on a roller test bench in accordance with test specification ECE R40. The exhaust gas temperature at the catalyst inlet was 150-420 ° C. The exhaust gas analysis was carried out according to the CVS principle. The following emission values were determined:
Figure imgb0002
The conversion types were therefore 53% for CO, 41% for HC and 13% for NO x .

Durch den Einsatz dieses speziell ausgebildeten Katalysators ist es möglich, die ab 30.09.1991 in Österreich geltenden Grenzwerte (CO = 8g/km, HC = 7,5 g/km, NOx = 0,1 g/km) für Zweitaktmotorräder einzuhalten.By using this specially designed catalytic converter, it is possible to comply with the limit values applicable in Austria from September 30, 1991 (CO = 8g / km, HC = 7.5 g / km, NO x = 0.1 g / km) for two-stroke motorcycles.

Beispiel 5Example 5

Ein monolithischer Metallträger mit 60 mm Durchmesser, 75 mm Länge und einer Zelldichte von 31 Zellen/cm² wird durch Eintauchen in eine wässrige Suspension aus γ-Al₂O₃, Ceracetat und Zirkonylacetat belegt und überschüssiges Beschichtungsmaterial durch Ausblasen entfernt. Nach dem Trocknen bei 120 °C und einstündigem Calzinieren bei 700 °C liegen 25 g Al₂O₃, 5 g CeO₂, und 1g ZrO₂ auf dem Träger vor. Die Katalysatorvorstufe wird anschließend mit einer Lösung von Pt(NH₃)₄(OH)₂ und Rh(NO₃)₃ imprägniert und bei 300°C getrocknet. Nach der Beschichtung befanden sich 0.36 g Edelmetall im Gewichtsverhältnis Pt:Rh = 5:1 auf dem Katalysator.A monolithic metal support with a diameter of 60 mm, a length of 75 mm and a cell density of 31 cells / cm² is coated by immersion in an aqueous suspension of γ-Al₂O₃, cerium acetate and zirconium acetate and excess coating material is removed by blowing out. After drying at 120 ° C and calcining for one hour at 700 ° C there are 25 g Al₂O₃, 5 g CeO₂, and 1g ZrO₂ on the support. The catalyst precursor is then impregnated with a solution of Pt (NH₃) ₄ (OH) ₂ and Rh (NO₃) ₃ and dried at 300 ° C. After coating, 0.36 g of precious metal in the Pt: Rh = 5: 1 weight ratio were on the catalyst.

Beispiel 6Example 6

Die Katalysatoren nach Beispiel 3 und 5 werden gemäß Fig. 3 in den Auspuff eines Zweitaktmotorrades integriert. Die Tests erfolgen entsprechend Beispiel 4.3 are integrated into the exhaust of a two-stroke motorcycle. The tests are carried out in accordance with Example 4.

Folgende Emissionswerte wurden gemessen:

Figure imgb0003
The following emission values were measured:
Figure imgb0003

Im Vergleich zu dem Beispiel 4 ergaben sich deutlich erhöhte Konvertierungsarten von 84% für CO und 86% für HC, bei nahezu gleichen Stickoxidemissionen. Ein solches Konzept eignet sich daher besonders, wenn zukünftige, schärfere Grenzwerte zu erfüllen sind.Compared to Example 4, there were significantly increased conversion types of 84% for CO and 86% for HC, with almost the same nitrogen oxide emissions. Such a concept is therefore particularly suitable when future, stricter limit values have to be met.

Bei alleiniger Verwendung des Katalysators nach Beispiel 5 bei einer Anordnung gemäß Fig. 3 können die hohen Konvertierungsarten nicht erzielt werden, da das Temperaturniveau ohne konischen Vorkatalysator zu niedrig ist.If the catalyst according to Example 5 is used alone with an arrangement according to FIG. 3, the high conversion types cannot be achieved, since the temperature level is too low without a conical precatalyst.

Ein motornäherer Einbau des Katalysators nach Beispiel 5 im Bereich des Vorkatalysators (Fig. 3) würde zu einer Störung der gasdynamischen Vorgänge und somit zu unakzeptablen Leistungsverlusten führen und ist daher nicht angezeigt.An installation of the catalytic converter according to Example 5 closer to the engine in the area of the pre-catalytic converter (FIG. 3) would lead to a disturbance of the gas dynamic processes and thus to unacceptable power losses and is therefore not indicated.

Claims (8)

Anordnung zur katalytischen Reinigung der Auspuffgase von Verbrennungsmotoren, insbesondere von Zweitaktmotoren,
gekennzeichnet durch
ein Mantelrohr (1), welches gegebenenfalls einen Abschnitt des Auspuffrohrs oder einen im Auspuffrohr angeordneten Expansionsraum bildet, ein innerhalb des Mantelrohrs und im Abstand von diesem angeordnetes, mit der Form des Mantelrohrs gegebenenfalls korrespondierendes und mit einem Abgasreinigungskatalysator (2) ein- oder beidseitig beschichtetes perforiertes Innenrohr (3), wobei der Abstand zwischen Mantelrohr und Innenrohr durch mindestens einen mit beiden Rohren verbundenen Steg (4) unter Ausbildung eines Ringraums (5), der durch Nasen oder Sicken im Innenrohr unterbrochen sein kann, hergestellt ist und in einem Bereich, gegeben durch das Verhältnis zwischen Mantelrohr-Innendurchmesser zu Innenrohr-Außendurchmesser, von 1,01 bis 1,20 liegt.
Arrangement for the catalytic cleaning of the exhaust gases from internal combustion engines, in particular from two-stroke engines,
marked by
a jacket pipe (1), which optionally forms a section of the exhaust pipe or an expansion space arranged in the exhaust pipe, an inside the jacket pipe and at a distance from it, which optionally corresponds to the shape of the jacket pipe and is coated on one or both sides with an exhaust gas purification catalyst (2) perforated inner tube (3), the distance between the casing tube and the inner tube being produced by at least one web (4) connected to both tubes to form an annular space (5) which can be interrupted by lugs or beads in the inner tube and in one area, given by the ratio between the inner tube diameter to the inner tube outer diameter, is from 1.01 to 1.20.
Anordnung nach Anspruch 1
dadurch gekennzeichnet,
daß der Ringraum (5) zumindest einseitig an beliebiger Stelle, vorzugsweise durch Aufweitung der Innenrohrenden oder durch Schweiß-oder Lötauftrag geschlossen ist.
Arrangement according to claim 1
characterized,
that the annular space (5) is closed at least on one side at any point, preferably by widening the inner tube ends or by welding or soldering.
Anordnung nach Anspruch 1 oder 2,
dadurch gekennzeichnet,
daß die Perforation als tiefgezogene auf- und/oder abwärts gerichtete Ausbuchtungen vorliegen.
Arrangement according to claim 1 or 2,
characterized,
that the perforation is present as deep drawn upward and / or downward bulges.
Anordnung nach den Ansprüchen 1 bis 3
dadurch gekennzeichnet,
daß das Innenrohr (3) aus zwei, gegebenenfalls miteinander verbundenen Halbschalen besteht.
Arrangement according to claims 1 to 3
characterized,
that the inner tube (3) consists of two half-shells, optionally connected to one another.
Anordnung nach den Ansprüchen 1 bis 4,
dadurch gekennzeichnet,
daß das Innenrohr bündig mit einem ebenfalls katalysatorbeschichteten Drahtnetz, Streckmetall oder weiterem perforiertem Rohr umgeben ist.
Arrangement according to claims 1 to 4,
characterized,
that the inner tube is flush with a catalyst-coated wire mesh, expanded metal or other perforated tube.
Anordnung nach den Ansprüchen 1 bis 5,
dadurch gekennzeichnet,
daß sie als Vorkatalysator vor einen gegebenenfalls monolithischen Hauptkatalysator (6) geschaltet ist.
Arrangement according to claims 1 to 5,
characterized,
that it is connected as a pre-catalyst upstream of a possibly monolithic main catalyst (6).
Anordnung nach den Ansprüchen 1 bis 6,
dadurch gekennzeichnet,
daß die Perforationen als Rundloch mit Lochdurchmessern von 0.75 bis 10, bevorzugt 1.5 bis 6 mm, vorliegen.
Arrangement according to claims 1 to 6,
characterized,
that the perforations are present as a round hole with hole diameters of 0.75 to 10, preferably 1.5 to 6 mm.
Anordnung nach den Ansprüchen 1 bis 7,
dadurch gekennzeichnet,
daß die Gesamtlochfläche 5 bis 80, bevorzugt 20 bis 60% beträgt.
Arrangement according to claims 1 to 7,
characterized,
that the total perforated area is 5 to 80, preferably 20 to 60%.
EP90122290A 1989-12-02 1990-11-22 Device for catalytic purification of exhaust gases of internal combustion two-stroke engines Expired - Lifetime EP0431405B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3939921A DE3939921A1 (en) 1989-12-02 1989-12-02 ARRANGEMENT FOR CATALYTICALLY CLEANING THE EXHAUST GAS FROM COMBUSTION ENGINES, IN PARTICULAR ACCORDING TO THE TWO-STOCK PRINCIPLE
DE3939921 1989-12-02

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EP0431405A1 true EP0431405A1 (en) 1991-06-12
EP0431405B1 EP0431405B1 (en) 1994-05-25

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JP (1) JP3140044B2 (en)
KR (1) KR0171890B1 (en)
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AT (1) ATE106112T1 (en)
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DE (2) DE3939921A1 (en)

Cited By (7)

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EP0556129A1 (en) * 1992-02-14 1993-08-18 Institut Francais Du Petrole Exhaust duct with a catalytic wall, for internal combustion engines
FR2713703A1 (en) * 1993-12-09 1995-06-16 Honda Motor Co Ltd Engine exhaust gas cleaning device.
EP0699829A3 (en) * 1994-09-05 1996-05-01 Honda Motor Co Ltd Engine exhaust purifying device
EP0787816A1 (en) * 1996-01-25 1997-08-06 Ecia - Equipements Et Composants Pour L'industrie Automobile Process for fabricating a coating on a catalytic exhaust system and coating obtained by this method
WO2000068550A1 (en) * 1999-05-10 2000-11-16 Emitec Gesellschaft Für Emissionstechnologie Mbh Honeycomb body structure comprising various sections in a casing tube
US9790836B2 (en) 2012-11-20 2017-10-17 Tenneco Automotive Operating Company, Inc. Loose-fill insulation exhaust gas treatment device and methods of manufacturing
IT201700061755A1 (en) * 2017-06-06 2018-12-06 Vins S R L THERMAL COMBUSTION INTERNAL THERMAL MOTOR WITH DRAINAGE CATALYST

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DE4244712C2 (en) * 1992-02-14 1996-09-05 Degussa Coating dispersion for the production of coatings promoting an alkaline, structure-strengthening body
US5958829A (en) * 1992-02-14 1999-09-28 Degussa-Huls Aktiengesellschaft Coating dispersion for exhaust gas catalysts
CN1044932C (en) * 1994-07-14 1999-09-01 财团法人工业技术研究院 Tubular catalyst purifying apparatus for locomotive
JP3369335B2 (en) * 1994-11-07 2003-01-20 本田技研工業株式会社 Exhaust gas purification device
JP2002070546A (en) * 2000-09-04 2002-03-08 Shinba Iron Works Inc Exhaust system pipe mounted with catalyst pipe and its manufacturing method
JP2011064192A (en) * 2009-08-21 2011-03-31 Nichias Corp Automobile exhaust pipe
WO2017164163A1 (en) * 2016-03-22 2017-09-28 ヤマハ発動機株式会社 Straddle-type vehicle
US11291951B2 (en) * 2016-05-20 2022-04-05 Cataler Corporation Exhaust gas purifying catalyst for 2-stroke general-purpose engines

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AT396170B (en) * 1989-06-01 1993-06-25 Laimboeck Franz EXHAUST SYSTEM FOR TWO-STROKE COMBUSTION ENGINES

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US3061416A (en) * 1957-11-22 1962-10-30 George P Kazokas Catalytic muffler
DE2942728A1 (en) * 1979-10-23 1981-05-07 Bremshey Ag, 5650 Solingen Exhaust pipe for IC engine - has double walled construction with perforated guide blades within to provide silencing

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0556129A1 (en) * 1992-02-14 1993-08-18 Institut Francais Du Petrole Exhaust duct with a catalytic wall, for internal combustion engines
FR2687431A1 (en) * 1992-02-14 1993-08-20 Inst Francais Du Petrole EXHAUST TUBE WITH CATALYTIC WALL FOR INTERNAL COMBUSTION ENGINES.
FR2713703A1 (en) * 1993-12-09 1995-06-16 Honda Motor Co Ltd Engine exhaust gas cleaning device.
EP0699829A3 (en) * 1994-09-05 1996-05-01 Honda Motor Co Ltd Engine exhaust purifying device
US5729972A (en) * 1994-09-05 1998-03-24 Honda Giken Kogyo Kabushiki Kaisha Engine exhaust purifying device
EP0787816A1 (en) * 1996-01-25 1997-08-06 Ecia - Equipements Et Composants Pour L'industrie Automobile Process for fabricating a coating on a catalytic exhaust system and coating obtained by this method
WO2000068550A1 (en) * 1999-05-10 2000-11-16 Emitec Gesellschaft Für Emissionstechnologie Mbh Honeycomb body structure comprising various sections in a casing tube
US9790836B2 (en) 2012-11-20 2017-10-17 Tenneco Automotive Operating Company, Inc. Loose-fill insulation exhaust gas treatment device and methods of manufacturing
IT201700061755A1 (en) * 2017-06-06 2018-12-06 Vins S R L THERMAL COMBUSTION INTERNAL THERMAL MOTOR WITH DRAINAGE CATALYST

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CN1027004C (en) 1994-12-14
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KR910012501A (en) 1991-08-08
DE3939921A1 (en) 1991-06-06
DE59005813D1 (en) 1994-06-30
KR0171890B1 (en) 1999-03-20
EP0431405B1 (en) 1994-05-25
JP3140044B2 (en) 2001-03-05
BR9006082A (en) 1991-09-24
CN1052355A (en) 1991-06-19
DE3939921C2 (en) 1992-11-05

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