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    • 专利摘要:
    catalyzed substrate monolith for use in the treatment of exhaust gas, exhaust system for a low-combustion internal combustion engine, low-combustion internal combustion engine, vehicle, and method for reducing or preventing a selective catalytic reduction catalyst. a catalyzed substrate monolith (12) for use in the treatment of exhaust gas emitted from a low-combustion internal combustion engine, whose catalyzed substrate monolith (12) comprising a first reactive coating (16) and a second reactive coating (coating 18), wherein the first reactive coating comprises a catalyst composition comprising at least one metal of the platinum group (pgm) and at least one support material for at least one pgm, where at least one pgm in the first reactive coating is liable to volatilize when the first reactive coating is described at relatively extreme conditions including relatively high temperatures, where the second reactive coating comprises at least one metal oxide to trap volatilized pgm and where the second reactive coating is oriented to contact exhaust gas that came into contact with the first reactive coating.
    公开号:BR112014013261B1
    申请号:R112014013261-5
    申请日:2012-12-11
    公开日:2021-02-23
    发明作者:Philip Blakeman；Gavin Michael Brown；Sougato Chatterjee；Andrew Francis Chiffey；Jane Gast；Paul Richard Phillips；Raj RAJARAM；Glen Spreitzer；Andrew Walker
    申请人:Johnson Matthey Public Limited Company；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [0001] The present invention relates to a catalyzed substrate monolith for use in the treatment of exhaust gas emitted from a low combustion internal combustion engine, particularly vehicular internal combustion engines, whose catalyzed substrate monolith comprising a first coating reactive and a second reactive coating. BACKGROUND OF THE INVENTION
    [0002] In general, there are four classes of pollutants that are controlled by intergovernmental organizations worldwide: carbon monoxide (CO), unburned hydrocarbons (HC), nitrogen oxides (NOx) and particulate matter (PM).
    [0003] As emission standards for the permissible emission of such pollutants in vehicle engine exhaust gases become progressively tighter, a combination of engine management and multiple catalytic exhaust gas aftertreatment systems is being developed. proposed and developed to meet these emission standards. For exhaust systems containing a particulate filter it is common for engine management to be used periodically (for example, every 500 km) to increase the temperature in the filter in order to burn substantially all the remaining soot kept in the filter thus returning the system to a baseline level. These engine-managed soot combustion events are often called “filter regeneration”. Although a primary focus of filter regeneration is to burn soot kept on the filter, an unintended consequence is that one or more catalyst coatings present in the exhaust system, for example, a filter coat on the filter itself (a so-called filter debris). catalyzed soot (CSF)) an oxidation catalyst (such as a diesel oxidation catalyst (DOC)) or a NO2 adsorbent catalyst (NAC) located upstream or downstream of the filter (for example, a first DOC followed by a particulate diesel filter, followed by a second DOC and finally an SCR catalyst) can be regularly described at high exhaust gas temperatures, depending on the level of engine management control in the system. Such conditions can also be experienced with modes of occasional unintended engine compromise or uncontrolled or poorly controlled regeneration events. However, some diesel engines, particularly heavy dirt diesel engines that operate at high load, can still expose catalysts to significant temperatures, for example,> 600 ° C under normal operating conditions.
    [0004] As vehicle manufacturers develop their engines and engine management systems to meet emission standards, vehicle manufacturers have asked the Applicant / Inventor to propose catalytic components and combinations of catalytic components to assist in the goal of meeting the standards of issue. Such components include DOCs to oxidize CO, HCs and optionally NO as well; CSFs to oxidize CO, HCs, optionally to oxidize NO as well, and to trap particulate matter for subsequent combustion; NACs to oxidize CO and HC and to oxidize nitrogen monoxide (NO) and absorb it from a poor exhaust gas and to desorb adsorbed NOx and to reduce it to N2 in a rich exhaust gas (see below) ; and selective catalytic reduction catalysts (SCR) to reduce NOx to N2 in the presence of a nitrogen reducer, such as ammonia (see below).
    [0005] In practice, catalyst compositions employed in DOCs and CSFs are very similar. In general, however, a major difference between the use of a DOC and a CSF is the substrate monolith on which the catalyst composition is coated: in the case of a DOC, the substrate monolith is typically a substrate monolith through the flow , comprising a metal or ceramic honeycomb monolith having an arrangement of elongated channels extending through it, whose channels are open at both ends; a CSF substrate monolith is a filter monolith, such as a wall flow filter, for example, a porous ceramic filter substrate comprising a plurality of input channels arranged in parallel with a plurality of output channels, where each input channel and each output channel is defined in part by a porous structure ceramic wall, where each input channel is alternately separated from an output channel by a porous ceramic wall and vice versa. In other words, the wall flow filter is a honeycomb arrangement that defines a plurality of primary channels plugged at an upstream end and a plurality of secondary channels not plugged at the upstream end, but plugged at a downstream end. Channels vertically and laterally adjacent to a primary channel are plugged at one end downstream. When viewed from either end, the alternately plugged and open ends of the channels take on the appearance of a board.
    [0006] Very complicated multi-layer catalyst arrangements, such as DOCs and NACs, can be coated on a substrate monolith through the flow. While it is possible to coat a surface of a filter monolith, for example, an inlet channel surface of a wall flow filter, with more than one layer of catalyst composition, a problem with coating filter monoliths is to avoid pressure of return that increases unnecessarily, when in use, overloading the filter monolith with reactive catalyst coating, thus restricting the passage of gas through it. Thus, although coating a surface of a substrate filter monolith sequentially with one or more different layers of catalyst is not impossible, it is more common for different catalyst compositions to be segregated in any zones, for example, axially segregated front and half-rear zones of a filter monolith, or by coating an inlet channel of a substrate monolith wall flow filter with a primary catalyst composition and an outlet channel with a second catalyst composition. However, in particular embodiments of the present invention, the filter inlet is coated with one or more layers, the layers of which may be of the same or different catalyst composition. It has also been proposed to coat a NAC composition on a substrate filter monolith (see, for example, EP 0766993).
    [0007] In exhaust systems comprising multiple components of the catalyst, each comprising a separate substrate monolith, typically the SCR catalyst is located downstream of a DOC and / or a CSF and / or a NAC by virtue of the knowledge that oxidizing some nitrogen oxide (NO) in the exhaust gas to nitrogen dioxide (NO2) so there is a ratio of about 1: 1 of NO: NO2 coming out of the DOC and / or the CSF and / or the NAC, the reaction of Downstream SCR is promoted (see below). It is also well known from EP341832 (the so-called Continuously Regenerating Trap or CRT®) that NO2, generated by oxidation of NO in exhaust gas to NO2, can be used to passively burn soot in a downstream filter. In exhaust system arrangements where the EP341832 process is important, they were the SCR catalyst to be located upstream of the filter, this can reduce or prevent the process of burning soot trapped in NO2, due to a majority of the NOx used for burning soot can probably be removed from the SCR catalyst.
    [0008] However, a preferred system arrangement for light dirt diesel vehicles is a diesel oxidation catalyst (DOC) followed by a nitrogen reducer injector, then an SCR catalyst and finally a catalyzed soot filter (CSF). A shortcut to an arrangement like this is “DOC / SCR / CSF”. This arrangement is preferred for light dirt diesel vehicles because an important consideration is to achieve conversion of NOx into an exhaust system as quickly as possible after a vehicle engine is started to enable (i) precursors to nitrogen reducers, such as as ammonia to be injected / decomposed in order to release ammonia for conversion of NOx; and (ii) NOx conversion as high as possible. Where a large thermal mass filter to be placed upstream of the SCR catalyst, that is, between the DOC and the SCR catalyst (“DOC / CSF / SCR”), (i) and (ii) may take longer to reach and convert of NOx that a whole of the emission pattern triggering cycle can reduce. Particulate removal can be done using oxygen and occasional forced regeneration of the filter using engine management techniques.
    [0009] It has also been proposed to coat a reactive coating SCR catalyst on a substrate filter monolith itself (see, for example, WO 2005/016497), in which case an oxidation catalyst can be located upstream of the coated filter substrate with SCR (whether the oxidation catalyst is a component of a DOC, a CSF or a NAC) in order to modify the NO / NO2 ratio to promote NOx reduction activity in the SCR catalyst. It has also been proposed to locate a NAC upstream of an SCR catalyst disposed in a substrate monolith through the flow, whose NAC can generate NH3 in situ during NAC regeneration (see below). A proposal like this is described in GB 2375059.
    [00010] NACs are known, for example, from US 5,473,887 and are designed to adsorb NOx from the poor exhaust gas (lambda> 1) and to desorb the NOx when the oxygen concentration in the exhaust gas decreases. Desorbed NOx can be reduced to N2 with a suitable reducer, for example engine fuel, promoted by a catalyst component, such as rhodium, from the NAC itself or located downstream from the NAC. In practice, oxygen concentration control can be adjusted to a desired redox composition intermittently in response to a calculated NAC remaining NOx adsorption capacity, for example, richer than normal engine running (but still stoichiometric or lambda composition = 1), stoichiometric or rich in stoichiometric (lambda <1). The oxygen concentration can be adjusted in a number of ways, for example, throttling, injecting additional hydrocarbon fuel into an engine cylinder, such as during the exhaust stroke or injecting hydrocarbon fuel directly into the exhaust gas downstream of a manifold the engine.
    [00011] A typical NAC formulation includes a catalytic oxidation component, such as platinum, a significant amount, (that is, substantially more that is required for use as a promoter, such as a promoter in a three-way catalyst), of a NOx storage component, such as barium, and a reduction catalyst, for example, rhodium. A commonly given mechanism for storing NOx from a poor exhaust gas for this formulation is: NO + / O2 - NO2 (l); and BaO + 2NO2 + / 02 - Ba (NO3) 2 (2), in which in reaction (1), nitric oxide reacts with oxygen at active oxidation sites on platinum to form NO2. Reaction (2) involves adsorption of NO2 by the storage material in the form of an inorganic nitrate.
    [00012] At lower concentrations of oxygen and / or at high temperatures, nitrate species become thermodynamically unstable and decomposes, producing NO or NO2 according to the reaction (3) below. In the presence of a suitable reducer, these nitrogen oxides are subsequently reduced by carbon monoxide, hydrogen and hydrocarbons to N2, which can happen on the reduction catalyst (see reaction (4)). BaíNO3) 2> BaO + 2NO + 3 / 2O2 or BaíNOar> BaO + 2NO; + / O; (3); and NO + CO / N2 + CO2 (4);
    [00013] (Other reactions include Ba (NO;); + 8H2 ^ BaO + 2NH3 + 5H2O followed by NH3 + NIL> N2 + yH; O or 2NH3 + 2O; + CO> N2 + 3H2O + CO2etc.).
    [00014] In the reactions of (l) - (4) including previously here, the reactive barium species are given as the oxide. However, it is understood that in the presence of air the majority of barium is in the form of carbonate or possibly hydroxide. Versed can adapt the previous reaction schemes according to the barium species other than the oxide and catalytic coatings sequence in the exhaust stream.
    [00015] Oxidation catalysts promote the oxidation of CO to CO2 and HCs not burned to CO2 and H2O. Typical oxidation catalysts include platinum and / or palladium on a high surface area support.
    [00016] The application of SCR technology to treat NOx emissions from vehicular internal combustion (IC) engines, particularly low-burn IC engines, is well known. Examples of nitrogen reducers that can be used in the SCR reaction include compounds, such as nitrogen hydrides, for example, ammonia (NH3) or hydrazine, or an NH3 precursor.
    [00017] NH3 precursors are one or more compounds from which NH3 can be derived, for example, by hydrolysis. Decomposition of the precursor to ammonia and other by-products can be by hydrothermal or catalytic hydrolysis. NH3 precursors include urea (CO (NH2) 2) as an aqueous solution or as an ammonium carbamate or solid (NH2COONH4). If urea is used as an aqueous solution, a eutectic mixture, for example, a 32.5% NH3 (aq) is preferred. Additives can be included in aqueous solutions to reduce the temperature of crystallization. Currently, urea is the preferred source of NH3 for mobile applications because it is less toxic than NH3 is easy to transport and handle is inexpensive and commonly available. Incomplete urea hydrolysis can lead to higher PM emissions in tests to meet the relevant emission test cycle due to solids or droplets of partially hydrolyzed urea being trapped by the filter paper used in the PM legislative test and counted as PM mass . In addition, the release of certain incomplete urea hydrolysis products, such as cyanuric acid, is environmentally undesirable.
    [00018] SCR has three main reactions (shown below in reactions (5) - (7) inclusive) that reduce NOx to elemental nitrogen. 4NH3 + 4NO + O2> 4N2 + 6H2O (i.e., 1: 1 H3: NO) 4 H3 + 2NO + 2NO2> 4N2 + 6H2O (i.e., 1: 1 H3: NOx) 8 H3 + 6NO2> 7N2 + 12H2O ( ie 4: 3 H3: NOx) An undesirable, non-selective side reaction of relevance is: 2 H3 + 2NO2> N2O + 3H2O + N2
    [00019] In practice, reaction (7) is relatively slow compared to reaction (5) and reaction (6) is the fastest of all. For this reason, when versed in technology they design exhaust after-treatment systems for vehicles, they often prefer to have an oxidation element catalyst (for example, a DOC and / or a CSF and / or a NAC) upstream of a SCR catalyst.
    [00020] When certain DOCs and / or NACs and / or CSFs are described at high temperatures, for example, encountered during filter regeneration and / or an engine compromise event and / or (in certain heavy dirt diesel applications) normal high temperature exhaust gas, it is possible to give sufficient time at high temperature for low levels of platinum group metal components, particularly Pt, to volatilize from DOC and / or NAC and / or CSF components and subsequently for the platinum group metal to be trapped in an SCR catalyst downstream. This can have a highly detrimental effect on the performance of the SCR catalyst, since the presence of Pt leads to a high activity for competitive, non-selective ammonia oxidation, such as in reaction (9) (which shows the complete oxidation of NH3) , thus producing secondary emissions and / or not productively consuming NH3. 4NH3 + 50; > 4NO + 6H2O (9)
    [00021] A vehicle manufacturer reported the observation of the same phenomenon on SAE 2009-01-0627 paper, which is entitled “Impact and Prevention of Ultra-Low Contamination of Metal of Platinum Groups on SCRs Catalysts Due to DOC Design” and includes data that compare the NOx versus temperature conversion activity for a Fe / zeolite SCR catalyst located in series behind four suppliers' DOCs containing platinum group metal (PGM) that were placed in contact with a flow model exhaust gas at 850 ° C for 16 hours. The results presented show that the conversion of NOx activity of a Fe / zeolite SCR catalyst disposed behind a DOC 20Pt: Pd at 2499gm-3 (70gft-3) total PGM was negatively altered at higher evaluation temperatures compared to evaluation temperatures lower as a result of Pt contamination. Two DOC 2Pt: Pds from different suppliers at 3748.5 gm-3 (105gft-3) total PGM were also tested. In a first DOC 2Pt: Pd, the activity of the SCR catalyst was affected to a similar extent as the test in the DOC 20Pt: Pd, while for the second DOC 2Pt: Pd the activity of the SCR catalyst was contaminated to a lesser extent, although the second DOC 2Pt: Pd still showed less conversion of NOx activity compared to the white control (no DOC, only one substrate discovered). The authors concluded that the supplier of the second DOC 2Pt: Pd, which showed more moderate conversion of NOx degradation, was more successful in stabilizing 2499gm-3 (70gft-3) Pt with 1249.5 gm-3 (35gft -3) Pd. A DOC of only Pd at 3748.5 gm-3 (150 gft-3) showed no impact on the SCR downstream with respect to the white control. Previous studies by the authors of SAE 200901-0627 have been published on SAE paper no. 2008-01-2488.
    [00022] EP 0622107 describes a catalyst to purify exhaust gas from diesel engines, where catalyst platinum is loaded on the upstream side of an exhaust gas stream, and palladium catalyst is charged on the lower stream side of the exhaust stream. exhaust gas. Hydrocarbons (HC) and soluble organic fraction (SOF) in the exhaust gas can be burned and removed by the platinum catalyst at low temperature.S02 is not oxidized at low temperature. The exhaust gas is heated to a high temperature in the upstream portion. HC and SOF is effectively oxidized and removed by palladium catalyst at high temperature. S02 is not oxidized evenly at a higher temperature. The description claims that no HC and SOF catalysts that purify exhaust gas can be removed at low temperature and SO2 is not oxidized. SUMMARY OF THE INVENTION
    [00023] Vehicle manufacturers began to ask the Applicant / Inventor for means to resolve the volatilization problem of relatively low levels of PGMs of components upstream of SCR catalysts. It would be highly desirable to develop strategies to prevent this movement of PGM in an SCR catalyst downstream at high temperatures. The present inventors have developed numerous strategies to meet this need.
    [00024] The inventors have observed that platinum volatilization of a PGM-containing catalyst comprising both platinum and palladium can occur in extreme temperature conditions when the weight ratio of Pt: Pd is greater than about 2: 1, It is also believed that where PGM consists of platinum, platinum volatilization can also be observed. The present inventors have designed a catalyzed substrate monolith comprising PGM for use in combination with a downstream SCR catalyst that avoids or reduces the PGM problem, particularly Pt, by migrating from a relatively highly charged upstream Pt catalyst to a downstream SCR catalyst .
    [00025] According to a first aspect, the invention provides a catalyzed substrate monolith for use in the treatment of exhaust gas emitted from a low-combustion internal combustion engine, whose catalyzed substrate monolith comprising a first reactive coating and a second reactive coating, wherein the first reactive coating comprises a catalyst composition comprising at least one platinum group metal (PGM) and at least one support material, wherein at least one PGM in the first reactive coating is liable to volatilize when the first reactive coating is described at relatively extreme conditions including relatively high temperatures, where the second reactive coating comprises at least one metal oxide to trap volatilized PGM and where the second reactive coating is oriented to come into contact with incoming exhaust gas in contact with the first reactive coating.
    [00026] In accordance with a second aspect, the invention provides an exhaust system for a low combustion internal combustion engine, the system of which comprising a first catalyzed substrate monolith according to the invention.
    [00027] In a further aspect, the invention provides an internal combustion engine with a low burn rate, particularly for a vehicle, comprising an exhaust system according to any preceding claim.
    [00028] In another aspect the invention provides a vehicle comprising an engine according to the invention.
    [00029] In accordance with another aspect, the invention provides a method of reducing or preventing a selective catalytic reduction catalyst (SCR) in an exhaust system of an internal combustion engine that is poorly burnt from getting poisoned with metal from the group of platinum (PGM) which can volatilize from a catalyst composition comprising at least one PGM supported on at least one support material and disposed on a substrate monolith upstream of the SCR catalyst when the catalyst composition comprising PGM is described under conditions relatively extreme including relatively high temperatures, the method of which entails trapping volatilized PGM in a reactive coating comprising at least one metal oxide, which is disposed on the same substrate monolith as the catalyst composition comprising PGM.
    [00030] A further aspect of the invention relates to the use of a metal oxide (i.e., at least one metal oxide) to reduce or prevent poisoning of a selective catalytic reduction catalyst (SCR) by a metal in the group of platinum (PGM), typically in an exhaust system of a low-combustion internal combustion engine, in which a second reactive coating comprises metal oxide and is oriented to come into contact with exhaust gas which came into contact with a first reactive coating, and wherein the first reactive coating comprises a catalyst composition comprising at least one platinum group metal (PGM) and at least one support material, and wherein a catalyzed substrate monolith comprises the first reactive coating and the second reactive coating. Generally, the metal oxide is to imprison volatilized PGM. Typically, at least one PGM in the first reactive coating is liable to volatilize when the first reactive coating is described under relatively extreme conditions including relatively high temperatures. BRIEF DESCRIPTION OF THE DRAWINGS
    [00031] In such a way that the invention can be more fully understood, reference is made to the following examples by way of illustration only and with reference to the attached drawings.
    [00032] Figure 1 is a schematic drawing of a laboratory reactor used to test contamination of platinum in a SCR catalyst of Fe / Beta zeolite or a SCR catalyst of Cu / CHA zeolite.
    [00033] Figure 2 is a graph that compares the conversion of NOx activity as a temperature function of four aged SCR catalyst cores, each of which was aged in a laboratory scale exhaust system configuration containing samples of the core of the examples 3, 5 and 6 of the invention or comparative example 2. The results of aged SCR activity are plotted against activity of a freshly prepared, that is, un aged SCR catalyst.
    [00034] Figure 3 is a graph that compares the conversion of NOx activity as a temperature function of three additional aged SCR catalyst cores, each of which has been aged in a laboratory scale exhaust system configuration containing core samples. of Examples 4 and 7 of the invention or Comparative Example 2. The results of the aged SCR activity are plotted against the activity of a freshly prepared, that is, un aged SCR catalyst.
    [00035] Figure 4 is a graph that compares the conversion of NOx activity as a temperature function of the three aged SCR catalyst cores, each of which was aged in a laboratory-scale exhaust system configuration containing a flow filter. catalyzed wall arranged upstream of the Fe / Beta zeolite SCR catalyst, a system comprising a coated filter in both the inlet and outlet channels with a weight ratio Pt: Pd 1: 1 (Example 7); a second system comprising a coated filter in both the inlet and outlet channel with a weight ratio Pt: Pd 5: 1 (Example 8); and a third, comparative system comprising a filter coated both in the inlet and outlet channel with a Pt-only catalyst. The results of the aged SCR activity are plotted against the activity of a freshly prepared, that is, un aged SCR catalyst .
    [00036] Figure 5 is a bar graph that compares the conversion of NOx activity as a function of temperature of the two aged SCR catalyst cores, each of which was aged in the laboratory-scale exhaust system shown in Figure 1 containing samples. of the diesel oxidation catalyst core of example 11 heated in a tube oven at 900 ° C for 2 hours in a synthetic exhaust gas flowing with the Cu / CHA zeolite SCR catalyst core maintained at 300 ° C located at downstream.
    [00037] Figures 6A and 6B are schematic drawings of the modalities of the exhaust system including substrate monolith catalyzed according to the invention. DETAILED DESCRIPTION OF THE INVENTION
    [00038] In general, at least one PGM in the first reactive coating comprises platinum. When at least one PGM in the first reactive coating is platinum, then platinum is the PGM liable to volatilize when the first reactive coating is described under relatively extreme conditions including relatively high temperatures. The relatively extreme conditions including relatively high temperatures are, for example, temperatures of> 700 ° C, preferably> 800 ° C, or more preferably> 900 ° C.
    [00039] Typically, the PGM in the first reactive coating comprises both platinum and palladium. Platinum and / or palladium may be the PGM liable to volatilize when the first reactive coating is described under relatively extreme conditions including relatively high temperatures. However, when both platinum and palladium are present, then normally platinum is more likely to be the PGM that is likely to volatilize when the first reactive coating is described under relatively extreme conditions including relatively high temperatures.
    [00040] It is possible that higher Pt: Pd weight ratios are used in the first reactive coating for the purposes of, for example, generating NO2 to promote combustion downstream of filtered particulate matter, due to any PGM that may volatilize from the first coating in use can be trapped in the second reactive coating. Typically, the first reactive coating comprises a Pt: Pd weight ratio of <10: 1, for example, 8: 1, 6: 1, 5: 1 or 4: 1.
    [00041] When the catalyzed substrate monolith is disposed immediately upstream of an SCR catalyst (i.e., without any substrate monolith intervention between the catalyzed substrate monolith of the present invention and the SCR catalyst), it is preferred that the ratio by weight of Pt: Pd is <2, preferably in the first reactive coating or in the whole catalyzed substrate monolith (i.e., general). Where at least one PGM in the first reactive coating comprises both platinum and palladium, preferably the weight ratio of Pt: Pd is <2, such as <1.5: 1, for example, about 1: 1, The significance of this characteristic is shown in the examples: the inventors have observed that the preferred Pt: Pd weight ratios are less volatile, by empirical testing, than a similar catalyst having a 4: 1 Pt: Pd weight ratio, in layered catalyst arrangements, we prefer if an outer layer has a Pt: Pd weight ratio of <2, or optionally the general Pt: Pd weight ratio of all combined layers is <2.
    [00042] Typically, the weight ratio of Pt: Pd in the first reactive or general coating is> 35:65 (for example,> 7: 13). It is preferred that the weight ratio Pt: Pd is> 40:60 (for example,> 2: 3), more preferably> 45:55 (for example,> 9: 11), particularly> 50:50 (for example ,> 1: 1), such as> 1.25: 1, and even more preferably> 1.5: 1 (e.g.,> 1.6: 1). The weight ratio of Pt: Pd, either in the first reactive or general coating is typically 10: 1 to 7: 13. It is preferred that the weight ratio of Pt: Pd is 8: 1 to 2: 3, more preferably 6 : 1 to 9: 11, even more preferably 5: 1 to 1: 1, such as 4: 1 to 1.25: 1, and even more preferably 2: 1 to 1.25: 1 (e.g., 2: 1 to 1.6: 1).
    [00043] In general, the total amount of the platinum group metal (PGM) (for example, the total amount of Pt and / or Pd) is 35.7 to 17850 gm-3 (1 to 500 gft-3). Preferably, the total amount of PGM is 178.5 to 14280 gm-3 (5 to 400 gft-3), more preferably 357 to 10710 gm-3 (10 to 300 gft-3), even more preferably, 892.5 to 8925 gm-3 (25 to 250 gft-3), and even more preferably 1249.5 to 7140 gm-3 (35 to 200 gft-3).
    [00044] In general, when the catalyzed substrate monolith of the present invention comprises platinum, then the platinum is not doped with bismuth and / or manganese. More preferably, the substrate monolith catalyst does not comprise bismuth and / or manganese.
    [00045] In general, the metal oxide (i.e., at least one metal oxide support of the second reactive coating) comprises a metal oxide selected from the group consisting of optionally stabilized alumina, amorphous silica-alumina, optionally stabilized zirconia , ceria, titania, an optionally stabilized mixed ceria-zirconium oxide and mixtures of any of the two or more of them. Suitable stabilizers include one or more silica and rare earth metals.
    [00046] The metal oxide of the second reactive coating and at least one support material of the first reactive coating can be the same or different. It is preferred that the metal oxide of the second reactive coating and at least one support material of the first reactive coating are different.
    [00047] The second reactive coating can typically comprise metal oxide in a total amount of 0.0061 to 0.305 gm-3 (0.1 to 5 g in-3), preferably 0.0122 to 0.244 g cm3 ( 0.2 to 4 g in-3) (for example, 0.0305 to 0.2135 g cm3 (0.5 to 3.5 g in-3)), more preferably 0.061 to 0.1525 g cm3 (1 to 2.5 g in-3).
    [00048] The inventors have observed that particularly metal oxides containing alumina and ceria per se are capable of trapping volatilized PGM, particularly ceria, which has a particular affinity for Pt. It is preferred that the metal oxide of the second reactive coating is selected from the group consisting of optionally stabilized alumina, ceria and an optionally stabilized mixed ceria-zirconium oxide. More preferably, the metal oxide is selected from the group consisting of optionally stabilized alumina and an optionally stabilized mixed ceria-zirconium oxide.
    [00049] In one embodiment, the second reactive coating does not comprise palladium and platinum. More preferably, the second reactive coating does not comprise a platinum group metal (PGM).
    [00050] In other embodiments, the second reactive coating may further comprise a catalyst composition comprising at least one metal selected from the group consisting of palladium, silver, gold and combinations of any of the two or more of the same, wherein at least a metal oxide support at least one metal. It is preferred that the second reactive coating comprises a supported combination of palladium and gold, for example, as an alloy, as described in Applicant / Inventor WO 2009/136206.
    [00051] When the second reactive coating comprises a catalyst composition comprising palladium and gold (for example, as an alloy), then typically palladium and gold are not doped with bismuth and / or manganese. More preferably, the second reactive coating does not comprise bismuth and / or manganese.
    [00052] Typically, the total amount of at least one metal in the second reactive coating is 357 to 12495 gm-3 (10 to 350 gft-3). It is preferred that the total amount is 714 to 10,710 gm-3 (20 to 300 gft-3), more preferably 1,071 to 8925 gm-3 (30 to 250 gft-3), even more preferably, 1606,5 to 7140 gm -3 (45 to 200 gft-3), and even more preferably 1785 to 6247.5 gm-3 (50 to 175 gft-3).
    [00053] When the second reactive coating comprises a catalyst composition comprising palladium, then preferably the second reactive coating does not comprise platinum.
    [00054] In general, the second reactive coating is substantially devoid of (i.e., does not comprise) copper and / or rhodium.
    [00055] The only PGM present in the second reactive coating is generally palladium. However, in a particular embodiment, the second reactive coating comprises platinum and palladium. Typically, the weight ratio of Pt: Pd in the second reactive coating is less than the weight ratio of Pt: Pd in the first reactive coating (i.e., the relative amount of Pt to Pd in the second reactive coating is less than the relative amount from Pt to Pd in the first reactive coating). The present inventors have observed that palladium, or a Pt / Pd catalyst having a relatively high Pd content, can act to trap volatilized Pt.
    [00056] The first reactive coating comprises a catalyst composition comprising at least one platinum group metal (PGM) and at least one support material for at least one PGM. The catalyst is typically applied to the substrate monolith as a reactive coating slurry comprising at least one PGM salt and one or more support material in the finished catalyst coating, before the coated filter is dried and then calcined. One or more support materials can be referred to as a "reactive coating component". It is also possible that at least one PGM is pre-fixed in one or more support materials before it is made into slurry, or for a combination of particles of support material to which PGM is pre-fixed to be made into slurry. in a PGM salt solution.
    [00057] By at least one "support material" here is meant a metal oxide selected from the group consisting of optionally stabilized alumina, amorphous silica-alumina, optionally stabilized zirconia, ceria, titania, an optionally stabilized ceria-zirconia oxide , a molecular sieve and mixtures or combinations of any of the two or more of them.
    [00058] Typically, at least one support material of the first reactive coating is selected from the group consisting of optionally stabilized alumina, amorphous silica-alumina, optionally stabilized zirconia, ceria, titania, an optionally stabilized mixed ceria-zirconium oxide, a sieve molecular and mixtures or combinations of any of the two or more of the same. It is preferred that the first reactive coating comprises at least one support material selected from the group consisting of optionally stabilized alumina, amorphous silica-alumina, ceria and mixtures or combinations of either or more of the two.
    [00059] At least one support material may include one or more molecular sieves, for example, an aluminosilicate zeolite. The primary rate of the molecular sieve in the PGM catalyst for use in the present invention is to improve hydrocarbon conversion during a rate cycle by storing hydrocarbon following a cold start or during cold phases of a rate cycle and releasing stored hydrocarbon at higher temperatures when associated with platinum group metal of the catalyst are more active for HC conversion. See, for example, Applicant / Inventor EP 0830201, Molecular sieves are typically used in catalyst compositions according to the invention for light dirt diesel vehicles, whereas they are rarely used in catalyst compositions for dirt diesel applications. heavy due to exhaust gas temperatures in heavy dirt diesel engines mean that hydrocarbon trapping functionality in general is not required.
    [00060] However, molecular sieves, such as aluminosilicate zeolite are not particularly good supports for platinum group metals because they are mainly silica, particularly relatively superior silica-to-alumina molecular sieves, which are favored by their greater durability thermal: which can thermally degrade during aging, in such a way that a molecular sieve structure can collapse and / or the PGM can sinter, giving less dispersion and consequently less HC and / or CO conversion activity. Thus, it is preferred that the first reactive coating and / or the second reactive coating comprise a molecular sieve at <30% by weight (such as <25% by weight, <20% by weight, for example, <15% by weight) weight) of the individual reactive coating layer. At least one support material remaining from the first reactive coating and / or the second reactive coating may comprise a metal oxide selected from the group consisting of optionally stabilized alumina, amorphous silica-alumina, optionally stabilized zirconia, ceria, titania, a mixed oxide optionally stabilized ceria-zirconia and mixtures of any of the two or more of them.
    [00061] Preferred molecular sieves for use as support material / hydrocarbon absorbers are mid-pore zeolites, preferably aluminosilicate zeolites, that is, those that have a maximum ring size of eight tetrahedral atoms, and large pore zeolites (maximum ten tetrahedral atoms) preferably aluminosilicate zeolite, include natural or synthetic zeolites, such as faujasite, clinoptilolite, mordenite, silicalite, ferrierite, zeolite X, zeolite Y, ultra-stable zeolite Y, zeolite ZSM-5, zeolite Z, Zeolite Z -3, SAPO-5 zeolite, offretite or a beta zeolite, preferably ZSM-5, beta and Y zeolites. Preferred zeolite adsorbent materials have a high silica to alumina ratio, for better hydrothermal stability. The zeolite can have a silica / alumina molar ratio of at least about 25/1, preferably at least about 50/1, with used ranges from about 25/1 to 1000/1, 50/1 to 500/1 , as well as about 25/1 to 100/1, 25/1 to 300/1, about 100/1 to 250/1.
    [00062] The first reactive coating can be arranged in a range of configurations with respect to the second reactive coating. The first reactive coating can be disposed in a first reactive coating zone of the substrate monolith and the second reactive coating can be disposed in a second reactive coating zone of the substrate monolith, in which there is substantially no overlap between the first coating zone. reactive and the second reactive coating zone (for example, there is no overlap between the first reactive coating and the second reactive coating). In general, the first reactive coating zone is disposed at one inlet end of the catalyzed substrate monolith and the second reactive coating zone is disposed at one outlet end of the catalyzed substrate monolith.
    [00063] Alternatively, or in addition, the second reactive coating can be layered above the first reactive coating. Certainly, when the first reactive coating and the second reactive coating are disposed in a filter, care must be taken with any layered arrangement, such that the characteristic “second reactive coating is oriented to come into contact with exhaust gas that came into contact with the first reactive coating ”of the invention is met, for example, it may be necessary to reverse the orientation of the first and second layers of reactive coating applied to the outlet channels of a wall flow filter.
    [00064] The substrate monolith for use in the invention can be a substrate monolith through the flow or a substrate filter monolith. The second reactive coating is generally oriented to contact exhaust gas which came into contact with the first reactive coating. This is to allow the first reactive coating to contact the first exhaust gas. The exhaust gas and any volatile PGM from the first reactive coating is then brought into contact with the second reactive coating which includes a metal oxide to trap the volatilized PGM.
    [00065] A substrate filter monolith typically has inlet and outlet surfaces, where the inlet surfaces are separated from the outlet surfaces by a porous structure. It is preferred that the substrate filter monolith is a wall flow filter, that is, a porous ceramic filter substrate comprising a plurality of input channels arranged in parallel with a plurality of output channels, where each channel of entrance and each exit channel is defined in part by a porous structure ceramic wall, in which each entrance channel is alternately separated from an exit channel by a porous structure ceramic wall and vice versa. In other words, the wall flow filter is a honeycomb arrangement that defines a plurality of primary channels plugged at an upstream end and a plurality of secondary channels not plugged at the upstream end, but plugged at a downstream end. Channels vertically and laterally adjacent to a primary channel are plugged at one end downstream. When viewed from either end, the alternately plugged and open ends of the channels take on the appearance of a board.
    [00066] Catalyzed filters, preferably wall flow filters, can be coated using the method described in Applicant / Inventor WO 2011/080525. That is, a method of coating a honeycomb monolith substrate comprising a plurality of channels with a liquid comprising a catalyst component, the method of which comprises the steps of: (i) maintaining a honeycomb substrate substantially vertically; (ii) introducing a predetermined volume of the liquid into the substrate through the open ends of the channels at a lower end of the substrate; (iii) retain the liquid introduced into the substrate in a sealed manner; (iv) inverting the substrate containing the retained liquid; and (v) applying a vacuum to the open ends of the substrate channels at the inverted, lower end of the substrate to remove the liquid along the substrate channels. The catalyst composition can be coated on the filter channels of a first end, after which the coated filter can be dried.
    [00067] Methods of preparing catalyzed substrate monoliths, including single layer reactive coating coatings and double layer arrangements (one layer of reactive coating above another layer of reactive coating) are known in the art and include WO 99/47260 of Applicant / Inventor, that is, comprising the steps of (a) locating a containment medium at the top end, first of a substrate monolith, (b) dosing a predetermined amount of a first coating of reactive coating component in said medium containment, either in order (a) to (b) or (b) to (a), and (c) applying pressure or vacuum, removing said first coating of reactive coating component on at least a portion of the substrate monolith, and retaining substantially all said amount in the substrate monolith. In a first step a coating of a first application end can be dried and the dry substrate monolith can be folded 180 degrees and the same procedure can be done on one top end, second of the substrate monolith, without substantially any overlap. layered between applications of the first and second ends of the substrate monolith. The resulting coating product is then dried, and then calcined. The process is repeated with a second coating of reactive coating component, to provide a catalyzed substrate monolith (bilayers) according to the invention.
    [00068] Use of a method like this can be controlled using, for example, vacuum resistance, vacuum duration, reactive coating viscosity, reactive coating solids, coating particle or agglomerate size and surface tension, in such a way that catalyst is coated predominantly on the entrance surfaces, but also optionally on the porous structure, but close to the entrance surfaces. Alternatively, the final finish component can be crushed to a size, for example, D90 <5μm, in such a way that they “permeate” the porous structure of the filter (see WO 2005/016497).
    [00069] It is preferred that the catalyzed substrate monolith comprises a substrate filter monolith (e.g., the catalyzed substrate monolith is a catalyzed substrate filter monolith) and a zone arrangement of the first reactive coating and the second coating reactive. More preferably, a first reactive coating zone comprises inlet surfaces of the substrate filter monolith and the second reactive coating zone comprises outlet surfaces of the substrate filter monolith. In this context, the inlet surfaces in general refer to the channel walls of the substrate filter monolith into which exhaust gas enters, and the outlet surfaces in general refer to the channel walls of the substrate filter monolith through from which the exhaust gas comes out. Thus, for example, the porous structure or walls that separate the entrance and exit surfaces define a transition between the first reactive coating zone and the second reactive coating zone.
    [00070] The first reactive coating can comprise an oxidation catalyst or a NOx adsorption catalyst (NAC), as described in the background of the invention above. A NAC contains significant amounts of alkaline earth metals and / or alkali metals with respect to an oxidation catalyst. NAC typically also includes ceria or a cerium-containing mixed oxide, for example, a mixed cerium and zirconium oxide, whose mixed oxide optionally still includes one or more additional lanthanide or rare earth elements.
    [00071] In addition to the first reactive coating and the second reactive coating, the catalyzed substrate monolith of the invention can still comprise additional final finish coatings. However, it is preferred that the catalyzed substrate monolith of the invention has only two final finishing coatings, the first reactive coating and the second reactive coating. Thus, the catalyzed substrate monolith consists of a first reactive coating and a second reactive coating.
    [00072] The invention also relates to an exhaust system. The exhaust system preferably further comprises a second catalyzed substrate monolith comprising a selective catalytic reduction catalyst (SCR), the second catalyzed substrate monolith of which is disposed downstream of the first catalyzed substrate monolith. An optionally catalyzed substrate filter monolith (ie, a third, optionally catalyzed substrate monolith) can be arranged downstream of the second catalyzed substrate monolith (for example, an exhaust system in a DOC / SCR / CSF arrangement discussed in together with the foundations of the previous invention) The substrate filter monolith (i.e., the third, optionally catalyzed substrate monolith) is preferably a wall flow filter. Where catalyzed, the catalyst for use in conjunction with the substrate filter monolith is an oxidation catalyst, but in alternative embodiments it may be a NAC composition. Alternatively, the substrate filter monolith may be non-catalyzed.
    [00073] Typically, the exhaust system of the invention comprises an injector for injecting a nitrogenous reducer in the exhaust gas between the first catalyzed substrate monolith and the second catalyzed substrate monolith. Alternatively, (that is, in addition to injecting a nitrogenous reducer, such as ammonia or a precursor thereof, such as urea is disposed between the first catalyzed substrate monolith and the second catalyzed substrate monolith), or in addition to injecting a nitrogen reducer (eg, ammonia or a precursor to it, such as urea), engine management means can be provided to enrich exhaust gas, such that ammonia gas is generated in situ by reducing NOx in the catalyst composition of the first reactive coating and / or a substrate monolith comprising a DOC or NAC disposed upstream of the first substrate monolith or downstream of the first substrate monolith. Where the substrate monolith comprising DOC or NAC is disposed downstream of the filter, it is preferably disposed upstream of the means for injecting ammonia or a precursor thereof.
    [00074] Nitrogen reducers and precursors thereof for use in the present invention include any of those mentioned above in conjunction with the fundamentals section. Thus, for example, the nitrogen reducer is preferably ammonia or urea.
    [00075] In combination with a properly designed and managed diesel compression ignition engine, enriched exhaust gas, that is, exhaust gas containing increased amounts of carbon monoxide and hydrocarbon with respect to normal lean running mode, comes into contact the NAC.
    [00076] Components in a NAC, such as ceria promoted by PGM or ceria-zirconia can promote the water-gas displacement reaction, that is, CO2 + H2O (vW CO. + H2 (g) evolving H2. Really the note of footer for side reaction for reactions (3) and (4) presented above, for example, Ba (NO3) 2 + 8H2 ^ BaO + 2NH3 + 5H2O, NH3 can be generated in situ and stored for NOx reduction in the SCR catalyst a downstream.
    [00077] When the first catalyzed substrate monolith is a substrate filter monolith (for example, a catalyzed wall flow filter), the exhaust system preferably still comprises a third catalyzed substrate monolith, wherein the third Catalyzed substrate is a flow-through substrate monolith comprising an oxidation catalyst, for example, a DOC or a NAC, the third catalyzed substrate monolith of which is arranged upstream of the first catalyzed substrate monolith.
    [00078] The second catalyzed substrate monolith typically comprises a catalyst to selectively catalyze the reduction of nitrogen oxides to dinitrogen with a nitrogen reducer, also known as a selective catalytic reduction (SCR) catalyst. The SCR catalyst can be coated as a coating on a substrate monolith, as described above. Alternatively, the SCR catalyst can be supplied as an extrudate (also known as a “catalyst body”), that is, the catalyst is mixed with components of the substrate structure monolith, which are both extruded, so the catalyst is part of the walls of the substrate monolith.
    [00079] The SCR catalyst of the second substrate monolith typically comprises a substrate filter monolith or a substrate monolith through the flow. It is also possible to prepare a wall flow filter from an extruded SCR catalyst (see WO 2009/093071 and WO 2011/092521 by Applicant / Inventor). SCR catalysts can be selected from the group consisting of at least one of Cu, Hf, La, Au, Em, V, lanthanides and transition metals of group VII, such as Fe, supported on a refractory oxide or molecular sieve. Suitable refractory oxides include A1203, Ti02, Ce02, Si02, Zr02 and mixed oxides containing two or more of the same. Non-zeolite catalyst may also include tungsten oxide, for example, V205 / W03 / Ti02. Preferred metals of particular interest are selected from the group consisting of Ce, Fe and Cu. Molecular sieves can be exchanged ionically with the previous metals.
    [00080] It is preferred that at least one molecular sieve is an aluminosilicate zeolite or a SAPO. At least one molecular sieve can be a small, medium or large pore molecular sieve, for example. By "small pore molecular sieve" here is meant molecular sieves containing a maximum ring size of 8 tetrahedral atoms, such as CHA; By "medium pore molecular sieve" here is meant a molecular sieve containing a maximum ring size of 10 tetrahedral atoms, such as ZSM-5; and by "large pore molecular sieve" here is meant a molecular sieve having a maximum ring size of 12 tetrahedral atoms, such as beta. Small-pore molecular sieves are potentially advantageous for use in SCR catalysts - see, for example, Applicant / Inventor WO 2008/132452. Molecular sieves for use in SCR catalysts according to the invention include one or more metals incorporated in a molecular sieve frame, for example, Fe "in-frame" Beta and Cu "in-frame" CHA.
    [00081] Particular molecular sieves for application in the present invention are selected from the group consisting of AEI, ZSM-5, ZSM-20, ERI including ZSm-34, mordenite, ferrierite, BEA including Beta, Y, CHA, LEV including Nu- 3, MCM-22 and EU-1, with CHA molecular sieves, for example, CHA aluminosilicate, currently preferred, particularly in combination with Cu as the ion exchange promoter, for example.
    [00082] The present invention also relates to a low combustion internal combustion engine. The low-burn internal combustion engine can be a positive ignition, for example, a spark ignition, engine that typically runs on gasoline fuel or combinations of gasoline fuel and other components, such as ethanol, but is preferably a compression ignition, for example, a diesel engine. Low combustion internal combustion engines include homogeneous charge compression ignition (HCCI) engines, powered by both gasoline and so on. fuel or diesel fuel.
    [00083] An exhaust system of the present invention is shown in figure 6A. Exhaust system 10 comprises series arrangement of an upstream downstream catalyzed wall flow filter 2; and a substrate 4 monolith wall flow filter coated with a Cu / CHA SCR catalyst. Each substrate monolith 2, 4 is arranged in a metal or "can" container including cone diffusers and they are connected by a series of conduit 3 with a smaller cross-sectional area than a cross-sectional area of any of the substrate monoliths 2, 4 Cone diffusers act to spread the flow of exhaust gas entering a "canned" substrate monolith housing, in such a way that the exhaust gas as a whole is directed through substantially the entire "touching" front ”Each substrate monolith. Exhaust gas exiting the substrate monolith 4 is emitted into the atmosphere in the “tail pipe” 5.
    [00084] Catalyzed wall flow filter 2 is coated with a NOx absorbent catalyst (NAC) composition in a zone 6 in its input channels and palladium supported on particulate alumina in a zone 8 in its outlet channels. In combination with a properly designed and managed diesel compression ignition engine (upstream of substrate monolith 2, not shown), enriched exhaust gas, ie exhaust gas containing increased amounts of carbon monoxide and hydrocarbon with respect to in normal lean running mode, contact the NAC. Components in a NAC, such as ceria promoted by PGM or ceria-zirconia can promote the water-gas displacement reaction, that is, CO (g) + H2O (V) ^ CO2 (g)) + Hfe) evolving H2. Really the footnote for side reaction for reactions (3) and (4) presented above, for example, Ba (NO3) 2 + 8H2 ^ BaO + 2NH3 + 5H2O, NH3 can be generated in situ and stored for NOx reduction in the downstream SCR catalyst.
    [00085] Figure 6B shows an alternative embodiment of an exhaust system 20 according to the present invention comprising, in series arrangement of a catalyzed substrate monolith through the upstream downstream flow 12; an ammonia source 13 comprising an injector for an ammonia precursor, urea; and a substrate monolith through flow 14 coated with a Fe / Beta SCR catalyst. Each substrate monolith 12, 14 is arranged in a metal or “can” container including cone diffusers and they are connected by a series of conduit 3 with a smaller cross-sectional area than a cross-sectional area of any of the substrate monoliths 12, 14 Exhaust gas exiting the substrate monolith 14 is emitted into the atmosphere in the “tail pipe” 5.
    [00086] Catalyzed substrate monolith through flow 12 comprises a first zone 16 defined in part by an end upstream of the same coated with a ratio 4: 1 Pt: Pd by weight catalyst in which Pt and Pd are supported on a material support; and a second zone 18 of about 50% of a total length of the substrate monolith through the flow without substantially any overlap with first zone 16, the second zone 18 of which comprises a two-layer arrangement in which a first layer (or base) comprises platinum supported on alumina and a second layer (or top) comprising palladium supported on alumina. The substrate monolith catalyzed through the flow is designed for the purpose of promoting reaction (1) and thus the reaction (6) in the downstream SCR catalyst. EXAMPLES EXAMPLE 1 - Preparation of substrate monolith coated with 5 wt% Fe / Beta Zeolite
    [00087] Commercially available beta zeolite was added to an aqueous solution of Fe (NO3) 3 with stirring. After mixing, binders and rheology modifiers were added to form a reactive coating composition.
    [00088] A cordierite substrate monolith through the flow of 400 cells per square inch (cpsi) (1 square inch 6.45 cm2) was coated with a 5% aqueous weight slurry of Fe / Beta zeolite sample using the method described in Applicant / Inventor WO 99/47260, that is, comprising the steps of (a) locating a containment medium on top of a support, (b) dosing a predetermined amount of a component liquid in said medium of containment, either in the order (a) then (b) or (b) then (a), and (c) applying pressure or vacuum, removing said component liquid in at least a portion of the support, and retaining substantially all said quantity in the support . This coated product (coated on one end only) is dried and then calcined and this process is repeated from the other ends, in such a way that substantially every substrate monolith is coated, with a minor overlap in the axial direction at the joint between the two. coatings. A 1-inch (2.54cm) diameter x 3-inch (7.62cm) core was cut from the finished article. COMPARATIVE EXAMPLE 2 - Preparation of wall flow filter catalyzed only with Pt
    [00089] A reactive coating composition comprising a mixture of crushed alumina particles to a relatively high particle size distribution, platinum nitrate, binders and rheology modifiers in deionized water was prepared. An aluminum titanate wall flow filter was coated with the catalyst composition at a reactive coating charge of 0.0122 g cm3 (0.2 g / in3) at a final total Pt charge of 178.5 g / m3 (5g / ft-3) using the method and apparatus described in Applicant / Inventor WO 2011/080525, in which channels at a first end intended for orientation to an upstream side were covered by 75% of their total length size with a reactive coating comprising platinum nitrate and particulate alumina intended for the upstream end thereof; and channels at the opposite end and intended to be oriented to a downstream side are coated to 25% of their total length size with the same reactive coating as the inlet channels. That is, the method comprised the steps of: (i) maintaining a substrate of the alveolar monolith substantially vertically; (ii) introducing a predetermined volume of the liquid into the substrate through the open ends of the channels at a lower end of the substrate; (iii) retain the liquid introduced into the substrate in a sealed manner; (iv) inverting the substrate containing the retained liquid; and (v) applying a vacuum to the open ends of the substrate channels at the inverted, lower end of the substrate to remove the liquid along the substrate channels. The catalyst composition was coated on the filter channels of a first end, after which the coated filter was dried. The dry coated filter of the first end was then spun and the method was repeated to coat the same catalyst with filter channels of the second end, followed by drying and calcination.
    [00090] A 1-inch (2.54 cm) diameter x 3-inch (7.62 cm) long core was cut from the finished article. The resulting part is described as “freshly prepared”, that is, not aged. EXAMPLE 3 - Preparation of catalyzed wall flow filter containing Pt inlet / Pd outlet
    [00091] A coated filter was prepared using the same method as in comparative example 2, except 100%) of the total channel length of the channels intended for orientation to the contact side of the gas was coated with a reactive coating containing platinum nitrate and alumina before the coated filter has been dried; and 35% of the total length of the filters coated with Pt channels intended for orientation to the outside were coated with a reactive coating containing palladium nitrate and alumina. The resulting fully coated filter was then dried, then calcined. The total Pt load on the coated filter was 178.5 gm-3 (5gft-3) and the total Pd load on the coated filter was 62.475 gm-3 (1.75 gft-3)
    [00092] A 1 inch (2.54 cm) diameter x 3 inch long core was cut from the finished article. The resulting part is described as “freshly prepared”, that is, not aged. EXAMPLE 4 - Preparation of catalyzed wall flow filter containing Pt inlet / Al outlet
    [00093] A coated filter was prepared using the same method as Example 3, except for 35% of the total length of the channels intended for orientation to the outside, they were coated with a reactive coating containing alumina only. The resulting coated filter was then dried, then calcined. The total load of Pt in the input channels of the coated filter was 178.5 gm-3 (5gft-3).
    [00094] A 1-inch (2.54 cm) diameter x 3-inch (7.62 cm) long core was cut from the finished article. The resulting part is described as “freshly prepared”, that is, not aged. EXAMPLE 5 - Preparation of catalyzed wall flow filter containing Pt inlet / single layer Pt: Outlet Pd
    [00095] A coated filter was prepared using the same method as in comparative example 2, except that no reactive coating applied to the filter outlet channels included palladium nitrate other than platinum nitrate. The load of the reactive coating on the input and output channels was conducted in such a way as to reach a load of 178.5 gm-3 (5gft3) Pt, 44.6 gm-3 (1.25g / ft3) Pd in both inlet and outlet surfaces, that is, a total PGM load of 223.1g / m3 (6.25g / ft3).
    [00096] A core 1 inch (2.54 cm) in diameter x 3 inches (7.62 cm) in length has been cut from the finished article. The resulting part is described as “freshly prepared”, that is, not aged. EXAMPLE 6 - Preparation of catalyzed wall flow filter containing layered Pt / Pt inlet / Pd outlet
    [00097] A coated filter was prepared using the same method as in comparative example 2, except that neither of the two layers of reactive coating was applied to the 25% of the total length of the outlet channel zone. In a first layer (or base), the reactive coating contained platinum nitrate and alumina. The coated filter was then dried and calcined before a second layer (or top) reactive coating was applied that contained palladium nitrate and alumina. The load of the reactive coating on the input and output channels was conducted in such a way as to arrive at a total combined load on the input channels and the output channels of 178.5 gm-3 (5g / ft3) Pt, 44.6 gm-3 (1.25g / ft3) Pd, that is, a total PGM load of 223.1g / m3 (6.25g / ft3).
    [00098] A 1 inch (2.54 cm) diameter x 3 inch long core was cut from the finished article. The resulting part is described as “freshly prepared”, that is, not aged. EXAMPLE 7 - Preparation of catalyzed wall flow filter containing 1: 1% by weight of Pt: Pd
    [00099] A coated filter was prepared using the same method as in comparative example 2, except that no reactive coating applied to both the inlet and outlet channels of the filter included palladium nitrate in addition to platinum nitrate. The load of the reactive coating in the inlet and outlet channels was conducted in such a way as to arrive at a load (178.5 gm-3) 5gft3 Pt, 178.5 gm-3 (5gft3) Pd on both the inlet and outlet surfaces on the outlet surfaces, that is, a total PGM load of 10g / ft3.
    [000100] A 1 inch (2.54 cm) diameter x 3 inch (7.62cm) long core was cut from the finished article. The resulting part is described as “freshly prepared”, that is, not aged. EXAMPLE 8 - Preparation of catalyzed wall flow filter containing 5: 1% by weight of Pt: Pd
    [000101] A coated filter was prepared using the same method as in comparative example 2, except that no reactive coating applied to both the inlet and outlet channels of the filter included palladium nitrate in addition to platinum nitrate. The load of the reactive coating on the input and output channels was conducted in such a way as to reach a load of 178.5 g / m3 (5g / ft3) Pt, 35.7 g / m3 (1g / ft3) of Pd both on the inlet and outlet surfaces, that is, a total PGM load of 214.2 g / m3 (6g / ft3).
    [000102] A 1 inch (2.54 cm) diameter x 3 inch long core was cut from the finished article. The resulting part is described as “freshly prepared”, that is, not aged. EXAMPLE 9 - System tests
    [000103] The tests were carried out in a first synthetic catalyst activity test (SCAT) reactor illustrated in figure 1, in which a freshly prepared core of the coated Fe / Beta zeolite SCR catalyst of example 1 is disposed in a conduit downstream of a core of either of the catalyzed wall flow filter of comparative example 2 or example 3, 4, 5, 6, 7 or 8. A mixture of synthetic gas was passed through the conduit at an oscillating volume of the 30,000 h-1 catalyst, an oven was used to heat (or “age”) the catalyzed wall flow filter sample to a steady state temperature at a filter inlet temperature of 900 ° C for 60 minutes, during which the temperature of the inlet SCR catalyst was 300 ° C. A cooling mechanism with air (heat exchanger) or water was used to effect the temperature drop between the filter and the SCR catalyst. The gas mixture during aging was 10% O2, 6% H2O, 6% CO2, 100 ppm CO, 400 ppm NO, 100 ppm HC as C I, N2 balance.
    [000104] After aging, the aged SCR catalysts were removed from the first SCAT reactor and inserted into a second SCAT reactor specifically to test the NH3-SCR activity of the aged samples. The aged SCR catalysts were then tested for SCR activity at 150, 200, 250, 300, 350, 450, 550 and 650 ° C using a mixture of synthetic gas (02 = 14%; H2O = 7%; CO2 = 5%; NH3 = 250ppm; NO = 250ppm; NO2 = 0 ppm; N2 = equilibrium) and the resulting NOx conversion for examples 3, 5 and 6 were plotted against temperature for each setting of temperature data in figure 2 against activity of freshly prepared SCR catalyst and against an aged SCR catalyst behind comparative example 2. The graph shown in figure 3 plots the resulting NOx conversion for examples 4 and 7 using the same comparisons. This graph essentially measures the competition between reaction (9) and reaction (5) and just as reaction (9) affects the conversion of NOx by the consumption of NH3 available for the SCR reaction (reaction (5)) *
    [000105] The results are shown in figures 2 and 3. It can be seen that the SCR catalysts for use in the exhaust system according to the present invention retain more activity than the SCR catalyst in comparative example 2, although they retain less activity SCR than a freshly prepared catalyst. The inventors interpreted this result by showing that the loss in SCR activity is caused in part by the deposition of the low Pt levels of the upstream catalyzed wall flow filter on the downstream SCR catalyst. Substantially no loss in activity was seen between a freshly prepared Fe / Beta catalyst and an Fe / Beta catalyst aged at 300 ° C for 1 hour with no catalyst present upstream (results not shown). EXAMPLE 10 - Preparation of substrate monolith coated with 3 wt% Cu / CHA Zeolite
    [000106] Commercially available CHA aluminosilicate zeolite was added to an aqueous solution of Cu (NO3) 2 with stirring. The slurry was filtered, then washed and dried. The procedure can be repeated to achieve a desired metal charge. The final product was calcined. After mixing, binders and rheology modifiers were added to form a reactive coating composition.
    [000107] A cordierite substrate monolith through the flow of 400 cpsi (1 square inch 6.45 cm2) was coated with a 3% by weight aqueous slurry of Cu / CHA zeolite sample using the method described in WO 99 Applicant / Inventor / 47260 described in example 1 above. The coated substrate monolith was aged in an air oven at 500 ° C for 5 hours. A 1 inch (2.54 cm) diameter x 3 inch (7.62 cm) long core was cut from the finished article. EXAMPLE 11 - Additional Pt: Pd weight ratio studies
    [000108] Two diesel oxidation catalysts were prepared as follows: Diesel oxidation catalyst A
    [000109] A single layer DOC was prepared as follows. Platinum nitrate and palladium nitrate were added to a silica-alumina slurry. Beta zeolite was added to the slurry, in such a way that it comprised <30% of the solids content as zeolite by mass. The reactive coating slurry was dosed onto a substrate through the flow of 400 cpsi (1 square inch 6.45 cm2) using the method of example 1 above. The dosed part was dried and then calcined at 500 ° C. The total load of the platinum group metal in the reactive coating was 2142 g / m3 (60gft-3) and the weight ratio of total Pt: Pd was 4: 1. A 1-inch (2.54 cm) diameter x core 3 inches (7.62 cm) in length was cut from the finished article. The resulting part can be described as "freshly prepared", that is, not aged. Diesel oxidation catalyst B
    [000110] A single layer DOC was prepared as follows. Platinum nitrate and palladium nitrate were added to a silica-alumina slurry. Beta zeolite was added to the slurry, in such a way that it comprised <30% of the solids content as zeolite by mass. The reactive coating slurry was dosed on a substrate through the flow of 400 cpsi (1 square inch 6.45 cm2) using the same method as used for DOC A. The dosed part was dried and then calcined at 500 ° C. The total PGM load on the single-layer DOC was 4284 g / m3 (120 g / ft3) and the Pt: Pd weight ratio was 2: 1. A 1-inch (2.54 cm) diameter x 3-inch core ( 7.62 cm) in length was cut from the finished article. The resulting part can be described as "freshly prepared", that is, not aged.
    [000111] Both catalysts were tested according to the protocols presented in example 12. The results are shown in figure 5 with reference to a control (aged SCR catalyst that has not yet been aged downstream of either DOC A or DOC B ). EXAMPLE 12 - System tests
    [000112] The tests were carried out in a first laboratory reactor of synthetic catalyst activity (SCAT) illustrated in figure 1, in which an aged core of the SCR catalyst coated with zeolite Cu / CHA of example 10 was disposed in a conduit downstream of a core of any diesel oxidation catalyst (DOC) A or B (according to Example 11). A mixture of synthetic gas was passed through the flue at a rate of 6 liters per minute. An oven was used to heat (or "age") the DOC samples to a steady state temperature at a catalyst outlet temperature of 900 ° C for 2 hours. The SCR catalyst was disposed downstream of the DOC sample and was maintained at a catalyst temperature of 300 ° C during the aging process by adjusting the length of the tube between the furnace outlet and the SCR inlet, although a jacket from the heat exchanger water-cooled can also be used. Temperatures were determined using appropriately positioned thermocouples (Ti and T2). The gas mixture used during aging was 40% air, 50% N2, 10% H2O.
    [000113] After the aging of the DOC, the SCR catalysts were removed from the first SCAT reactor and inserted into a second SCAT reactor specifically to test H3-SCR activity of the aged samples. SCR catalysts were then tested for SCR activity at 500 ° C using a synthetic gas mixture (02 = 10%; H2O = 5%; CO2 = 7.5%; CO = 330ppm; NH3 = 400ppm; NO = 500ppm; NO2 = 0 ppm; N2 = equilibrium, that is, an alpha value of 0.8 was used (NH3: NOx ratio), in such a way that the maximum possible conversion of NOx available was 80%) and the resulting NOx conversion was plotted against temperature in the bar graph attached in figure 5. This graph essentially measures the competition between reaction (9) and reaction (5) and how much reaction (9) affects the conversion of NOx by the consumption of available NH3 required for the SCR reaction (reaction (5)). Weight ratio study Pt: Pd - Conclusions
    [000114] Taken as a whole, the results of example 9 shown in figure 4 together with Examples 7 and 8 and Comparative example 2 indicate that a weight ratio Pt: Pd of between 1: 1 and 5: 1 is beneficial in reducing the problem of loss of conversion of NOx activity through volatilization of platinum group metal, mainly platinum, from a platinum group metal containing catalyst to a downstream SCR catalyst; and
    [000115] The results of example 12 shown in figure 5 in conjunction with diesel oxidation catalysts A and B show that for aged SCR catalyst downstream of a DOC having a weight ratio 2: 1 Pt: Pd overall, the loss of conversion of NOx activity is relatively slight to 67% conversion of NOx activity compared to the control to 72% conversion of NOx activity (an aged SCR catalyst behind a 1: 1 weight ratio Pt: overall DOC Pd (not described) here) using the same protocol had a NOx activity conversion of 69%). However, when the general weight ratio Pt: Pd was increased to 4: 1, SCR activity was significantly reduced to 48%.
    [000116] The inventors conclude, in this way, that there is a limit to about a 2: 1 Pt: weight ratio: general Pd above which Pt volatility is more likely to happen. Thus, limiting to a general weight ratio Pt: Pd of 2: 1 in the DOC as a whole, and the <weight ratio 2: 1 Pt: Pd in the second layer of reactive coating, Pt in the DOC is less likely to volatilize and migrate to an SCR catalyst downstream.
    [000117] To avoid any doubt, all the contents of any and all documents cited here are incorporated by reference in this patent application.
    权利要求:
    Claims (14)
    [0001]
    1. Exhaust system for a low-combustion internal combustion engine, characterized by the fact that the system comprises: a first substrate monolith catalyzed by flow for use in the treatment of exhaust gas emitted from the low-combustion internal combustion engine, that the first substrate monolith catalyzed by flow comprises: a first reactive coating and a second reactive coating, wherein the first reactive coating comprises a catalyst composition comprising at least one platinum group metal (PGM) and at least one material support for at least one PGM, wherein the at least one PGM in the first reactive coating comprises platinum; or both platinum and palladium in a weight ratio> 1.5: 1, which is liable to volatilize when the first reactive coating is exposed to relatively extreme conditions including relatively high temperatures of> 700 ° C, where the second reactive coating comprises , to trap volatilized PGM, at least one metal oxide selected from the group consisting of optionally stabilized alumina, amorphous silica-alumina, optionally stabilized zirconia, ceria, titania, an optionally stabilized ceria-zirconia oxide and mixtures of any of the two or more of them bearing at least one metal which is palladium, in which the second reactive coating is oriented to come into contact with exhaust gas which came in contact with the first reactive coating; a second catalyzed substrate monolith comprising a selective catalytic reduction catalyst (SCR), the second catalyzed substrate monolith of which is disposed downstream of the first catalyzed substrate monolith through the flow; and an injector for injecting a nitrogenous reducer in the exhaust gas between the first catalyzed substrate monolith through the flow and the second catalyzed substrate monolith.
    [0002]
    2. Exhaust system according to claim 1, characterized in that the first reactive coating of the first substrate monolith catalyzed through the flow is arranged in a first reactive coating zone of the first substrate monolith catalyzed through the flow, and the second reactive coating is disposed in a second reactive coating zone of the first substrate monolith catalyzed through the flow, in which there is no overlap between the first reactive coating zone and the second reactive coating zone.
    [0003]
    Exhaust system according to claim 1, characterized by the fact that the second reactive coating is arranged in a layer above the first reactive coating.
    [0004]
    Exhaust system according to any one of claims 1 to 3, characterized in that at least the first reactive coating comprises an oxidation catalyst or a NOx adsorption catalyst.
    [0005]
    Exhaust system according to any one of claims 1 to 4, characterized in that the first reactive coating comprises a weight ratio of Pt: Pd of <10: 1.
    [0006]
    Exhaust system according to any one of claims 1 to 5, characterized in that the total amount of the metal of the platinum group in the first reactive coating is 1249.5 to 7140 gm-3.
    [0007]
    Exhaust system according to any one of claims 1 to 6, characterized in that the stabilized metal oxide is one or more of silica and rare earth metals.
    [0008]
    Exhaust system according to any one of claims 1 to 7, characterized in that the metal oxide of the second reactive coating and the at least one support material of the first reactive coating are different.
    [0009]
    Exhaust system according to any one of claims 1 to 8, characterized in that the second reactive coating comprises at least one metal oxide in a total amount of 0.0061 to 0.305 gm-3.
    [0010]
    Exhaust system according to any one of claims 1 to 9, characterized in that the metal oxide of the second reactive coating is selected from the group consisting of optionally stabilized alumina and an optionally stabilized mixed ceria-zirconium oxide.
    [0011]
    Exhaust system according to any one of claims 1 to 10, characterized in that the total amount of palladium in the second reactive coating is 1785 to 6247.5 gm-3.
    [0012]
    Exhaust system according to any one of claims 1 to 11, characterized in that it comprises a third substrate monolith, wherein the third substrate monolith is a substrate filter monolith, the third substrate monolith of which is arranged downstream of the second catalyzed substrate monolith.
    [0013]
    Exhaust system according to claim 12, characterized in that the third substrate monolith comprises an oxidation catalyst.
    [0014]
    14. Method for reducing or preventing a selective catalytic reduction catalyst (SCR) in a second substrate monolith in an exhaust system for a low-burn internal combustion engine as defined in claim 1 from being poisoned with platinum group metal (PGM) that can volatilize from the first reactive coating of the first substrate monolith catalyzed through the flow when the first reactive coating is exposed to relatively extreme conditions, including relatively high temperatures of> 700 ° C, characterized by trapping volatile PGM from the first coating reactive in the second reactive coating of the first flow-catalyzed substrate monolith through the flow.
    类似技术:
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    BR112014013261B1|2021-02-23|exhaust system for a low-combustion internal combustion engine, and method to reduce or prevent a selective catalytic reduction catalyst
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    同族专利:
    公开号 | 公开日
    KR20140110932A|2014-09-17|
    BR112014013261A2|2017-06-13|
    US20150238934A1|2015-08-27|
    RU2618058C2|2017-05-02|
    GB201200780D0|2012-02-29|
    EP2790816A1|2014-10-22|
    GB2497597A|2013-06-19|
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    JP2017060946A|2017-03-30|
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    GB201402437D0|2014-03-26|
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    EP2790816B1|2019-12-11|
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    GB201222280D0|2013-01-23|
    GB2497659B|2015-04-22|
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    WO2013088133A1|2013-06-20|
    RU2014128623A|2016-02-10|
    CN106423260A|2017-02-22|
    JP6104272B2|2017-03-29|
    CN103974759A|2014-08-06|
    DE102012025746A1|2015-06-25|
    DE102012222801B4|2020-06-04|
    JP6573862B2|2019-09-11|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-09-08| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2021-02-02| B09A| Decision: intention to grant|
    2021-02-23| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161569523P| true| 2011-12-12|2011-12-12|
    US61/569,523|2011-12-12|
    GB1200780.3|2012-01-18|
    GB1200780.3A|GB2497597A|2011-12-12|2012-01-18|A Catalysed Substrate Monolith with Two Wash-Coats|
    PCT/GB2012/053090|WO2013088133A1|2011-12-12|2012-12-11|Catalysed substrate monolith|
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