EP1759097B1 - Apparatus for purifying exhaust gases of an internal combustion engine - Google Patents

Apparatus for purifying exhaust gases of an internal combustion engine Download PDF

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Publication number
EP1759097B1
EP1759097B1 EP05767079A EP05767079A EP1759097B1 EP 1759097 B1 EP1759097 B1 EP 1759097B1 EP 05767079 A EP05767079 A EP 05767079A EP 05767079 A EP05767079 A EP 05767079A EP 1759097 B1 EP1759097 B1 EP 1759097B1
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EP
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Prior art keywords
iron
containing material
catalytically active
active coating
combustion engine
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EP05767079A
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German (de)
French (fr)
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EP1759097A1 (en
Inventor
Henning Bockhorn
Sven Kureti
Thomas Schroeder
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Robert Bosch GmbH
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Robert Bosch GmbH
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
    • F01N3/0231—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles using special exhaust apparatus upstream of the filter for producing nitrogen dioxide, e.g. for continuous filter regeneration systems [CRT]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2250/00—Combinations of different methods of purification
    • F01N2250/02—Combinations of different methods of purification filtering and catalytic conversion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/06—Ceramic, e.g. monoliths
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/065—Surface coverings for exhaust purification, e.g. catalytic reaction for reducing soot ignition temperature

Definitions

  • the invention relates to a device for cleaning exhaust gases of an internal combustion engine. Furthermore, the invention relates to an exhaust system for an internal combustion engine.
  • a catalytic diesel soot filter which comprises a catalytically active coating of metal-doped zeolite.
  • the zeolite is loaded with a Group IB, IIB, VB, VIB or VIIB metal of the Periodic Table or a combination thereof, preferably using nickel, copper, manganese, vanadium, silver or a combination thereof.
  • the DE 37 31 889 A1 describes a diesel particulate filter incorporating a filter element as a support for a catalyst prepared using at least one metal oxide having.
  • the carrier consists of a ceramic or metal foam body, the pore surfaces are coated continuously with one or more metal oxides of groups Ib, Vb, Vib, VIIb or the Fe group.
  • this particulate filter still has no satisfactory effectiveness in terms of NO x reduction.
  • a device for purifying exhaust gases of an internal combustion engine which comprises a particle filter, which is provided with a catalytically active coating
  • the catalytically active coating comprises a carrier material and an iron-containing material connected to the carrier material and present at least on the surface thereof, wherein the carrier material is, for example, a silicon oxide (silica).
  • an iron-containing material which is bonded to the support material and is present on the surface thereof, is very active as a catalytically active substance with respect to the conversion of the exhaust gases has good effect. It could thus be stated that, due to the composition according to the invention of the catalytically active coating, nitrogen oxides react with those in the exhaust gas Existing soot particles are excited, wherein even at temperatures of about 220 ° C, a reduction of NO x to N 2 , ie a nitrogen formation, has been found and in the exhaust gas leaving the device are almost no harmful NO molecules contained more, with a additional reducing agent can be dispensed with.
  • the soot particles contained in the exhaust gas are held in a conventional manner to the particulate filter and thus prevented from leaving the exhaust pipe in which the device according to the invention is preferably installed.
  • the soot particles retained on the pores of the particulate filter serve to reduce the nitrogen oxides as described above, so that the amount of soot increases far less than with known particulate filters and, correspondingly, less frequently regeneration is required.
  • the catalytic coating with the iron-containing material also causes a reduction in the ignition temperature of the soot in addition to the triggering of these reactions.
  • the support material is an aluminosilicate or a silicon oxide
  • a very fine distribution of the present at the surface of the support material iron-containing material is achieved, whereby a significant increase in reactivity is achieved.
  • the iron-containing material has iron oxide.
  • Iron oxide is a very good oxidation catalyst for carbon black and is advantageously nontoxic.
  • the iron-containing material consists of 100% iron oxide.
  • the iron-containing material has pure iron.
  • the iron-containing material consists of 100% pure iron.
  • the catalytically active coating comprises a noble metal.
  • the precious metals platinum and in particular palladium have proved to be particularly effective.
  • An exhaust system for an internal combustion engine with an inventive device for purifying exhaust gases is specified in claim 16.
  • An internal combustion engine 1 is provided with an exhaust system 2, which has an exhaust pipe 2a, are discharged through the produced in the internal combustion engine 1 in a conventional manner exhaust gases.
  • an exhaust pipe 2a In the exhaust pipe 2a, a device 3 for cleaning the exhaust gases of the internal combustion engine 1 is arranged, which will be described in more detail below.
  • the internal combustion engine 1 is preferably an internal combustion engine operating on the diesel principle, in the exhaust of which, in addition to other pollutants, soot particles are contained.
  • the device 3 has a particle filter 4 shown in a highly schematic manner, which preferably consists of ceramic, such as silicon carbide, but which may also consist of aluminum oxide or another suitable material.
  • the particle filter 4 in turn has a plurality of inlet channels 5 and outlet channels 6, which are mutually closed. It is therefore a reciprocal channel system. Alternatively, an open system with any channel shape and geometry would be possible.
  • the inlet channels 5 and the outlet channels 6 are separated from one another by respective walls 7 indicated by dashed lines, so that the exhaust gases have to flow through the walls 7 in order to pass from the inlet channels 5 into the outlet channels 6 and in this way leave the particle filter 4.
  • the material of the walls 7 of the particulate filter 4 is formed in a manner known per se porous, so that the gaseous exhaust gas constituents can flow through the walls 7, the soot particles, however, remain at the same or are deposited.
  • the particulate filter 4 and the same forming walls 7 is provided with a catalytically active coating 8, which has a carrier material 9 and connected to the substrate 9, the same on the surface thereof, iron-containing material 10.
  • the carrier material 9 of the catalytically active coating 8 is connected to the particle filter 4 by means of a binding agent 11 made of cerium oxide.
  • the iron-containing material 10 may in one embodiment of the device 3 comprise iron oxide, it is also possible in this context that the iron-containing material 10 consists of 100% iron oxide. Alternatively, it is also possible that the iron-containing material 10 has pure iron or consists of 100% pure iron. Furthermore, a mixture of iron oxide and pure iron to form the iron-containing material 10 is possible. In addition, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, Zinc, zirconium, niobium, tungsten and / or rhenium be included in the ferrous material 10, with iron oxide or pure iron always make the largest part of the iron-containing material 10.
  • the known ion exchange method can be used, but it is also possible to connect the carrier material 9 with the iron-containing material 10 by means of a coating method.
  • the catalytically active coating 8 in addition to the carrier material 9 and the iron-containing material 10, a noble metal 12, which is applied in the illustrated case as an additional layer on the catalytically active coating 8.
  • a noble metal 12 which is applied in the illustrated case as an additional layer on the catalytically active coating 8.
  • Palladium or platinum is preferably used as the noble metal 12, but the use of ruthenium, rhodium, silver, osmium, iridium or gold could also be provided.
  • the noble metal 12 may be present as an oxide or as a pure element.
  • the support material 9 preferably consists of an amorphous or crystalline aluminosilicate, for example of a ⁇ -zeolite, a zeolite of the type Y or a zeolite of the type ZSM5.
  • This porous carrier material 9 having a very large surface area is modified with the iron-containing material 10 such that the iron-containing material 10 is finely distributed over at least approximately the entire surface of the carrier material 9.
  • a crystalline zeolite beta prove to be particularly suitable, especially because it does not decompose even after a long time in which it is exposed to the exhaust gas, and just with the iron-containing material 10 causes an extremely good effect of the catalytically active coating 8.
  • amorphous silicon oxide (SiO 2 ) for the carrier material 9, the framework structure of which may be, for example, of the MCM41 type.
  • the operation of the device 3 is as follows: On the particulate filter 4, the soot particles contained in the exhaust gas settle and reduce by the action of the catalytically active coating 8 contained in the exhaust NO 2 - and NO molecules to N 2 molecules, said at the same time oxidizes the carbon black essentially forming carbon to CO 2 .
  • the following reaction equations or at least one of them apply: 2NO + C -> N 2 + CO 2 respectively. 2NO 2 + 2C -> N 2 + 2CO 2
  • Fig. 1 is also shown that the device 3, an additional, commercially available oxidation catalyst 13, for example based on platinum and / or palladium, may be upstream, in order to produce from the present in the exhaust NO, the more reactive NO 2 .
  • Another object of the oxidation catalyst 13 may be to oxidize hydrocarbons and CO. Since just hydrocarbons could be stored in the zeolite, the danger of deactivation of the zeolite is avoided in this way.

Abstract

A device for purifying exhaust gases of an internal combustion engine has a particle filter, which is provided with a catalytically active coating. The catalytically active coating includes a supporting material and an iron-containing material, which is joined to the supporting material and is present on at least the surface of the same. The supporting material is an aluminosilicate or a silicon oxide.

Description

Die Erfindung betrifft eine Vorrichtung zur Reinigung von Abgasen einer Verbrennungskraftmaschine. Des weiteren betrifft die Erfindung eine Abgasanlage für eine Verbrennungskraftmaschine.The invention relates to a device for cleaning exhaust gases of an internal combustion engine. Furthermore, the invention relates to an exhaust system for an internal combustion engine.

Aus der DE 37 16 446 A1 ist ein katalytischer Dieselrußfilter bekannt, welcher eine katalytisch aktive Beschichtung aus metalldotiertem Zeolith aufweist. Vorzugsweise ist der Zeolith mit einem Metall der Gruppe IB, IIB, VB, VIB oder VIIB des Periodensystems oder einer Kombination derselben beladen, wobei vorzugsweise Nickel, Kupfer, Mangan, Vanadium, Silber oder eine Kombination derselben verwendet wird.From the DE 37 16 446 A1 For example, a catalytic diesel soot filter is known which comprises a catalytically active coating of metal-doped zeolite. Preferably, the zeolite is loaded with a Group IB, IIB, VB, VIB or VIIB metal of the Periodic Table or a combination thereof, preferably using nickel, copper, manganese, vanadium, silver or a combination thereof.

Problematisch bei diesem bekannten Filter ist jedoch, dass die gewünschte Wirkung erst dann einsetzt, wenn ein Reduktionsmittel zugegeben wird, was jedoch einen verhältnismäßig großen Aufwand darstellt. Ein weiterer Nachteil dieses bekannten Partikelfilters ist die Tatsache, dass in dem Abgas enthaltene NO-Moleküle erst oberhalb einer Temperatur von 400°C zu N2 umgesetzt werden, was entweder eine sehr motornahe Anordnung dieses Partikelfilters oder die Erzeugung von hohen Temperaturen in der Abgasleitung notwendig macht.The problem with this known filter, however, is that the desired effect only starts when a reducing agent is added, which, however, represents a relatively large expense. A further disadvantage of this known particle filter is the fact that NO molecules contained in the exhaust gas are converted to N 2 only above a temperature of 400 ° C., which necessitates either a very close-to-motor arrangement of this particle filter or the generation of high temperatures in the exhaust gas line power.

Die DE 37 31 889 A1 beschreibt einen Dieselruß-Partikelfilter, der ein Filterelement als Träger für einen unter Verwendung von mindestens einem Metalloxid hergestellten Katalysator aufweist. Der Träger besteht aus einem Keramik- oder Metallschaumkörper, dessen Porenflächen durchgängig mit einem oder mehreren Metalloxiden der Gruppen Ib, Vb, Vib, VIIb oder der Fe-Gruppe beschichtet sind. Auch dieser Partikelfilter weist jedoch noch keine zufriedenstellende Wirksamkeit hinsichtlich der NOx-Minderung auf.The DE 37 31 889 A1 describes a diesel particulate filter incorporating a filter element as a support for a catalyst prepared using at least one metal oxide having. The carrier consists of a ceramic or metal foam body, the pore surfaces are coated continuously with one or more metal oxides of groups Ib, Vb, Vib, VIIb or the Fe group. However, this particulate filter still has no satisfactory effectiveness in terms of NO x reduction.

Weiterhin ist aus der EP 0 600 442 A eine Vorrichtung zur Reinigung von Abgasen einer Verbrennungskraftmaschine bekannt, die einen Partikelfilter, der mit einer katalytisch aktiven Beschichtung versehen ist, umfasst. Die katalytisch aktive Beschichtung umfasst ein Trägermaterial und ein mit dem Trägermaterial verbundenes, zumindest an der Oberfläche desselben vorliegendes, eisenhaltiges Material, wobei das Trägermaterial beispielsweise ein Siliziumoxid (Silica) ist.Furthermore, from the EP 0 600 442 A a device for purifying exhaust gases of an internal combustion engine, which comprises a particle filter, which is provided with a catalytically active coating comprises. The catalytically active coating comprises a carrier material and an iron-containing material connected to the carrier material and present at least on the surface thereof, wherein the carrier material is, for example, a silicon oxide (silica).

Bei aus dem allgemeinen Stand der Technik bekannten Verfahren und Vorrichtungen zur Abgasreinigung ist häufig ein zusätzliches Reduktionsmittel, wie z. B. Harnstoff oder ein Kohlenwasserstoff, erforderlich, um die Umsetzung von NOx zu erzielen, was jedoch mit zusätzlichem Aufwand und höheren Kosten verbunden ist.In known from the general state of the art methods and apparatus for exhaust gas purification is often an additional reducing agent, such. As urea or a hydrocarbon, required to achieve the implementation of NO x , which is associated with additional effort and higher costs.

Es ist daher Aufgabe der vorliegenden Erfindung, eine Vorrichtung zur Reinigung von Abgasen einer Verbrennungskraftmaschine zu schaffen, welche auch bei verhältnismäßig niedrigen Temperaturen eine sehr gute Reinigungswirkung zeigt und bei welcher auf ein zusätzliches Reduktionsmittel verzichtet werden kann.It is therefore an object of the present invention to provide an apparatus for purifying exhaust gases of an internal combustion engine, which shows a very good cleaning effect even at relatively low temperatures and in which can be dispensed with an additional reducing agent.

Erfindungsgemäß wird diese Aufgabe durch die in Anspruch 1 genannten Merkmale gelöst.According to the invention, this object is achieved by the features mentioned in claim 1.

Es wurde überraschenderweise festgestellt, dass ein mit dem Trägermaterial verbundenes, an der Oberfläche desselben vorliegendes, eisenhaltiges Material als katalytisch aktive Substanz eine bezüglich der Umsetzung der Abgase sehr gute Wirkung besitzt. So konnte festgestellt werden, dass durch die erfindungsgemäße Zusammensetzung der katalytisch aktiven Beschichtung Stickstoffoxide zur Reaktion mit den im Abgas vorhandenen Rußpartikeln angeregt werden, wobei bereits bei Temperaturen von ca. 220°C eine Reduzierung von NOx zu N2, also eine Stickstoffbildung, festgestellt wurde und in dem die Vorrichtung verlassenden Abgas annähernd keine schädlichen NO-Moleküle mehr enthalten sind, wobei auf ein zusätzliches Reduktionsmittel verzichtet werden kann.It has surprisingly been found that an iron-containing material, which is bonded to the support material and is present on the surface thereof, is very active as a catalytically active substance with respect to the conversion of the exhaust gases has good effect. It could thus be stated that, due to the composition according to the invention of the catalytically active coating, nitrogen oxides react with those in the exhaust gas Existing soot particles are excited, wherein even at temperatures of about 220 ° C, a reduction of NO x to N 2 , ie a nitrogen formation, has been found and in the exhaust gas leaving the device are almost no harmful NO molecules contained more, with a additional reducing agent can be dispensed with.

Dabei werden die in dem Abgas enthaltenen Rußpartikel in an sich bekannter Weise an dem Partikelfilter festgehalten und so daran gehindert, die Abgasleitung, in der die erfindungsgemäße Vorrichtung vorzugsweise eingebaut ist, zu verlassen. Gleichzeitig dienen die an den Poren des Partikelfilters festgehaltenen Rußpartikel zu der oben beschriebenen Reduktion der Stickstoffoxide, sodass sich die Rußmenge weitaus weniger stark erhöht als bei bekannten Partikelfiltern und dementsprechend erheblich seltener eine Regeneration desselben erforderlich ist. Vorteilhafterweise bewirkt die katalytische Beschichtung mit dem eisenhaltigen Material zusätzlich zu der Auslösung dieser Reaktionen auch eine Verringerung der Zündtemperatur des Rußes.In this case, the soot particles contained in the exhaust gas are held in a conventional manner to the particulate filter and thus prevented from leaving the exhaust pipe in which the device according to the invention is preferably installed. At the same time, the soot particles retained on the pores of the particulate filter serve to reduce the nitrogen oxides as described above, so that the amount of soot increases far less than with known particulate filters and, correspondingly, less frequently regeneration is required. Advantageously, the catalytic coating with the iron-containing material also causes a reduction in the ignition temperature of the soot in addition to the triggering of these reactions.

Es ergaben sich hierbei folgende Reaktionsgleichungen:

        2NO + C -> N2 + CO2

        bzw.

        2NO2 + 2C -> N2 + 2CO2

The following reaction equations resulted:

2NO + C -> N 2 + CO 2

respectively.

2NO 2 + 2C -> N 2 + 2CO 2

Besonders hervorzuheben ist der Effekt der simultanen Stickstoffoxid-Reduktion und der Ruß-Oxidation im Abgas der Verbrennungskraftmaschine, der eine besonders gute Reinigung des Abgases zur Folge hat und somit die Einhaltung verschärfter Abgasgrenzwerte erlaubt.Particularly noteworthy is the effect of the simultaneous reduction of nitrogen oxides and soot oxidation in the exhaust gas of the internal combustion engine, which is a particularly good cleaning of the exhaust gas and thus allows the compliance with more stringent exhaust emission limits.

Dadurch, dass das Trägermaterial ein Alumosilikat oder ein Siliziumoxid ist, wird eine sehr feine Verteilung des an der Oberfläche des Trägermaterials vorliegenden eisenhaltigen Materials erreicht, wodurch eine erhebliche Steigerung der Reaktivität erreicht wird.The fact that the support material is an aluminosilicate or a silicon oxide, a very fine distribution of the present at the surface of the support material iron-containing material is achieved, whereby a significant increase in reactivity is achieved.

Besonders gute Ergebnisse hinsichtlich der Ruß-NOx-Umsetzung können erzielt werden, wenn als Trägermaterial ein Zeolith verwendet wird.Particularly good results with regard to the soot NO x conversion can be achieved if a zeolite is used as support material.

Alternativ kann jedoch auch ein Siliziumoxid als Trägermaterial eingesetzt werden, dessen Gerüststruktur vom Typ MCM41 oder MCM48 ist. Auch hiermit wurden gute Ergebnisse hinsichtlich der Ruß-NOx-Umsetzung erreicht.Alternatively, however, it is also possible to use a silicon oxide as support material whose framework structure is of the MCM41 or MCM48 type. Again, good results have been achieved in terms of soot NO x conversion.

Als bezüglich der katalytischen Reaktionen besonders vorteilhaft hat es sich herausgestellt, wenn das eisenhaltige Material Eisenoxid aufweist. Eisenoxid ist ein sehr guter Oxidationskatalysator für Ruß und ist vorteilhafterweise nicht toxisch.As with respect to the catalytic reactions, it has been found particularly advantageous if the iron-containing material has iron oxide. Iron oxide is a very good oxidation catalyst for carbon black and is advantageously nontoxic.

Hierbei kann es besonders vorteilhaft sein, wenn das eisenhaltige Material zu 100 % aus Eisenoxid besteht.It may be particularly advantageous if the iron-containing material consists of 100% iron oxide.

Alternativ ist auch eine gute Reinigungswirkung zu erwarten, wenn das eisenhaltige Material Reineisen aufweist.Alternatively, a good cleaning effect is to be expected if the iron-containing material has pure iron.

Analog ist auch hier denkbar, dass das eisenhaltige Material zu 100 % aus Reineisen besteht.Analogously, it is also conceivable here that the iron-containing material consists of 100% pure iron.

Eine verbesserte Reaktion der Abgasbestandteile und somit eine besonders gute Reinigungswirkung konnte beobachtet werden, wenn die katalytisch aktive Beschichtung ein Edelmetall aufweist.An improved reaction of the exhaust components and thus a particularly good cleaning effect could be observed if the catalytically active coating comprises a noble metal.

Als besonders wirkungsvoll haben sich dabei die Edelmetalle Platin und insbesondere Palladium herausgestellt.The precious metals platinum and in particular palladium have proved to be particularly effective.

Eine Abgasanlage für eine Verbrennungskraftmaschine mit einer erfindungsgemäßen Vorrichtung zur Reinigung von Abgasen ist in Anspruch 16 angegeben.An exhaust system for an internal combustion engine with an inventive device for purifying exhaust gases is specified in claim 16.

Weitere vorteilhafte Ausgestaltungen und Weiterbildungen der Erfindung ergeben sich aus den restlichen Unteransprüchen. Nachfolgend ist ein Ausführungsbeispiel der Erfindung anhand der Zeichnung prinzipmäßig dargestellt.Further advantageous embodiments and modifications of the invention will become apparent from the remaining dependent claims. Hereinafter, an embodiment of the invention with reference to the drawing is shown in principle.

Es zeigt:

Fig. 1
eine Verbrennungskraftmaschine mit einer Abgasleitung, in der eine erfindungsgemäße Vorrichtung zur Reinigung der Abgas der Verbrennungskraftmaschine angeordnet ist; und
Fig. 2
eine schematische Darstellung des Schichtaufbaus einer bevorzugten Ausführungsform der Erfindung.
It shows:
Fig. 1
an internal combustion engine with an exhaust pipe in which a device according to the invention for cleaning the exhaust gas of the internal combustion engine is arranged; and
Fig. 2
a schematic representation of the layer structure of a preferred embodiment of the invention.

Eine Verbrennungskraftmaschine 1 ist mit einer Abgasanlage 2 versehen, die eine Abgasleitung 2a aufweist, durch die in der Verbrennungskraftmaschine 1 in an sich bekannter Weise produzierte Abgase abgeführt werden. In der Abgasleitung 2a ist eine Vorrichtung 3 zur Reinigung der Abgase der Verbrennungskraftmaschine 1 angeordnet, welche nachfolgend ausführlicher beschrieben wird. Bei der Verbrennungskraftmaschine 1 handelt es sich vorzugsweise um eine nach dem Dieselprinzip arbeitende Verbrennungskraftmaschine, in deren Abgas neben anderen Schadstoffen Rußpartikel enthalten sind.An internal combustion engine 1 is provided with an exhaust system 2, which has an exhaust pipe 2a, are discharged through the produced in the internal combustion engine 1 in a conventional manner exhaust gases. In the exhaust pipe 2a, a device 3 for cleaning the exhaust gases of the internal combustion engine 1 is arranged, which will be described in more detail below. The internal combustion engine 1 is preferably an internal combustion engine operating on the diesel principle, in the exhaust of which, in addition to other pollutants, soot particles are contained.

Die Vorrichtung 3 weist einen stark schematisiert dargestellten Partikelfilter 4 auf, der vorzugsweise aus Keramik, wie z.B. Siliziumkarbid, besteht, der jedoch auch aus Aluminiumoxid oder einem anderen geeigneten Material bestehen kann. Der Partikelfilter 4 seinerseits weist mehrere Einlasskanäle 5 und Auslasskanäle 6 auf, die wechselseitig verschlossen sind. Es handelt sich demnach um ein wechselseitiges Kanalsystem. Alternativ wäre auch ein offenes System mit jedweder Kanalform und -geometrie möglich. Die Einlasskanäle 5 und die Auslasskanäle 6 sind durch jeweilige, mittels gestrichelter Linien angedeutete Wandungen 7 voneinander getrennt, sodass die Abgase die Wandungen 7 durchströmen müssen, um von den Einlasskanälen 5 in die Auslasskanäle 6 zu gelangen und auf diese Weise den Partikelfilter 4 zu verlassen. Hierzu ist das Material der Wandungen 7 des Partikelfilters 4 in an sich bekannter Weise porös ausgebildet, so dass die gasförmigen Abgasbestandteile die Wandungen 7 durchströmen können, die Rußpartikel jedoch an denselben verbleiben bzw. abgeschieden werden.The device 3 has a particle filter 4 shown in a highly schematic manner, which preferably consists of ceramic, such as silicon carbide, but which may also consist of aluminum oxide or another suitable material. The particle filter 4 in turn has a plurality of inlet channels 5 and outlet channels 6, which are mutually closed. It is therefore a reciprocal channel system. Alternatively, an open system with any channel shape and geometry would be possible. The inlet channels 5 and the outlet channels 6 are separated from one another by respective walls 7 indicated by dashed lines, so that the exhaust gases have to flow through the walls 7 in order to pass from the inlet channels 5 into the outlet channels 6 and in this way leave the particle filter 4. For this purpose, the material of the walls 7 of the particulate filter 4 is formed in a manner known per se porous, so that the gaseous exhaust gas constituents can flow through the walls 7, the soot particles, however, remain at the same or are deposited.

Wie in der schematischen Darstellung gemäß Fig. 2 erkennbar ist, ist der Partikelfilter 4 bzw. die denselben bildenden Wandungen 7 mit einer katalytisch aktiven Beschichtung 8 versehen, welche ein Trägermaterial 9 und ein mit dem Trägermaterial 9 verbundenes, an der Oberfläche desselben vorliegendes, eisenhaltiges Material 10 aufweist. Das Trägermaterial 9 der katalytisch aktiven Beschichtung 8 ist mittels eines Bindemittels 11 aus ceroxid mit dem Partikelfilter 4 verbunden.As in the schematic representation according to Fig. 2 can be seen, the particulate filter 4 and the same forming walls 7 is provided with a catalytically active coating 8, which has a carrier material 9 and connected to the substrate 9, the same on the surface thereof, iron-containing material 10. The carrier material 9 of the catalytically active coating 8 is connected to the particle filter 4 by means of a binding agent 11 made of cerium oxide.

Zur Verbindung der katalytisch aktiven Beschichtung 8 mit dem Partikelfilter 4 über das Bindemittel 11 können an sich bekannte und daher nachfolgend nicht näher erläuterte Verfahren zur Anwendung kommen.For the connection of the catalytically active coating 8 with the particle filter 4 via the binder 11, known processes, which are therefore not explained in detail below, can be used.

Die in Fig. 2 dargestellten Schichtdicken sind selbstverständlich als rein beispielhaft anzusehen.In the Fig. 2 Of course, layer thicknesses shown are to be regarded as purely exemplary.

Das eisenhaltige Material 10 kann in einer Ausführungsform der Vorrichtung 3 Eisenoxid aufweisen, es ist in diesem Zusammenhang auch möglich, dass das eisenhaltige Material 10 zu 100 % aus Eisenoxid besteht. Alternativ ist es ebenfalls möglich, dass das eisenhaltige Material 10 Reineisen aufweist bzw. zu 100 % aus Reineisen besteht. Des weiteren ist auch eine Mischung aus Eisenoxid und Reineisen zur Bildung des eisenhaltigen Materials 10 möglich. Zusätzlich können Titan, Vanadium, Chrom, Mangan, Kobalt, Nickel, Kupfer, Zink, Zirkonium, Niob, Wolfram und/oder Rhenium in dem eisenhaltigen Material 10 enthalten sein, wobei Eisenoxid oder Reineisen stets den größten Bestandteil des eisenhaltigen Materials 10 stellen.The iron-containing material 10 may in one embodiment of the device 3 comprise iron oxide, it is also possible in this context that the iron-containing material 10 consists of 100% iron oxide. Alternatively, it is also possible that the iron-containing material 10 has pure iron or consists of 100% pure iron. Furthermore, a mixture of iron oxide and pure iron to form the iron-containing material 10 is possible. In addition, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, Zinc, zirconium, niobium, tungsten and / or rhenium be included in the ferrous material 10, with iron oxide or pure iron always make the largest part of the iron-containing material 10.

Zur Verbindung des eisenhaltigen Materials 7 mit dem Trägermaterial 9 kann das an sich bekannte Ionenaustauschverfahren eingesetzt werden, es ist jedoch auch möglich, das Trägermaterial 9 mit dem eisenhaltigen Material 10 mittels eines Beschichtungsverfahrens zu verbinden.To connect the iron-containing material 7 with the carrier material 9, the known ion exchange method can be used, but it is also possible to connect the carrier material 9 with the iron-containing material 10 by means of a coating method.

Im vorliegenden Fall weist die katalytisch aktive Beschichtung 8 zusätzlich zu dem Trägermaterial 9 und dem eisenhaltigen Material 10 ein Edelmetall 12 auf, welches im dargestellten Fall als zusätzliche Schicht auf die katalytisch aktive Beschichtung 8 aufgebracht ist. In nicht dargestellter Weise ist es auch möglich, das Edelmetall 12 in der katalytisch aktiven Beschichtung 8 zu verteilen. Als Edelmetall 12 wird vorzugsweise Palladium oder Platin verwendet, es könnte jedoch auch die Verwendung von Ruthenium, Rhodium, Silber, Osmium, Iridium oder Gold vorgesehen sein. Das Edelmetall 12 kann als Oxid oder als reines Element vorhanden sein.In the present case, the catalytically active coating 8 in addition to the carrier material 9 and the iron-containing material 10, a noble metal 12, which is applied in the illustrated case as an additional layer on the catalytically active coating 8. In a manner not shown, it is also possible to distribute the precious metal 12 in the catalytically active coating 8. Palladium or platinum is preferably used as the noble metal 12, but the use of ruthenium, rhodium, silver, osmium, iridium or gold could also be provided. The noble metal 12 may be present as an oxide or as a pure element.

Das Trägermaterial 9 besteht vorzugsweise aus einem amorphen oder kristallinen Alumosilikat, beispielsweise aus einem β-Zeolith, einem Zeolith des Typs Y oder einem Zeolith des Typs ZSM5. Dieses poröse, eine sehr große Oberfläche aufweisende Trägermaterial 9 ist mit dem eisenhaltigen Material 10 modifiziert, sodass das eisenhaltige Material 10 über wenigstens annähernd der gesamten Oberfläche des Trägermaterials 9 fein verteilt ist. In der Praxis hat sich ein kristalliner β-Zeolith als besonders geeignet erweisen, insbesondere weil er sich auch nach längerer Zeit, in der er dem Abgas ausgesetzt ist, nicht zersetzt und gerade mit dem eisenhaltigen Material 10 eine äußerst gute Wirkung der katalytisch aktiven Beschichtung 8 hervorruft. Alternativ wäre es auch möglich, für das Trägermaterial 9 amorphes Siliziumoxid (SiO2) zu verwenden, wobei dessen Gerüststruktur beispielsweise vom Typ MCM41 sein kann.The support material 9 preferably consists of an amorphous or crystalline aluminosilicate, for example of a β-zeolite, a zeolite of the type Y or a zeolite of the type ZSM5. This porous carrier material 9 having a very large surface area is modified with the iron-containing material 10 such that the iron-containing material 10 is finely distributed over at least approximately the entire surface of the carrier material 9. In practice, a crystalline zeolite beta prove to be particularly suitable, especially because it does not decompose even after a long time in which it is exposed to the exhaust gas, and just with the iron-containing material 10 causes an extremely good effect of the catalytically active coating 8. Alternatively, it would also be possible to use amorphous silicon oxide (SiO 2 ) for the carrier material 9, the framework structure of which may be, for example, of the MCM41 type.

Die Wirkungsweise der Vorrichtung 3 ist folgendermaßen: An dem Partikelfilter 4 setzen sich die in dem Abgas enthaltenen Rußpartikel ab und reduzieren durch die Einwirkung der katalytisch aktiven Beschichtung 8 die in dem Abgas enthaltenen NO2- und NO-Moleküle zu N2-Molekülen, wobei zugleich der die Rußpartikel im wesentlichen bildende Kohlenstoff zu CO2 oxidiert. Es gelten dabei nachfolgende Reaktionsgleichungen bzw. zumindest eine derselben:

        2NO + C -> N2 + CO2

        bzw.

        2NO2 + 2C -> N2 + 2CO2

The operation of the device 3 is as follows: On the particulate filter 4, the soot particles contained in the exhaust gas settle and reduce by the action of the catalytically active coating 8 contained in the exhaust NO 2 - and NO molecules to N 2 molecules, said at the same time oxidizes the carbon black essentially forming carbon to CO 2 . The following reaction equations or at least one of them apply:

2NO + C -> N 2 + CO 2

respectively.

2NO 2 + 2C -> N 2 + 2CO 2

Dies bedeutet, dass in dem die Vorrichtung 3 verlassenden Abgas nur noch eine erheblich verringerte Menge an NOx-Molekülen und im wesentlichen nur N2-Moleküle enthalten sind, und dass gleichzeitig die Rußpartikel an dem Partikelfilter 4 abgeschieden und danach durch NO und NO2 oxidiert werden. Durch die Einwirkung des eisenhaltigen Materials 7 in der katalytisch aktiven Beschichtung 8 laufen die beschriebenen Reaktionen bereits bei Temperaturen von ca. 220°C ab, so dass es nicht erforderlich ist, die Vorrichtung 3 besonders nah an der Verbrennungskraftmaschine 1 anzuordnen oder zusätzliche Reduktionsmittel in die Abgasleitung 2a einzuleiten. Es ist somit möglich, mittels einer einzigen Vorrichtung 3 die beiden Schadstoffe NOx und Ruß aus dem Abgas der Verbrennungskraftmaschine 1 zu entfernen.This means that in the exhaust gas leaving the device 3 only a significantly reduced amount of NO x molecules and substantially only N 2 molecules are contained, and that at the same time the soot particles deposited on the particulate filter 4 and then by NO and NO 2 be oxidized. Due to the action of the iron-containing material 7 in the catalytically active coating 8, the reactions described already proceed at temperatures of about 220 ° C., so that it is not necessary that the device 3 be particularly to arrange close to the internal combustion engine 1 or to introduce additional reducing agent in the exhaust pipe 2a. It is thus possible to remove the two pollutants NO x and soot from the exhaust gas of the internal combustion engine 1 by means of a single device 3.

In Fig. 1 ist außerdem dargestellt, dass der Vorrichtung 3 ein zusätzlicher, kommerziell erhältlicher Oxidationskatalysator 13, beispielsweise auf Basis von Platin und/oder Palladium, vorgeschaltet sein kann, um aus dem in dem Abgas vorhandenen NO das reaktivere NO2 zu erzeugen. Eine weitere Aufgabe des Oxidationskatalysators 13 kann darin bestehen, Kohlenwasserstoffe und CO zu oxidieren. Da gerade Kohlenwasserstoffe in dem Zeolith eingespeichert werden könnten, wird auf diese Weise die Gefahr der Deaktivierung des Zeoliths vermieden. In Fig. 1 is also shown that the device 3, an additional, commercially available oxidation catalyst 13, for example based on platinum and / or palladium, may be upstream, in order to produce from the present in the exhaust NO, the more reactive NO 2 . Another object of the oxidation catalyst 13 may be to oxidize hydrocarbons and CO. Since just hydrocarbons could be stored in the zeolite, the danger of deactivation of the zeolite is avoided in this way.

Claims (17)

  1. Device (3) for the purification of exhaust gases of an internal combustion engine (1), having a particle filter (4) which is provided with a catalytically active coating (8), with the catalytically active coating (8) having a substrate material (9) and an iron-containing material (10) which is connected to the substrate material (9) and which is present at least on the surface of the latter, with the substrate material (9) being an aluminosilicate or a silicon oxide, characterized in that the substrate material (9) is connected to the particle filter (4) by means of a binding agent (11), with the binding agent being cerium oxide.
  2. Device according to Claim 1,
    characterized in that
    the substrate material (9) is a zeolite.
  3. Device according to Claim 1,
    characterized in that
    the substrate material (9) is a silicon oxide whose framework structure is of type MCM41 or MCM48.
  4. Device according to Claim 1, 2 or 3,
    characterized in that
    the iron-containing material (10) has iron oxide.
  5. Device according to Claim 4,
    characterized in that
    the iron-containing material (10) is 100% iron oxide.
  6. Device according to Claim 1, 2 or 3,
    characterized in that
    the iron-containing material (10) has pure iron.
  7. Device according to Claim 6,
    characterized in that
    the iron-containing material (10) is 100% pure iron.
  8. Device according to one of Claims 1 to 7,
    characterized in that
    the iron-containing material (10) is connected by means of a coating to the substrate material (9).
  9. Device according to one of Claims 1 to 7,
    characterized in that
    the iron-containing material (10) is applied to the substrate material (9) by means of ion exchange.
  10. Device according to one of Claims 1 to 9,
    characterized in that
    the catalytically active coating (8) has a noble metal (12).
  11. Device according to Claim 10,
    characterized in that
    the noble metal (12) is applied as an additional layer to the catalytically active coating (8).
  12. Device according to Claim 10,
    characterized in that
    the noble metal (12) is dispersed in the catalytically active coating (8).
  13. Device according to Claim 10, 11 or 12,
    characterized in that
    the noble metal (12) is platinum or palladium.
  14. Device according to one of Claims 2 or 4 to 11,
    characterized in that
    the zeolite (9) is a β-zeolite.
  15. Device according to one of Claims 1 to 14,
    characterized in that the particle filter (4) is composed of ceramic or of metal, with an alternating duct system or an open system.
  16. Exhaust system (2) for an internal combustion engine (1), having an exhaust line (2a) and having a device (3) for the purification of exhaust gases, which is arranged in the exhaust line (2a), according to one of Claims 1 to 15.
  17. Exhaust system according to Claim 16,
    characterized in that an oxidation catalytic converter (13) is positioned upstream of the device (3).
EP05767079A 2004-06-11 2005-06-09 Apparatus for purifying exhaust gases of an internal combustion engine Not-in-force EP1759097B1 (en)

Applications Claiming Priority (2)

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DE102004028276A DE102004028276B4 (en) 2004-06-11 2004-06-11 Device for cleaning exhaust gases of an internal combustion engine
PCT/EP2005/006219 WO2005121514A1 (en) 2004-06-11 2005-06-09 Apparatus for purifying exhaust gases of an internal combustion engine

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EP1759097B1 true EP1759097B1 (en) 2008-10-15

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CN (1) CN101184909B (en)
AT (1) ATE411450T1 (en)
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DE102004028276B4 (en) 2008-08-21
DE502005005700D1 (en) 2008-11-27
ATE411450T1 (en) 2008-10-15
DE102004028276A1 (en) 2006-01-05
WO2005121514A1 (en) 2005-12-22
CN101184909B (en) 2010-06-23
EP1759097A1 (en) 2007-03-07
CN101184909A (en) 2008-05-21
ES2312002T3 (en) 2009-02-16

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