Patent Application
20130202507
The present invention relates to a method for the treatment of an exhaust gas and to exhaust gas treatment systems. The present invention further relates to the use of a catalytic converter having oxygen storage capacity for prolonging the rich phase of an exhaust gas treatment system.
During the combustion of fuels in internal combustion engines, an exhaust gas is developed which contains unburned hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx) and particles as pollutants. Exhaust gas catalysts for the simultaneous conversion of hydrocarbons, carbon monoxide and nitrogen oxides, so-called three-way catalysts, require a stoichiometric composition of exhaust gas, with an oxygen concentration of about 0.7 vol-.%, for the reaction to take place. The exhaust gas composition is usually described by the normalized air to fuel ratio λ, which is defined as the air/fuel ratio normalized to stoichiometric conditions. The air/fuel ratio states how many kilograms of air are required for complete combustion of one kilogram of fuel. With conventional fuels, the stoichiometric air/fuel ratio has a value of 14.6, which corresponds to a normalized air/fuel ratio λ of 1.
In lean-mix engines, such as diesel engines and lean-burning gasoline engines, which are generally operated at a normalized air to fuel ratio λ higher than 1, removal of the nitrogen oxides and particles causes special difficulties. Due to the high oxygen concentration in the exhaust gas from these engines, which can be up to 15 vol.-%, the nitrogen oxides (NOx) contained in the exhaust gas cannot readily be reacted with the hydrocarbons (HC) and carbon monoxide (CO) on a conventional exhaust gas catalyst, because in this case the reducing components (HC and CO and also small amounts of hydrogen H2) are oxidized directly by oxygen.
In order to convert the nitrogen oxides developed during combustion, two different catalytic methods have proven to be successful in the past: on the one hand, there is the NOx adsorber technology in which, during lean operating states of the engine, the nitrogen oxides are adsorbed on a so-called NOx storage catalyst and, during rich operating states, are re-desorbed and reduced; and on the other hand, the selective catalytic reduction (SCR) technology in which the nitrogen oxides contained in the oxygen-rich exhaust gas are reduced selectively to nitrogen and water using ammonia (NH3) or a corresponding precursor substance convertible into ammonia.
In the NOx adsorber technology, the nitrogen oxides are stored in the form of nitrates during lean-mix operation of the internal combustion engine, with the aid of so-called nitrogen oxide storage catalysts, for example, alkaline earth metal oxides, in particular barium oxide. For storage purposes, the nitrogen oxides, between 50 and 90 vol. % of which consists of nitrogen monoxide depending on the type of engine and mode of operation of the engine, first have to be oxidized to nitrogen dioxide before they can form nitrates with the storage materials. Oxidation takes place mainly on the storage catalyst itself and this is provided, for example, with platinum as a catalytically active component.
Depending on the driving conditions, the storage material has to be regenerated at certain intervals. To this end, the internal combustion engines can be operated for brief periods with rich air/fuel mixtures. Under the reducing exhaust gas conditions which then prevail, the nitrates are decomposed and the nitrogen oxides being released are converted into nitrogen, with simultaneous oxidation of the reducing components. The acceleration phases may sometimes be used for regeneration of the storage material. However, in the absence of acceleration phases, targeted regeneration is required and this has to be achieved by appropriate regulation of the engine. The fuel required for this reduces the theoretical fuel saving when using lean-mix engines.
Current storage catalysts still exhibit high sensitivity towards sulfur oxides contained in the exhaust gas from internal combustion engines. Sulfur oxides, after oxidation to sulfur trioxide on the storage catalyst, react with the storage material to form stable sulfates which are thermally very stable and continuously reduce the storage capacity for nitrogen oxides.
The SCR technology involves the reduction of NOx by ammonia over a SCR catalyst that is typically composed of base metals. This reaction can take place even in an oxidizing environment. SCR can achieve NOx reduction in excess of 90%. However, one of the major disadvantages of this technology is the need for an on-board reservoir for ammonia or a suitable precursor thereof, such as urea. Further, there is concern over the lack of infrastructure for distributing ammonia or the precursor and over the possible release of ammonia into the environment. A further difficulty using this type of exhaust gas treatment is that both the hydrolysis of urea and the SCR reaction using the common SCR catalysts shows insufficient reaction rates at temperatures below 150° C. Typically the light-off temperature under the chosen conditions is above 150° C. As used herein, the light-off temperature of a catalyst refers to the temperature upstream of the catalyst at which the catalyst converts the pollutant in question (here the nitrogen oxides) just at a 50% rate.
Lean-mix operated gasoline engines, and in particular diesel engines, often achieve exhaust gas temperatures of less than 350° C. when operating under part loads. Therefore catalysts are required which develop their maximum rates of conversion at the lowest possible exhaust gas temperatures of less than 350° C., preferably less than 300° C.
Both the NOx adsorber technology and the SCR technology often provide only low conversion rates at temperatures below 250° C. In an attempt to increase the conversion rates at low temperatures, catalyst systems have been developed containing an upstream NOx storage catalytic converter and a downstream SCR catalytic converter. In these systems, nitrogen oxides are stored on the NOx storage catalytic converter during lean operation phases (λ>1). During short rich operation phases (λ<1), the nitrogen oxides are reduced to nitrogen, but partially also to ammonia, i.e. ammonia is produced “on-board”. The downstream SCR catalytic converter captures ammonia produced by the NOx storage catalytic converter during rich operation phases. During the subsequent lean operation phase, the ammonia stored on the SCR catalytic converter can contribute to the overall NOx conversion.
For example, US 2004/0076565 describes an emission control system for controlling NOx and NH3 emissions from an exhaust stream. The system comprises a lean NOx trap in communication with the exhaust stream for reducing NOx emissions; and a NH3—SCR catalyst in communication with the exhaust stream for adsorbing NH3, wherein the NH3 adsorbed by the NH3—SCR catalyst reacts with NOx in the exhaust stream to improve the reduction of NOx and NH3. WO 2005/047663 relates to an emissions treatment system for an exhaust stream, comprising a certain NOx storage reduction catalyst and a certain SCR catalyst disposed downstream of the NOx storage reduction catalyst. US-A-2006/0010857 describes further exhaust treatment systems having a SCR reactor downstream of a NOx adsorber. In one embodiment, syn gas from a fuel reformer is used to regenerate the NOx adsorber. In another embodiment, an additional ammonia source is included. US-A-2006/0153761 discloses a specific exhaust gas aftertreatment installment utilizing a nitrogen oxide storage catalytic converter, a SCR catalytic converter and a particulate filter upstream of the nitrogen oxide storage catalytic converter or between the latter and the SCR catalytic converter or downstream of the SCR catalytic converter. US-A-2006/0010859 relates to an exhaust aftertreatment system comprising two or more branches, at least one of which contains a NOx adsorber-catalyst. The branches unite downstrem into a trailing conduit that contains an ammonia-SCR catalyst. U.S. Pat. No. 7,043,902 discloses an exhaust gas purification system equipped, from an upstream side toward downstream side through which an exhaust gas flows, with a plasma reactor and a catalyst unit charged with a catalyst acting on NOx in the exhaust gas in this order, and equipped with a reducing agent supplying device to supply a reducing agent at an upstream side of the plasma reactior, wherein the catalyst has a NO2 adsorptive catalyst layer and a NO2 selective reduction catalyst layer contacting the NO2 adsorptive catalyst layer.
U.S. Pat. No. 7,178,331 relates to a certain exhaust system for a lean-burn internal combustion engine comprising a nitrogen oxide absorbent, a catalyst for catalyzing the selective catalytic reduction of NOx with a NOx specific reactant, first means for introducing a NOx specific reactant or a precursor thereof into an exhaust gas upstream of the SCR catalyst and, means for controlling the introduction of the NOx-specific reactant or precursor thereof into the exhaust gas via the first introducing means, wherein the SCR catalyst is disposed upstream of the NOx absorbent.)
While the above systems provide some improvements as compared to the use of the NOx adsorber technology or the SCR technology alone, still further improvements in exhaust gas treatment systems are desired.
An object of the present invention is to provide a method of the treatment of exhaust gas with an improved conversion rate of the nitrogen oxides at low exhaust gas temperatures as compared to the prior art. Moreover, the invention is to provide an exhaust gas treatment system which has improved activity for the conversion of nitrogen oxides at low exhaust gas temperatures. In particular, it is an object of the present invention to improve the conversion rate of the nitrogen oxides at low exhaust gas temperatures without affecting an undesirable increase in hydrocarbon and carbon monoxide as well as ammonia emissions.
The present inventors surprisingly found that these objects can be achieved by the method and the exhaust gas treatment system of the present invention. Accordingly, in a first aspect the present invention relates to a method for the treatment of an exhaust gas comprising NOx, wherein the method comprises the step of subjecting the exhaust gas to an exhaust gas treatment system comprising, in order of the exhaust stream:
The present invention further relates to exhaust gas treatment systems that can suitably be employed in the present method. In particular, in a second aspect the present invention relates to an exhaust gas treatment system comprising, in order of the exhaust stream:
In a third aspect the present invention relates to an exhaust gas treatment system comprising, in order of the exhaust stream:
In a fourth aspect, the present invention relates to an exhaust gas treatment system comprising, in order of the exhaust stream:
The present invention further relates in a fifth aspect to the use of a catalytic converter having oxygen storage capacity for prolonging the rich phase of an exhaust gas treatment system operated in alternating rich and lean phases, the exhaust gas treatment system comprising, in order of the exhaust stream:
As compared to the prior art exhaust gas treatment systems described above which comprise a NOx storage catalytic converter and a downstream SCR catalytic converter, the present method and exhaust gas treatment systems are advantageous in that a higher NOx conversion can be achieved at lower temperatures; while an increase in HC/CO emissions can be avoided.
Without wishing to be bound by theory, the advantageous properties achieved by the present invention may be explained as follows. The prior art exhaust gas treatment systems are often controlled by terminating the lean phase at a point when the NOx breakthrough downstream of the first NOx storage catalytic converter or downstream of the SCR catalyst increases. Conversely, the rich phase is terminated at a point when reductant breakthrough increases. Ammonia is formed on the NOx storage catalytic converter. However, ammonia leaves the NOx storage catalytic converter at about the same time as the breakthrough of reductant occurs. Hence, even though some ammonia may be stored on the downstream SCR catalytic converter, reductant breakthrough occurs relatively fast, leading to termination of the rich phase before larger amounts of ammonia can leave the NOx storage catalytic converter and be stored on the downstream SCR catalytic converter. In particular, zeolite-containing SCR catalytic converters typically have low oxygen storage capacities and a low conversion rate for the oxidation of hydrocarbons and carbon monoxide.
It has now been found that in prior art exhaust gas treatment systems comprising a NOx storage catalytic converter and a downstream SCR catalytic converter termination of the rich phase often occurs at an earlier stage than would be desirable for an optimal NOx conversion. It has now been found that by supplying a larger amount of reducing components by e.g. prolonging the rich phase or applying lower air/fuel ratios, larger amounts of ammonia are formed on the NOx storage catalytic converter. Undesirable emissions of carbon monoxide and hydrocarbons that may be associated with the supply of a larger amount of reducing components can, for example, be avoided by adding a catalytic converter having oxygen storage capacity downstream of the SCR catalytic converter.
In the present method, the exhaust gas treatment system is operated in alternating rich and lean phases, i.e. the exhaust gas entering the exhaust gas treatment system alters between rich air/fuel ratios and lean air/fuel ratios. The exhaust gas composition can be altered from a lean to a rich air/fuel ratio, for example, by fuel injection into the exhaust pipe or by suitable engine control.
The lean phase can be terminated when nitrogen oxides start leaving the downstream catalytic converter having oxygen storage capacity. This point can, for example, be determined by an engine control unit which is modelling the NOx-loading of the NOx storage catalytic converter online or by direct measurement of the NOx breakthrough with e.g. a NOx-sensor.
The rich phase is terminated when the amount of reducing components leaving the first NOx storage catalytic converter is at least 0.05 times the amount of reducing components consumed by the first NOx storage catalytic converter during the time interval beginning when the air/fuel ratio upstream of the first NOx storage catalytic converter turns from lean to rich conditions and ending when the air/fuel ratio downstream of the NOx storage catalyst turns from lean to rich conditions. Alternatively, the rich phase is terminated when the amount of reducing components leaving the first NOx storage catalytic converter is at least 0.1 times or at least 0.2 times or at least 0.5 times the amount of reducing components consumed by the first NOx storage catalytic converter during the time interval beginning when the air/fuel ratio upstream of the first NOx storage catalytic converter turns from lean to rich conditions and ending when the air/fuel ratio downstream of the NOx storage catalyst turns from lean to rich conditions. The rich phase is terminated at the latest when the air/fuel ratio in the exhaust gas downstream of the catalytic converter having oxygen storage capacity turns from lean to rich conditions.
Reducing components entering the first NOx storage catalytic converter mainly include hydrocarbons, hydrogen and carbon monoxide. Further reducing components, such as ammonia and hydrogen sulphide, may also be present in small amounts.
The amount of reducing components refers to the mass-oxygen-equivalent of the reducing components, i.e. the mass of oxygen that is necessary for oxidizing the reducing components, i.e. the sum of the mass of oxygen that is necessary to convert the hydrocarbons and carbon monoxide to carbon dioxide, to convert ammonia to nitrogen and water, to convert hydrogen to water and to convert other reducing components, which may be present in small amounts, into the oxidized derivative thereof. Oxidizing components which are able to oxidize the reducing components (i.e. to consume the reducing components) and which are stored at the NOx storage catalytic converter include oxygen, nitrogen oxides and sulphur oxides.
The amount of reducing components in the first NOx storage catalytic converter can be calculated as mass-oxygen-equivalent, for example, by measuring the air/fuel ratio upstream and downstream of the NOx storage catalytic converter during a switch from lean to rich exhaust conditions. The delay of the air/fuel ratio shift from lean to rich conditions upstream and downstream of the NOx storage catalyst enables to calculate the amount of reducing components consumed by the NOx storage catalytic converter as mass-oxygen-equivalent.
In particular, the amount of reducing components in mass-oxygen-equivalents can be determined as follows. By switching from lean to rich operation, the reducing components are oxidized by the oxygen stored at the oxygen storage materials in the NOx storage catalytic converter as well as by the nitrogen oxides which are released from the NOx storage materials and reduced in the NOx storage catalytic converter during rich operation. The amount of reducing components consumed by the first NOx storage catalytic converter at the temperature at which a given system is operated can be calculated as mass-oxygen-equivalent by measuring the air/fuel ratio upstream and downstream of the first NOx storage catalytic converter during a switch from lean to rich exhaust conditions using the following equation:
The amount of reducing components leaving the first NOx storage catalytic converter during) rich operation can be calculated by using the following equation:
In the above equations, the variables have the following meaning:
As discussed above, in the present method the rich phase is terminated at the earliest when the amount of reducing components leaving the first NOx storage catalytic converter is 0.05 times the amount of reducing components consumed by the first NOx storage catalytic converter during the time interval beginning when the air/fuel ratio upstream of the first NOx storage catalytic converter turns from lean to rich conditions and ending when the air/fuel ratio downstream of the first NOx storage catalytic converter turns from lean to rich conditions. Preferably, the rich phase is terminated just before the reducing components break through the catalytic converter having oxygen storage capacity downstream of the SCR catalytic converter to prevent the emission of ammonia, hydrocarbons and carbon monoxide. The breakthrough of reducing components can, for example, be detected by a lambda sensor.
In one embodiment, the duration of the rich phase is controlled by a lambda sensor configured downstream of the first NOx storage catalytic converter or the SCR catalytic converter. Alternatively, the duration of the rich phase is controlled by a lambda sensor configured downstream of the catalytic converter having oxygen storage capacity. It is also possible to use two lambda sensors, one being configured downstream of the first NOx storage catalytic converter or the SCR catalytic converter, the other being configured downstream of the catalytic converter having oxygen storage capacity. In the context of the position of the lambda sensors; the term “downstream of has the meaning of “directly downstream of”, i.e. no other catalytic converter is interposed between the lambda sensor and the converter the lambda sensor is downstream of Any of the lambda sensors which are commonly employed in the field of automotive exhaust gas treatment can be used in the present invention. For example, HEGO (heated exhaust gas oxygen) lambda sensor or linear lambda sensors as well as the oxygen sensing function of NOx sensor can be suitably employed.
The catalytic converter having oxygen storage capacity can, for example, be a second NOx storage catalytic converter, a three-way catalytic converter, or a diesel oxidation catalytic converter.
For example, any of the three-way catalytic converters that are conventionally employed in the treatment of automotive exhaust gases can be used as the catalytic converter having oxygen storage capacity. Any of the three-way catalytic converters that are commonly employed in the field of automotive exhaust gas treatment systems can be used in the present invention as long as the three-way catalytic converter comprises an oxygen storage material. Oxygen storage materials store oxygen and/or NOx under lean conditions and release oxygen and/or NOx under rich conditions. Examples of oxygen storage materials include palladium, cerium oxide, cerium/zirconium mixed oxides and cerium/zirconium mixed oxides doped with rare earth metals, iron or manganese, as well as the NOx-storage materials described below. The three-way catalytic converter can, for example, comprise platinum, palladium or rhodium as catalytically active components. The three-way catalytic converter can further comprise alumina, titania, earth alkali metal oxides or combinations thereof as support oxides for the precious metals.
Any of the diesel oxidation catalytic converters that are conventionally employed in the treatment of automotive exhaust gases can be used as the catalytic converter having oxygen storage capacity as long as the diesel oxidation catalytic converter comprises an oxygen storage material, such as those described above. The diesel oxidation catalytic converter can, for example, comprise platinum or palladium as catalytically active components, preferably platinum and palladium. In this embodiment, palladium can stabilize platinum against sintering at elevated temperatures. The diesel oxidation catalytic converter can further comprise support materials for the catalytically active components, such as zeolites, alumina, silica, titania or zirconia or combinations thereof, preferably zeolites, alumina or silica or combinations thereof.
In a preferred embodiment, the catalytic converter having oxygen storage capacity is a second NOx storage catalytic converter, for example any of the NOx storage catalytic converters described below. This embodiment provides advantages in particular at higher temperatures. An aged SCR catalytic converter typically is capable of completely adsorbing ammonia at temperatures up to about 300° C. At higher temperatures, however, a continuous breakthrough of ammonia can typically be observed, which increases with temperature. In embodiments, wherein the catalytic converter having oxygen storage capacity is, for example, a three-way catalytic converter or a diesel oxidation catalytic converter, ammonia which may be leaving the SCR catalytic converter can be oxidized to NOx on the catalytic converter having oxygen storage capacity during a lean phase, which would lead to a decrease in the overall NOx conversion rate. In contrast, when the catalytic converter having oxygen storage capacity is a second NOx storage catalytic converter, ammonia which may be leaving the SCR catalytic converter can be oxidized and stored on the second NOx storage catalytic converter or can react with NOx that had previously been stored on the second NOx storage catalytic converter to give nitrogen. In particular, when switching from rich phase to lean phase, the first NOx storage catalytic converter starts storing NOx entering into the exhaust gas treatment system, i.e. during the initial stage of the lean phase no NOx is available at the SCR catalytic converter which could react with ammonia. Ammonia is meanwhile being desorbed from the SCR catalytic converter at higher temperatures (this explains the decrease in performance of system 3 as compared to system 2 in
In addition to prolonging the rich phase, the second NOx storage catalytic converter can prolong the lean phase. Without wishing to be bound by theory, the following mechanism may be responsible for this effect. The second NOx storage catalytic converter can adsorb NOx, i.e. it will take longer for NOx to leave the exhaust gas treatment system leading to the termination of the lean phase being delayed. Due to the prolonging of the lean phase, the first NOx storage catalytic converter can adsorb a larger amount of NOx as compared to a system having a diesel oxidation or three way catalytic converter downstream of the SCR catalytic converter or having no catalytic converter with oxygen storage capacity downstream of the SCR catalytic converter at all. The increase in NOx loading on the first NOx storage catalytic converter during the lean phase can result in an increase in ammonia formation during the subsequent rich phase.
In a preferred embodiment, the first NOx storage catalytic converter comprises less oxygen storage material than the second NOx storage catalytic converter. This embodiment can be advantageous, since oxygen storage materials can reduce the amount of ammonia formation during rich operation.
It is further preferred to adjust the volume of the SCR catalytic converter such that the ammonia formed during the rich phase on the upstream NOx storage catalytic converter can be completely stored on the subsequent SCR catalytic converter.
It can further be preferred to choose the catalyst volume of the first NOx storage catalytic converter to be smaller than the catalyst volume of the second NOx storage catalytic converter. In this embodiment, slip of ammonia through the SCR catalytic converter, which may occur at higher temperatures (such as above 300° C.), can be reduced. This may be due to a reduction of the time period until NOx breaks through the first NOx storage catalytic converter during the lean phase, leading to earlier consumption of the ammonia stored on the SCR catalytic converter.
In an alternative embodiment, depending on the aging temperatures and the temperature management of the system, it can be preferred to choose the catalyst volume of the first NOx storage catalytic converter to be larger than the catalyst volume of the second NOx storage catalytic converter. In this embodiment, the SCR catalytic converter can be protected from high temperatures. Further, it may be preferred to incorporate a large portion of the total NOx storage components and catalytically active components (i.e. contained in the first and second NOx storage catalytic converter) into the first NOx storage catalytic converter in embodiments, wherein the temperature of the exhaust gas stream is low (such as 200° C.) upstream of the first NOx storage catalytic converter.
It is further preferred that the exhaust gas treatment system does not contain a second SCR catalytic converter downstream of the catalytic converter having oxygen storage capacity. When an exhaust gas treatment system is operated as defined in the present invention, substantially no ammonia leaves the second NOx storage catalytic converter, i.e. a second SCR catalytic converter downstream of the catalytic converter having oxygen storage capacity is not required.
The NOx storage catalytic converters employed in the present invention comprise catalyst materials, in particular NOx storage materials and catalytically active components. The NOx storage materials in turn can comprise the actual nitrogen oxides storage components, deposited in highly dispersed form on a support material. Any of the nitrogen oxides storage components, support materials and catalytically active components which are conventionally employed in the field of automotive exhaust gas treatment can also be employed in the present invention.
The NOx storage catalytic converters preferably comprise one or more storage components selected from compounds of alkali metals, alkaline-earth metals and rare earth metals and one or more catalytic components selected from platinum, palladium and rhodium. More preferably, the NOx storage catalysts employed in the present invention comprise barium oxide as a storage component and one or more catalytic components selected from platinum, palladium and rhodium.
The oxidation activity of the NOx storage catalytic converters for nitrogen monoxide may be increased further if the NOx storage catalytic converter additionally includes catalytically active components on the basis of support oxides selected from aluminum oxide, silicon dioxide, cerium oxide, zirconium oxide, titanium oxide, magnesium oxide or mixed oxides thereof which are coated with at least one of the platinum group metals platinum, palladium and rhodium. Particularly preferred support oxides are magnesium oxide, aluminum oxide, zirconium oxide and cerium oxide or mixtures thereof.
It is especially preferred that the NOx storage catalytic converter includes storage components on the basis of cerium oxide, which can be coated with platinum, and additionally platinum as a catalytic component on a support based on aluminum oxide. The storage components on the basis of cerium oxide are able to store nitrogen oxides at low temperatures and are therefore particularly suitable for the exhaust gas treatment system according to the invention.
Cerium oxide may be employed as a pure material or as a mixed oxide, preferably with zirconium oxide. Preferred are cerium/zirconium mixed oxides having a content of zirconium oxide between 2 and 50 wt. %, preferably between 2 and 40 wt. %, most preferably between 2 and 30 wt. % referred to the mixed oxide's total weight. The above-mentioned mixed oxides are particularly resistant to high temperature stresses which may occur, for example, during full-load operation of a diesel engine. A further increase of temperature resistance may be obtained by doping the mixed oxide with rare earth metal oxides such as praseodymium oxide.
The aluminum oxide which can be used as a support for platinum is an aluminum oxide of the so-called transition series, which has a high specific surface area between 10 and 400 m2/g. Doping this material with 2 to 10 wt. % lanthanum oxide may also stabilize it against thermal stresses. An aluminum silicate having a silicon dioxide content between 1 and 40 wt. % based on the total weight of the aluminum silicate is also particularly suitable.
Further NOx storage catalytic converters which can be employed in the present invention have previously been described. For example, EP-A-1 317 953 discloses a catalyst for lowering the amount of nitrogen oxides in the exhaust gas from lean burn engines comprising at least one noble metal of the platinum group of the periodic table of the elements, as well as at least one nitrogen oxides storage material comprising at least one nitrogen oxides storage component on one or more support materials, in combination with a homogeneous Mg/Al mixed oxide of magnesium oxide and aluminum oxide, wherein magnesium oxide is present in a concentration of 1 to 40 wt.-%, based on the total weight of the Mg/Al mixed oxide. As examples of the nitrogen oxides storage material oxides, carbonates or hydroxides of elements selected from the group consisting of magnesium, calcium, strontium, barium, alkali metals, rare earth metals or mixtures thereof are given. Preferably, the surface of the Mg/Al mixed oxide is loaded with one or more rare earth oxides, such as praseodymium oxide and/or cerium oxide. The NOx storage catalytic converters described in EP-A-1 317 953 provide excellent properties with regard to the width of their temperature window for NOx conversion nitrogen oxides and the conversion rate in this window, their storage capacity and their thermal stability. WO 2005/092481 describes further NOx storage catalytic converters which can be employed in the present invention. In particular, a nitrogen oxide storage material is disclosed which comprises at least one nitrogen oxide storage component on a homogeneous magnesium-aluminum mixed oxide doped with rare earth oxides as support material, with the magnesium-aluminum mixed oxide containing from 1 to 30% by weight of magnesium oxide, based on the total weight of the magnesium-aluminum mixed oxide.
Preferably, the first NOx storage catalytic converter comprises components which promote the formation of ammonia under rich exhaust gas conditions, such as compounds of iron, nickel or cobalt, for example oxides of iron, nickel or cobalt.
The SCR catalytic converters employed in the present invention can comprise any catalytic component which catalyzes the ammonia-SCR reaction. These include zeolite-containing catalytic components, in particular zeolites exchanged with copper and/or iron, tungsten-containing catalytic components, molybdenum-containing catalytic components, cerium-containing catalytic components, zirconium-containing catalytic components, titanium-containing catalytic components, niobium-containing catalytic components, vanadium-containing catalytic components or combinations thereof.
Zeolites are oxidic silicon/aluminum compounds with a specific crystal structure. They have the general composition
M2/nO.Al2O3.xSiO2.yH2O
wherein M represents a cation with the valency n and x is the modulus. The modulus is always greater than or equal to 2.
The SCR catalytic converter preferably includes zeolites, wherein the zeolites may be present in the acid H-form or be exchanged with metal ions. In addition, the SCR catalytic components may entirely consist of zeolites, wherein the zeolites are present in the acid H-form or are exchanged with metal ions. The zeolites can in particular be exchanged with iron and copper, within or exceeding their exchange capacity. Alternatively, the SCR catalytic converter may include a solid acid system of titanium dioxide and vanadium. In addition, this material may include at least one component selected from tungsten oxide, molybdenum oxide, silicon dioxide and sulfate. As a further alternative, the SCR catalytic converter may include tungsten-containing catalytic components, molybdenum-containing catalytic components, cerium-containing catalytic components, zirconium-containing catalytic components (such as zirconium dioxide), titanium-containing catalytic components (such as titanium dioxide), niobium-containing catalytic components, vanadium-containing catalytic components or combinations thereof.
In the above-described NOx storage catalytic converters and SCR catalytic converters, the catalyst materials can be applied on a carrier, such as an inert, ceramic or metal honeycomb carrier, in the form of a coating.
Preferred embodiments of the present invention are shown in
The arrangement shown in
It is further possible to interpose a particulate filter in any of the arrangements shown in
The following examples illustrate the invention.
System 1 (Comparative Example): Close-coupled three-way catalytic converter (TWC)+underfloor NOx storage catalytic converter and downstream SCR catalytic converter.
System 2 (Comparative Example): Close-coupled three-way catalytic converter (TWC)+two underfloor NOx storage catalytic converters.
System 3: Close-coupled three-way catalytic converter (TWC)+underfloor NOx storage catalytic converter, downstream SCR catalytic converter and further downstream second NOx storage catalytic converter.
The three-way catalytic converter comprised platinum, palladium and rhodium in a total loading of 128 g/cft, the NOx underfloor catalytic converters comprised platinum, palladium and rhodium in a total loading of 100 g/cft and barium as NOx storage component, and the SCR catalytic converter comprised a zeolite exchanged with iron.
For each of the three Systems 1 to 3, the close-coupled three-way catalytic converter had a volume of 0.8 1, and each underfloor catalytic converter had a volume of 1.0 1. Before measurements were taken, each system was aged on the engine test bench for 30 hours at λ=1, with an average temperature of 810° C. at the upstream NOx storage catalytic converter.
The evaluation of the systems at the engine test bench were carried out by operating the engine in 8 different stationary operation points resulting in different temperatures in the first NOx storage catalytic converter from 250 to 550° C. In each point the engine was operated with a lean air/fuel mix. Termination of the lean and rich phases was controlled by sensors with the NOx sensor being located downstream of the ultimate catalyst in the system. The lean phase was terminated when the NOx-sensor detected a NOx slip of 100 ppm NOx and the rich phase was terminated when the lambda signal of the NOx sensor detected rich conditions (λ<1).
System 1 and System 3 are compared in
An exhaust gas treatment system having a close-coupled TWC and underfloor first NOx storage catalytic converter, SCR catalytic converter and second NOx storage catalytic converter was investigated at the engine test bench. The system was aged at the engine for 30 hours at a lambda value of 1 at 820° C. inside the first NOx storage underfloor catalytic converter. In the subsequent test, three lambda sensors were configured upstream of the first NOx storage catalytic converter, downstream of the first NOx storage catalytic converter, and downstream of the second NOx storage catalytic converter, respectively. Additionally, the emissions of hydrocarbons and carbon monoxide as well as ammonia were recorded in three positions in the exhaust system: downstream of the first NOx storage catalytic converter, downstream of the SCR catalytic converter and downstream of the second NOx storage catalytic converter. The test was carried out under stationary engine operation conditions at an average temperature of 300° C. inside the first NOx storage catalytic converter.
It was found that when the lambda value at the first lambda sensor falls below a value of 1 (line 2 in
The SCR catalytic converter can adsorb ammonia very efficiently as can be seen from a comparison of lines 4 and 5 in
When lambda at the lambda sensor downstream of the second NOx storage catalytic converter falls below a value of 1 the rich phase should be terminated at the latest in order to keep breakthrough of reducing components at a minimum. As can be seen from lines 6 in
For the exhaust gas system described in Example 2, the amount of ammonia leaving the first NOx storage catalytic converter was determined when the amount of reducing components entering the first NOx storage catalytic converter during the rich phase is increased stepwise by engine management.
The average temperature in the first NOx storage catalytic converter during the rich/lean cycling was about 270° C. The lean phase was terminated when a NOx sensor downstream of the first NOx storage catalytic converter detected a NOx signal of about 100 ppm NOx. The rich phase was terminated by time control. In the first cycle the rich phase was chosen to last 8 seconds. The rich phase was prolonged in each consecutive cycle by 1.5 seconds in order to increase the amount of reducing components during the rich phase. A constant lambda of 0.94 was chosen during the rich phase. Similar results were obtained using decreasing lambda values in the rich phases of consecutive cycles in order to increase the amount of reducing components and keeping the duration of the rich phase constant in each cycle.
With increasing amounts of reducing components leaving the first NOx storage catalytic converter, the amount of ammonia formed over the first NOx storage catalytic converter increased. In cycle No. 8 164 mg ammonia were formed during the rich phase. In cycle No. 9 reducing components started to leave the second NOx storage catalytic converter and ammonia could be detected downstream of the second NOx storage catalytic converter (triangles).
When the same test as described above was carried out at an average temperature of about 300° C. inside the first NOx storage catalytic converter, 78 mg ammonia were formed over a rich/lean cycle when the amount of reducing components leaving the first NOx storage catalytic converter was 0.05 times the amount of reducing components consumed by the first NOx storage catalytic converter.
| Number | Date | Country | Kind |
|---|---|---|---|
| 07150308.0 | Dec 2007 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP08/09482 | 11/10/2008 | WO | 00 | 9/10/2010 |
