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    • 专利摘要:
    catalyzed substrate monolith, exhaust system for a low-burn internal combustion engine, low-burn internal combustion engine, and method for reducing or preventing a selective catalytic reduction catalyst from platinum poisoning the invention provides a catalyst for exhaust gas cleaning oxidation and, in particular, an oxidation catalyst to clean the exhaust gas discharged by internal combustion engines of the compression ignition type (particularly diesel engines). the invention further relates to a catalyzed substrate monolith, comprising an oxidation catalyst on a substrate monolith, for use in the treatment of exhaust gas emitted by a low-burn internal combustion engine. in particular, the invention relates to a catalyzed substrate monolith, comprising a first reactive coating and a second reactive coating, wherein the second reactive coating is arranged in a layer above the first reactive coating.
    公开号:BR112014008228B1
    申请号:R112014008228
    申请日:2012-10-05
    公开日:2019-12-24
    发明作者:Francis Chiffey Andrew；Walker Andrew；Michael Gavin；Oyamada Hanako；Gast Jane；Wang Lifeng；Richard Phillips Paul；Blakeman Philip；Rao Rajaram Raj；Sumiya Satoshi；Chatterjee Sougato
    申请人:Johnson Matthey Japan Godo Kaisha；Johnson Matthey Plc；
    IPC主号:
    专利说明:

    CATALYSTED SUBSTRATE MONOLITH, EXHAUST SYSTEM FOR A POOR BURNT INTERNAL COMBUSTION ENGINE, POOR BURNT INTERNAL COMBUSTION ENGINE, AND, METHOD TO REDUCE OR PREVENT A SELECTIVE CATALYTIC REDUCTION CATALYST FROM ENVENENING WITH PLATINUM
    FIELD OF THE INVENTION [0001] The invention relates to an exhaust gas cleaning oxidation catalyst and, in particular, to an oxidation catalyst for cleaning exhaust gas discharged by compression ignition type internal combustion engines (particularly diesel engines). The invention also relates to a catalyzed substrate monolith, comprising an oxidation catalyst on a substrate monolith, for use in the treatment of exhaust gas emitted by a low-burn internal combustion engine. In particular, the invention relates to a catalyzed substrate monolith, comprising a first reactive coating and a second reactive coating, wherein the second reactive coating is layered on top of the first reactive coating. The invention also relates to the use of such catalyzed substrate monoliths from exhaust systems of low-burn internal combustion engines, particularly vehicular low-burn internal combustion engines.
    BACKGROUND OF THE INVENTION [0002] There are generally four classes of pollutants that are legislated by government organizations worldwide: carbon monoxide (CO), unburned hydrocarbons (HC), nitrogen oxides (NO X ) and particulate matter (PM ).
    [0003] Oxidation catalysts have been used to clean hydrocarbon (HC), carbon monoxide (CO) and also the soluble organic fraction (SOF) in the exhaust gas produced by combustion of fuel in internal combustion engines of the type compression ignition (see
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    2/63
    Japanese Patent Kokai No. 9-271674). Recently, attention has also been focused on the treatment of particulate matter (PM), produced by combustion of fuel in internal combustion engines of the compression ignition type, and filters that can collect PM (diesel particulate filters (DPF)). An oxidation catalyst was placed in the upstream part of the DPF in order to improve the efficiency of the treatment of PM in the DPF (see Japanese Patent Kokai No. 2006-272064.
    [0004] Heavier fuels contain a higher fraction of sulfur. In compression-type internal combustion engines, which use diesel oil as fuel, sulfur oxides (SOx) are emitted in the fuel combustion and catalytic process, and the oxidation catalyst activity has been reduced by the presence of SOx, (sulfur poisoning) ). To combat this problem, oxidation catalysts, having resistance to sulfur poisoning, have been proposed, which have zeolite as a mixture containing specific proportions by weight of ZSM-5 and zeolite-β (see Japanese Patent Kokai No. 2007-229679). In addition, to make exhaust gas cleaning more efficient, a NO3 cleaning catalyst, having a double layer structure, has been proposed that comprises two different catalyst layers, namely, a camadaχ oxidation catalyst layer and a selective reduction catalyst NO X (see Japanese Patent Kokai No. 2008-279352).
    [0005] As emission standards for permissible emission of pollutants in exhaust gases from vehicle engines become progressively more rigid, a combination of engine control and multiple catalytic exhaust gas aftertreatment systems are being proposed and developed to meet these emission standards. For exhaust systems containing a particulate filter, it is common to use engine control periodically (eg, every 500 km), to increase the temperature inside the filter, in order to burn substantially
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    3/63 all the remaining soot retained in the filter, to thereby return the system to a baseline level. These soot combustion events faced by an engine are often called “filter regeneration”. Although a primary focus of filter regeneration is to burn the soot trapped in the filter. An unintended consequence is that one or more catalyst coatings, present in the exhaust system, e.g. eg a filter coating on the filter itself (a so-called catalyzed soot filter (CSF)), an oxidation catalyst (such as a diesel oxidation catalyst (DOC)) or a NO X adsorber catalyst (NAC), located upstream or downstream of the filter (eg, a first DOC followed by a particulate diesel filter, followed in turn by a second DOC and, finally, an SCR catalyst), can be regularly exposed to high gas temperatures exhaust, depending on the level of engine handling control in the system. Such conditions can also be experienced with occasional unintended engine disturbance modes or uncontrolled or poorly controlled regeneration events. However, some diesel engines, particularly heavy duty diesel engines, operating at high load, may even expose the catalysts to significant temperatures, e.g. > 600 ° C, under normal operating conditions.
    [0006] As vehicle manufacturers develop their engines and engine control systems to meet emission standards, the Claimant / Assignee is being asked by vehicle manufacturers to propose catalytic components and combinations of catalytic components, to assist in the goal of meet emission standards. Such components include DOCS to oxidize CO, HCs and, optionally, also NO; 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 lean exhaust gas and to desorb adsorbed NO X and to reduce it by
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    N 2 in a rich exhaust gas (see below); and selective catalytic reduction (SCR) catalysts to reduce ΝΟχ in NO 2 , in the presence of a nitrogen reducing agent, such as ammonia (see below).
    [0007] In practice, the catalyst compositions employed in DOCs and CSFs are very similar. Generally, 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 through-flow substrate monolith, comprising a metal or ceramic honeycomb monolith, having an elongated channel formation extending through it, channels being opened at both ends; a CSF substrate monolith is a filtering monolith, such as a wall flow filter, e.g. 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 are defined in part by a porous ceramic wall , in which each input channel is alternatively separated from an output channel by a porous ceramic wall and vice versa. In other words, the wall flow filter is a honeycomb arrangement defining a plurality of first channels plugged at an upstream end and a plurality of second channels not plugged at the upstream end, but plugged at a downstream end. The channels vertically and laterally adjacent to a first 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 chessboard.
    [0008] Multiple very complicated red catalyst arrangements, such as DOCs and NACs, can be coated on a through-flow substrate monolith. Although it is possible to coat a surface of a filter monolith, e.g. eg a channel surface
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    5/63 inlet of a wall flow filter, with more than one layer of catalyst composition, a problem with the coating filtration monoliths is to avoid unnecessarily increasing back pressure when in use by overloading the filter monolith with catalyst wash layer, thereby restricting the passage of gas through it. Consequently, although coating the surface of a filter substrate 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 zones, e.g. e.g., axially segregated front and rear semi-zones of a filter monolith, or by coating an inlet channel of a wall flow filter substrate monolith with a first catalyst composition and an outlet channel with a second composition catalyst. However, in particular embodiments of the present invention, the filter inlet is coated with one or more layers, which layers may be the same or different catalyst composition. It has also been proposed to coat a NAC composition on a filter substrate monolith (see, eg, EP 0766993).
    [0009] In exhaust systems comprising multiple catalyst components, each comprising a separate substrate monolith, typically the SCR catalyst is located downstream of a DOC and / or a CSF and / or a NAC, because it is known that oxidizing some oxide of nitrogen (NO) in the exhaust gas into nitrogen dioxide (NO 2 ), so that there is a ratio of about 1: 1 of NO: NO 2 leaving DOC and / or CSF and / or NAC, downstream SCR reaction is promoted (see below). It is also well known from EP341832 (the so-called continuously regenerating collector or CRT®) that NO 2 , generated by oxidizing NO in the exhaust gas to NO 2 , can be used to passively burn soot in a downstream filter. In exhaust system arrangements, where the EP341832 process is important, if the SCR catalyst was located upstream of the filter, this
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    6/63 would reduce or prevent the process of trapped soot by burning NO2, because most of the ΝΟχ used to burn soot would likely be removed in the SCR catalyst.
    [00010] However, a preferred system arrangement for light duty diesel vehicles is a diesel oxidation catalyst (DOC) followed by a nitrogen reducing injector, then an SCR catalyst and, finally, a catalyzed soot filter (CSF). An abbreviation for such an arrangement is “DOC / SCR / CSF”. This arrangement is preferred for light duty diesel vehicles, because an important consideration is to get the conversion of NO X into an exhaust system as quickly as possible after a vehicle's engine is started to enable (i) the gearbox precursors nitrogens, such as ammonia, are injected / decomposed in order to release ammonia for conversion of NO x; and (ii) conversion as high as possible from NO X. If a large thermal mass filter were placed upstream of the SCR catalyst, that is, between the DOC and the SCR catalyst (“DOC / CSF / SCR”), the processes of (i) and (ii) would take much longer to if performed and the conversion of NO X , as a whole, from the standard emission drive cycle, could be reduced. The removal of particulates can be done using oxygen and occasional forced regeneration of the filter using engine control techniques.
    [00011] It has also been proposed to coat an SCR catalyst wash coating on the filter substrate monolith itself (see, eg, WO 2005/016497), in which case an oxidation catalyst can be located upstream of the substrate of SCR coated filter (that the oxidation catalyst is a component of a DOC, a CCSF or a NAC), in order to modify the NO / NO2 ratio to promote the NO X reduction activity on the SCR catalyst. There have also been proposals to locate a NAC upstream of an SCR catalyst placed on a through-flow substrate monolith, which can generate NH3 in situ during
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    7/63 NAC regeneration (see below). Such a proposal is described in GB 2375059.
    [00012] NACs are known, p. by US 5,473,887 and are designed to adsorb NO X from poor exhaust gas (lambda> 1) and to desorb NO X when the oxygen concentration in the exhaust gas is decreased. The desorbed NO X can be reduced to N2 with a suitable reducer, e.g. engine fuel, promoted by a catalyst component, such as rhodium, from the NAC itself or located downstream from the NAC. In practice, control of oxygen concentration can be adjusted to a desired redox composition intermittently in response to an adsorption capacity of NO x remaining calculated NAC, p. eg richer than normal engine operation (but still poor in stoichiometric composition or lambda = 1), stoichiometric or rich in stoichiometric (lambda <1). The oxygen concentration can be adjusted by numerous means, e.g. eg, strangulation, injection of additional hydrocarbon fuel into an engine cylinder, such as during the exhaust stroke or injection of hydrocarbon fuel directly into the exhaust gas downstream of an engine manifold.
    [00013] A typical NAC formulation includes a catalytic oxidation component, such as platinum, a significant amount (that is, substantially more than is required for use as a promoter, such as a promoter in a three-way catalyst) of a NO X storage component, such as barium, and a reduction catalyst, e.g. rhodium. A commonly provided mechanism for storing NO X of a poor exhaust gas for this formulation is:
    NO + V2 O 2 -> NO 2 (1); AND
    BaO + 2NO 2 + V2 O 2 -> Ba (NO 3 ) 2 (2), in which in reaction (1) nitric oxide reacts with oxygen in active oxidation sites on the platinum to form NO2. Reaction (2) involves
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    8/63 adsorption of NO 2 by the storage material, in the form of an inorganic nitrate.
    [00014] At lower oxygen concentrations and / or at high temperatures, the nitrate species becomes thermodynamically unstable and decomposes, producing NO or NO 2 , according to reaction (3) below. In the presence of a suitable reducer, these nitrogen oxides are subsequently reduced by carbon monoxide, hydrogen and hydrocarbons in N 2 , which can occur through the reduction catalyst (see reaction (4)).
    Ba (NO 3) 2 - + BaO + 2NO + 3/2 - O 2 or Ba (NO 3) 2 BaO + 2NO 2 + Vi 2 (3); and NO + CO Yi N 2 + CO 2 (4);
    (Other reactions include Ba (NO 3 ) 2 + 8H 2 -> BaO + 2NH 3 + 5H 2 O followed by NH 3 + NO X -► N 2 + yH 2 O or 2NH 3 + 2O 2 + CO -> N 2 + 3H 2 O + CO 2 etc.).
    [00015] In the reactions of (1) - (4) including here above, the reactive barium species is provided as the oxide. However, it is understood that, in the presence of air, most of the barium is in the form of carbonate or, possibly, hydroxide. The skilled person can adapt the above reaction schemes correspondingly to barium species other than the oxide and catalytic coating sequence of the exhaust stream.
    [00016] Exhaust catalysts promote the oxidation of CO to unburned CO 2 and HCS in CO 2 and H 2 O. Typical oxidation catalysts include platinum and / or palladium on a high surface area support.
    [00017] The application of SCR technology to treat NO X emissions from vehicle internal combustion (IC) engines, particularly low-burn IC engines, is well known. Examples of nitrogenous reducers, which can be used in the SCR reaction, include compounds such as nitrogen hydrides, e.g. eg, ammonia (NH 3 ) or hydrazine, or a precursor to NH 3 .
    [00018] NH 3 precursors are one or more compounds of which NH 3
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    9/63 can be derived, p. by hydrolysis. The decomposition of the precursor into ammonia and other by-products can be by hydrothermal or catalytic hydrolysis. NH 3 precursors include urea (CO (NH 2 ) 2 ) as an aqueous solution or as an ammonium carbamate or solid (NH 2 COONH 4 ). If urea is used as an aqueous solution, a eutectic mixture, e.g. , a 32.5% NH 3 (aq.) is preferred. Additives can be included in the aqueous solutions to reduce the crystallization temperature. Currently, urea is the preferred source of NH 3 for mobile applications, because it is less toxic than NH 3 , it is easy to transport and handle, it is cheap and it is generally available. Incomplete hydrolysis of urea can result in increased PM emissions in the tests to satisfy the relevant emission test cycle, because solids or droplets of partially hydrolyzed urea will be trapped by the filter paper used in the PM legislative test and considered as PM mass. In addition, the release of certain incomplete urea hydrolysis products, such as cyanuric acid, is environmentally undesirable.
    [00019] SCR has three main reactions (represented below in reactions (5) - (7) inclusive), which reduce NO X in elemental nitrogen.
    4NH 3 + 4NO + O 2 -► 4N 2 + 6H 2 O (ie 1: 1 NH 3 : NO) (5) 4NH 3 + 2NO + 2NO 2 4N 2 + 6H 2 O (ie 1: 1 NH 3 : NO X ) (6) 8NH 3 + 6NO 2 7N 2 + 12H 2 O (ie 4: 3 NH 3 : NO X ) (7) [00020] A non-selective, undesirable, relevant side reaction is: 2NH 3 + 2NO 2 N 2 O + 3H 2 O + N 2 (8) [00021] In practice, reaction (7) is relatively slow compared to reaction (5) and reaction (6) is the fastest of all. For this reason, when skilled technologists design exhaust after-treatment systems for vehicles, they often prefer to have an oxidation catalyst element (eg, a DOC and / or a CSF and / or a NAC) upstream of an SCR catalyst.
    [00022] It was brought to the Claimant's / Assignee's attention for his
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    10/63 customers who, when certain DOCs and / or NACs and / or CSFs are exposed to high temperatures encountered, p. eg during filter regeneration and / or an engine disturbance event and / or (in certain heavy duty diesel applications) normal high temperature exhaust gas, it is possible, given sufficient time at high temperature for low levels of metal components of the platinum group, particularly Pt, volatize from the DOC and / or NAC and / or CSF components and, subsequently, to the metal of the platinum group to be trapped in a downstream SCR catalyst. This can have a highly detrimental effect on the performance of the SCR catalyst, since the presence of Pt results in a high competition activity, of non-selective ammonia oxidation, as in reaction (9) (which shows the complete oxidation NH3), thereby producing secondary emissions and / or consuming NH3 unproductively.
    4NH 3 + 5O 2 - ^ · 4NO + 6H 2 O (9) [00023] A vehicle manufacturer reported the observation of this phenomenon in the SAE 2009-01-0627, which is entitled “Impact and Prevention of Ultra-Low Contamination of Platinum Group Metals on SCR catalysts Due to DOC Design ”and includes data comparing NO X conversion activity in relation to temperature for a SCR Fe / zeolite catalyst, located in series behind four DOCs containing platinum group metal (PGM) from suppliers, who were contacted with a model exhaust gas flowing at 850 ° C for 16 hours. The results presented show that the NO X conversion activity of a Fe / zeolite SCR catalyst disposed behind a DOC 20Pt: Pd in total PGM 70 gft ' 3 (2331 g / m 3 ) was negatively altered at higher temperatures of evaluation, compared to lower evaluation temperatures, as a result of Pt contamination. Two DOCs 2Pt: Pd from different suppliers of total PGM at 105 gft ' 3 (3496.5 g / m 3 ) were also tested. In a first DOC 2Pt: Pd, SCR catalytic activity was affected to a similar extent as the test in DOC 20
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    Pt: Pd, whereas for the second DOC 2Pt: Pd tested the SCR catalytic activity was contaminated to a lesser extent although the second DOC 2Pt: Pd still showed reduced NO X conversion activity compared to the white control (no DOC , just a bare substrate). The authors concluded that the supplier of the second DOC 2Pt: Pd, which showed more moderate NO X conversion degradation, was more successful in stabilizing 70 gft ' 3 (2331 g / m 3 ) Pt present with 35 gft' 3 (1165.5 g / m 3 ) Pd. A Pd-only DOC at 150 gft ' 3 (4995 g / m 3 ) showed no impact on the SCR downstream compared to the white control. Previous work by the authors of SAE 2009-01-0627 was published in the SAENo newspaper. 2008-01-2488.
    [00024] Vehicle manufacturers began to ask the Claimant / Assignee for measures to resolve the volatilization problem of PGMs with relatively low levels of components upstream of SCR catalysts. It would be highly desirable to develop strategies to prevent this movement of PGM over an SCR catalyst downstream at high temperatures. Numerous strategies have been developed to address this need.
    [00025] US 7,576,031 describes a diesel oxidation catalyst Pt-Pd with light-off (before reaching operating temperature) CO / HC and HC storage function. In particular, the diesel oxidation catalyst comprises a reactive coating composition, comprising two distinct wash layers. A first (or top) wash layer comprises a support material with a high surface area, one or more hydrocarbon storage components and a precious metal catalyst containing platinum (Pt) and palladium (Pd). The second (or base) wash layer comprises a support material with a high surface area and a precious metal catalyst containing platinum (Pt) and palladium (Pd), where the support is a support material substantially free of silica and not
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    12/63 contains a hydrocarbon storage component.
    [00026] The two layers of the diesel oxidation catalyst, described in US 7,576,031, have two distinctly different weight ratios of Pt: Pd relative to each other, in which the weight ratio of Pt: Pd of a first layer ( the first wash layer or top) is greater than the weight ratio Pt: Pd of a second layer (the second layer of the wash layer, or base). For example, the first (or top) layer of reactive coating may contain a Pt: Pd weight ratio of at least 2: 1. Pt: Pd weight ratios of at least about 2: 1 to about 10: 1, from about 3: 1 to about 5: 1, or from about 3: 1 to about 4: 1, are also exemplified. It is explained that it is important to use a high amount of Pt in the first (or top) layer of reactive coating in order to reinforce the sulfur tolerance, while maintaining some stabilization of the metallic phase in relation to sintering. The first (or top) layer of the wash layer contains a hydrocarbon (HC) storage component, e.g. eg a zeolite in order to store HCs during the cold start period of the drive cycle. After heating the catalyst, the hydrocarbon storage (HC) component will release the stored HCs, which are subsequently converted via the catalyst. It is important, the description continues, that the hydrocarbon (HC) storage component (eg, zeolite) be incorporated within the layer with the highest Pt: Pd weight ratio, in order to ensure an efficient conversion of the released paraffins .
    [00027] The second or base layer of the diesel oxidation catalyst described in US 7,576,031 contains a low Pt: Pd weight ratio to replace a maximum of Pt with Pd for reasons of maximum cost savings. The second or base layer of the wash layer has a Pt: Pd weight ratio less than about 2: 1. Also exemplified are the Pt: Pd ratios of less than about 2: 1 to about 1: 2, or less than
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    13/63 than about 2: 1 to about 1.4: 1 (7: 5). However, a minimum ratio of 1.4: 1 (7: 5) is preferred, in order to ensure sufficient light-off CO / olefin activity after thermal aging.
    SUMMARY OF THE INVENTION [00028] Therefore, the development of an oxidation catalyst for an internal combustion engine, particularly a compression ignition internal combustion engine, whereby SOF, HC and CO can be continuously and effectively cleaned and preferably, also where sulfur poisoning can be largely avoided, it has now become a matter of urgency. In recent years, the need arose to develop catalysts that reduce the amount of expensive and rare noble metals used until now, although having the same processing capacity as the existing exhaust gas cleaning catalysts.
    [00029] It has been found that differences in the amount of noble gmpo metal and hydrocarbon adsorbent present (the charge) in the catalyst layer can produce advantageous catalytic activity, particularly for the treatment of HC and CO (particularly CO) in a gas escape, converting them to water and carbon dioxide.
    [00030] In a first aspect, the invention provides an oxidation catalyst for the oxidative treatment of an exhaust hydrocarbon (HC) and carbon monoxide (CO), the oxidation catalyst comprising a support substrate and a plurality of catalyst layers, supported by the support substrate, where the plurality of catalyst layers comprises a reactive coating material, an active metal and a hydrocarbon adsorbent, and where a catalyst layer is located on the side of the surface layer catalyst layer and one or more other catalyst layers are located on the lower side than said catalyst layer; and where:
    (a) the amount of hydrocarbon adsorbent in said
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    14/63 catalyst layer is greater than the amount of hydrocarbon adsorbent in said one or more other catalyst layers, and the concentration of the active metal in said catalyst layer is the same as or less than the concentration of the active metal in said one or more other catalyst layers; or (b) the amount of hydrocarbon adsorbent in said catalyst layer is the same as the amount of hydrocarbon adsorbent in said one or more other catalyst layers, and the concentration of the active metal in said catalyst layer is less than the concentration of the active metal in said one or more other catalyst layers.
    [00031] Using the hydrocarbon (HC) adsorption and storage function, the oxidation catalyst of the invention can efficiently process carbon monoxide (CO), even at relatively low temperatures. When the exhaust temperature increases, the stored hydrocarbon (HC) is released and becomes receptive to oxidative treatment with the catalyst, because of the high temperature. The advantageous ability to clean the exhaust gas by the catalyst of the invention is associated with the distribution of the hydrocarbon adsorbent and active metal between the layers. It is believed that, by providing an adsorption and storage function on the “one catalyst layer” of the surface layer on the side of the exhaust gas catalyst, the blocking effect on the CO oxidation reaction on the “other catalyst layer ”On the side of the catalyst surface layer, close to the substrate support, is inhibited and, when the noble metal concentration in the“ a catalyst layer ”on the side of the catalyst surface layer is low, the formation of CO due to partial oxidation of the hydrocarbon is inhibited when the adsorbed and stored hydrocarbon is released.
    [00032] Typically, the oxidative catalyst of the first aspect of
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    The invention is a catalyzed substrate monolith and the support substrate is a substrate monolith. The one catalyst layer can be a first reactive coating, as defined here, and one of the other catalyst layers can be a second reactive coating, as defined here. [00033] Thus, the first aspect of the invention also relates to a catalyzed substrate monolith for the oxidative treatment of a hydrocarbon (HC) and carbon monoxide (CO) in an exhaust gas, this catalyzed substrate monolith comprising a substrate monolith, a first reactive coating and a second reactive coating, wherein the second reactive coating is arranged on a layer above the first reactive coating, where the first reactive coating comprises a catalyst composition comprising an active metal and at least one material support for the active metal, and the second reactive coating comprises a hydrocarbon adsorbent and in which:
    (a) the amount of hydrocarbon adsorbent in the first reactive coating, and the concentration of active metal in the second reactive coating is the same as or less than the concentration of active metal in the first reactive coating; or (b) the amount of hydrocarbon adsorbent in the second reactive coating is the same amount as the hydrocarbon adsorbent in the first reactive coating, and the concentration of active metal in the second reactive coating is less than the concentration of active metal in the first reactive coating .
    [00034] It has also been found that platinum volatilization of a PGM-containing catalyst, comprising both platinum and palladium, can occur under 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. An incarnated PGM catalyst composition has been planned for use in
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    16/63 combination with a downstream SCR catalyst, which avoids or reduces the problem of PGM, particularly Pt, migrating from a relative and highly charged upstream Pt catalyst to a downstream SCR catalyst.
    [00035] A second aspect of the invention provides a catalyzed substrate monolith, comprising an oxidizing catalyst in a substrate monolith, for use in the treatment of exhaust gas emitted by a low-combustion internal combustion engine, whose catalyzed substrate monolith comprises a first reactive coating (typically having a length L) and a second reactive coating, where the second reactive coating is arranged in a layer above the first reactive coating (typically for at least part of the length L), where the first reactive coating comprises a catalyst composition comprising platinum and at least one support material for platinum, wherein the second reactive coating comprises a catalyst composition comprising both platinum and palladium and at least one support material for platinum and palladium and in which a ratio weight of platinum for palladium of the second reactive coating is <2 , such as 1.5: 1 or about 1: 1, e.g. e.g., <1: 1. A significance of the last detail is shown in some of the Examples: it was found that the preferred Pt: Pd weight ratios are less volatile, through empirical testing, than a similar catalyst, having a Pt: Pd weight ratio of 4: 1.
    [00036] A third aspect of the invention provides an exhaust system for a low-burn internal combustion engine, this system comprising a first catalyzed substrate monolith according to the present invention, particularly the catalyzed substrate monolith according to second aspect of the invention.
    [00037] A fourth aspect of the invention provides a low-burn internal combustion engine, particularly for a vehicle, comprising an exhaust system according to the present invention. The engine
    Petition 870190074061, of 08/01/2019, p. 26/155 / 63 low-burn internal combustion can be a positive ignition engine, p. spark ignition, which typically works on gasoline fuel or mixtures of gasoline fuel and other components, such as ethanol, but is preferably a compression ignition, e.g. eg a diesel engine. Poorly combustion internal combustion engines include homogeneous charge compression ignition (HCCI) engines, powered by gasoline fuel, etc. or diesel fuel.
    [00038] A fifth aspect of the invention provides a method of reducing or avoiding platinum poisoning of a selective catalytic reduction catalyst (SCR) of an exhaust system of an internal combustion engine with poor combustion, platinum being able to volatilize from one first reactive coating (typically having a length L), comprising a catalyst composition comprising platinum and at least one platinum support material disposed on a substrate monolith upstream of the SCR catalyst, when the catalyst composition, comprising platinum, is exposed to relatively extreme conditions, including relatively high temperatures, this method comprising trapping volatilized platinum in a second reactive coating arranged in a layer above the first reactive coating (typically at least part of length L), the second reactive coating comprising a catalyst composition comprising both pl acts as palladium and at least one support material for platinum and palladium and where a weight ratio of platinum to palladium in the second reactive coating is <2.
    [00039] A sixth aspect of the invention provides an exhaust system for an internal combustion engine, particularly a compression-ignition internal combustion engine, such as a diesel engine, this system comprising an oxidation catalyst or a catalyzed substrate monolith , according to a first aspect of the invention.
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    18/63 [00040] A seventh aspect of the invention provides an internal combustion engine, particularly for a vehicle, comprising an exhaust system according to the sixth aspect of the invention. The internal combustion engine can be a positive ignition, e.g. , spark ignition engine, which typically runs on gasoline fuel or mixtures of gasoline fuel and other components, such as ethanol, but is preferably a compression ignition, e.g. e., a diesel type engine.
    [00041] A seventh aspect of the invention provides a vehicle comprising an engine, in accordance with the present invention.
    BRIEF DESCRIPTION OF THE DRAWINGS [00042] Figure 1 is a schematic drawing of a laboratory reactor used to test platinum contamination on a CHA / Cu zeolite SCR catalyst from Example 2 or a Beta / Fe zeolite SCR catalyst from example 6.
    [00043] Figure 2 is a bar graph comparing the NO X conversion activity of two SCR catalyst cores aged at 500 ° C (alpha 0.8, that is, NH 3 : NO X ), each of which was aged in the laboratory scale exhaust system shown in Figure 1, containing core samples of the diesel oxidation catalyst from Reference Example 6 and Example 4, heated in a tube oven at 900 ° C for 2 hours, in a gas synthetic exhaust flowing, with the CHA / Cu zeolite SCR catalyst core maintained at 300 ° C located downstream;
    [00044] Figure 3 is a graph plotting the results of NO X conversion activity as a function of temperatures for a Beta / Fe zeolite SCR catalyst, compared with the activity of Beta / Fe zeolite SCR catalysts aged in a laboratory scale escape shown in Figure 1, containing catalyzed soot filter cores from Reference Example 7 and Examples 7 and 8.
    [00045] Figure 4 is a bar graph showing the activity of
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    19/63 NO X conversion of two different SCR CHA / Cu catalysts, each of which was aged downstream of the diesel oxidation catalysts of Example 10 and having a total Pt: Pd weight ratio of 4: 1 and 2: 1 , for a control sample of the SCR catalyst.
    [00046] Figure 5 is a schematic drawing of an exhaust system according to the first most preferred embodiment, according to the third aspect of the present invention.
    [00047] Figure 6 is a schematic drawing of an exhaust system according to the second most preferred embodiment, according to the third aspect of the present invention.
    [00048] Figure 7 is a schematic drawing of an exhaust system according to the third most preferred embodiment, according to the third aspect of the present invention.
    DETAILED DESCRIPTION OF THE INVENTION
    Oxidation catalyst and catalyzed substrate monolith [00049] Typically, each layer of catalyst or reactive coating layer has an average thickness of 25 to 200 pm, particularly 50 to 150 pm and, more particularly, 75 to 125 pm (e.g. ., 100 pm).
    [00050] The average thickness of each layer of catalyst or layer of reactive coating can be the same or different. In an embodiment of the invention, the average thickness of a catalyst layer (e.g., second reactive coating) and at least one of the other catalyst layers (e.g., first reactive coating) is approximately the same.
    [00051] The oxidation catalyst or catalyzed substrate monolith of the invention comprises a plurality of catalyst layers or reactive coating. Typically, the oxidized catalyst or catalyzed substrate monolith consists of 2, 3, 4 or 5 catalyst layers or
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    20/63 reactive coating. It is preferred that the oxidized catalyst or catalyzed substrate monolith consists of two layers of catalyst or reactive coating. In the context of the first aspect of the invention, the "one catalyst layer" and one or more "other catalyst layers" among the plurality of catalyst layers, the invention positions the "one catalyst layer" among the plurality of catalyst layers, in the side of the catalyst surface layer and the "other catalyst layers" on the lower side than the "one catalyst layer" (on the supporting substrate side).
    [00052] Generally, the component that adsorbs hydrocarbons (eg, the adsorbent or hydrocarbon adsorber) has a specific surface elevation for contact with the exhaust gas. Typically, the hydrocarbon adsorbent has a specific surface area of 50 to 1500 m 2 / g, preferably 50 to 1500 m 2 / g, 200 to 1000 m 2 / g, more preferably 200 to 900 m 2 / g. The specific surface area is measured by the BET nitrogen adsorption method, using nitrogen as the adsorbed-desorbed gas.
    [00053] Typically, the hydrocarbon adsorbent is selected from zeolite, silica, aluminum, titania, zirconia, magnesium oxide, calcium oxide, ceria, niobium, active charcoal, porous graphite and combinations of two or more of them. Preferably, the hydrocarbon adsorbent is a zeolite. Examples of suitable zeolites include natural zeolites, such as analcima, chabazite, erionite, natrolite, mordenia, heulandite, stylbite and laumantila, and synthetic zeolites, such as type A zeolite, type Y zeolite, type X zeolite, type L zeolite, erionite, mordenite, beta zeolite and ZSM-5.
    [00054] The ratio by quantity of hydrocarbon adsorbent (i.e. hydrocarbon adsorbent) in said layer of catalyst or second reactive coating for said one or more other layers of catalyst to first reactive coating, is typically 10: 1 to 1.1: 1,
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    21/63 particularly 7.5: 1 to 1.2: 1, more particularly 5: 1 to 1.3: 1, even more particularly 4: 1 to 1.4: 1, even more particularly 3: 1 to 1, 5: 1.
    [00055] Typically, a catalyst layer or second reactive coating has a hydrocarbon adsorbent concentration (i.e. hydrocarbon adsorbent) of 0.05 to 3.00 gin 3 (0.0031 to 0.183 g / m 3 ) , particularly 0.10 to 2.0 gin 3 (0.0061 to 0.122 g / m 3 ), more particularly 0.25 to 0.75 gin ' 3 (0.015 to 0.046 g / m 3 ). The amount of hydrocarbon adsorbent present in one layer or throughout is related to the trapping capacity of the oxidized catalyst or catalyzed substrate monolith.
    [00056] Characteristically, the amount of adsorbent hydrocarbon present in "a layer of catalyst" is greater than the amount of adsorbent hydrocarbon present in "other layers of catalyst" and the concentration of the aforementioned active metal, present in "a layer of catalyst ”is less than the concentration of the aforementioned active metal present in the“ other catalyst layers ”; the catalyst layers can also be stacked with the “one catalyst layer” and the adjacent “other catalyst layers”, and can have an intermediate catalyst layer (or another layer, a layer of the same or different composition) interposed between them . In addition, the invention selects any two catalyst layers from the plurality of catalyst layers and positions them so that “a catalyst layer” is located on the side of the catalyst surface layer and the “other catalyst layer” is located on the lower side than the catalyst layer mentioned above (the side of the substrate it supports); where, if “one layer of catalyst” is defined, the other is automatically defined as “another layer of catalyst”.
    [00057] A catalyst layer or second reactive coating typically has a hydrocarbon adsorbent concentration of 10 to
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    22/63
    50% by weight of the reactive coating or coating, particularly 15 to 40% by weight, more particularly 20 to 30% by weight.
    [00058] The active metal serves as the catalytically active component of the oxidation catalyst or catalyzed substrate monolith. The active metal is a noble metal, a base metal or a metal of the platinum group (PGM).
    [00059] Examples of suitable noble metals include platinum, palladium, rhodium, ruthenium, iridium, osmium, gold and silver. When the active metal is a noble metal, then preferably the active metal is platinum, palladium or gold. Noble metals can be used alone or as a mixture of two or more, such as a mixture of platinum and palladium, or a mixture of platinum, palladium and gold.
    [00060] Examples of base metals include nickel, copper, manganese, iron, cobalt and zinc. When the active metal is a base metal, then preferably the active metal is nickel, copper, manganese or iron. The base metals can also be used alone or as a mixture of two or more.
    [00061] The active metal of the catalyst layer or the second reactive coating may be the same as or different from the active metal of the one or more other layers of catalyst or first reactive coating.
    [00062] It is preferred that the active metal is a metal of the platinum group. Most preferably, the active metal is platinum, palladium or a mixture of them.
    [00063] When an active metal is present in both a catalyst layer and the second reactive coating and one or more layers of catalyst or first reactive coating, then the active metal can be the same or different.
    [00064] Typically, the concentration ratio of active metal, such as platinum group metal (PGM), from said catalyst layer (or second reactive coating) to said one or more other catalyst layers (or first reactive coating) is 1:50 to 1: 1.1,
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    23/63 particularly 1:35 to 1: 1,2, more particularly 1:20 to 1: 1,3, even more particularly 1:15 to 1: 1,4, more particularly 1:10 to 1: 1,5 (e.g., 1: 5 1: 1.5). [00065] Generally, one or more other layers of catalyst (or first reactive coating) have an active metal concentration, such as PGM, of 0.05 to 3.5 gin 3 (0.0031 g / cm 3 to 0 , 21 g / cm 3 ), particularly 0.1 to
    1.5 gin ' 3 (0.061 g / cm 3 to 0.092 g / cm 3 ), more particularly 0.25 to 0.75 gin' 3 (0.015 g / cm 3 to 0.046 g / cm 3 ) (e.g. , 0.1 to 0.75 gin 3 (0.061 g / cm 3 to 0.046 g / cm 3 ) The amount of active metal present determines the number of active sites that are available for catalysis.
    [00066] Typically, one or more other layers of catalyst (or first reactive coating) have a concentration of active metal, such as PGM, from 0.05 to 7.5% by weight, particularly 0.5 to 5% by weight, more particularly 1 to 3% by weight.
    [00067] A catalyst layer (or second reactive coating) typically has an active concentration, such as PGM, of 0.01 to 5% by weight, particularly 0.05 to 0.5% by weight, more particularly 0 , 1 to 0.3% by weight.
    [00068] In an embodiment of the invention, there is no hydrocarbon adsorbent (i.e., hydrocarbon adsorbent) in one or more other catalyst layers or in the first reactive coating. In relation to the first aspect of the invention, when there is no hydrocarbon adsorbent in one or more other catalyst layers or in the first reactive coating, then there may be no active metal in the catalyst layer or second reactive coating, or it is present in a concentration or relationship as defined above.
    [00069] When a hydrocarbon adsorbent (i.e. hydrocarbon adsorbent) is present in both a catalyst layer or second reactive coating and one or more other layers of catalyst or first reactive coating, then the hydrocarbon adsorbent can be the
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    24/63 same or different. Preferably the hydrocarbon adsorbent of each layer of catalyst or reactive coating is the same.
    [00070] When the amount of hydrocarbon adsorbent (i.e., hydrocarbon adsorbent) in said catalyst layer or second reactive coating is greater than the amount of hydrocarbon adsorbent (i.e., hydrocarbon adsorbent) in said one or more other catalyst layers or first reactive coating, then the weight of the catalyst is not a catalyst layer or second reactive coating and is typically less than or approximately the same weight as the catalyst of the one or more other catalyst layers or first reactive coating.
    [00071] Typically, the wash layer material is a support material for the active metal. The support material is, for example, a metal oxide selected from an oxide of Mg, Si, Ca, Sr, Ba, Al, Ga, In, Sn, a transition metal element, a lanthanide, its complex oxide and mixtures of two or more of them. Preferably, the support material is selected from S1O2, AI2O3, CeO2 and T1O2 or is a complex oxide having S1O2, AI2O3, CeO2 or T1O2 as its main constituent.
    [00072] The oxidized catalyst or catalyzed substrate monolith may further comprise a catalyst promoter, such as cerium oxide, zirconium oxide or titanium oxide.
    [00073] Generally, the support substrate contains the catalyst (eg, the active metal, hydrocarbon adsorbent, reactive coating material, promoter, etc.). The support substrate can be any one that does not decrease the combustion efficiency of the engine through problems with pressure loss, etc. and have both durability and reliability.
    [00074] Typically, the support substrate is a ceramic or metallic material. It can, for example, be in a tubular, fibrous or particulate form. Examples of suitable support substrates include a
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    25/63 monolithic alveolar cordierite type substrate, monolithic alveolar SiC type substrate, red fiber or knitted fabric type substrate, foam type substrate, cross flow type substrate, mesh type substrate metallic wire, a porous metallic body type substrate and a ceramic particle type substrate. The support substrate can be selected from cordierite (SiO2-AliO 3 -MgO), silicon carbide (SiC), Fe-Cr-Al, Ni-Cr-Al and a stainless steel.
    [00075] Preferably, the support substrate is a substrate monolith.
    [00076] Typically, the substrate monolith for use in the invention, particularly in the second aspect of the invention, can be a filter substrate monolith, having inlet surfaces and outlet surfaces, where the inlet surfaces are separated from the outlet surfaces. porous structure. A particularly preferred filter substrate monolith is a wall flow filter. However, in a particularly preferred embodiment, the substrate monolith is a flow substrate monolith.
    [00077] The at least one support material (i.e., reactive coating material) of the first reactive coating 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 and an optionally stabilized mixed ceria-zirconium oxide or molecular sieve or a mixture of any two or more of them.
    [00078] The first reactive coating can span substantially an entire length of the substrate monolith channels. In a first particular embodiment, the second reactive coating substantially covers the first reactive coating.
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    26/63
    In a second embodiment, the second reactive coating is arranged in a zone of substantially uniform length at one end downstream of the substrate monolith, this zone being defined at one end downstream by the outlet end of the substrate monolith itself and in an upstream end by a point less than the entire length of the first reactive coating. That is, in the second embodiment, the second reactive coating does not cover the entire first reactive coating. Methods of producing red coatings of differential lengths are known in the art, e.g. see WO 99/47260 and below.
    [00079] In any of the first, second and third preferred embodiments of the substrate monolith catalyzed according to the present invention, the first reactive coating may comprise 2575% by weight of the platinum group metal present in the first reactive coating and in the second reactive coating combined, e.g. 35-65% by weight of it. That is, the second reactive coating can comprise 75-25%, e.g. 65-35% by weight of the total platinum group metal present in the first reactive coating and the second reactive coating combined. It was found that PGM volatilization is largely dependent on the PGM load of a reactive coating cover layer and more dependent on the Pt: Pd weight ratio, as explained above. Preferably, however, more total PGM is placed in the second reactive coating, because mass transfer is more accessible. It is therefore preferred that> 50% by weight of the metal of the total platinum group, present in the first reactive coating and the second reactive coating, combined, is present in the second reactive coating.
    [00080] One aspect of the catalyst design related to a division of the metal of the total platinum group and the second reactive coating is a reactive coating charge for each of the first coatings
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    27/63 reactive and second reactive coatings. In embodiments, the reactive coating charge for each of the first reactive coatings and the second reactive coating is individually selected from the range of 0.1-3.5 gin ' 3 (0.061 g / cm 3 to 0.21 g / cm 3 ), p. 0.5-1.5 gin ' 3 (0.031 g / cm 3 - 0.09 g / cm 3 ), such as> 1.5 gin-3 (0.09 g / cm 3 - 0.18 g / cm 3 ),> 2.0 gin 3 (0.122 g / cm 3 ) or <2.0 gin 3 (0.122 g / cm 3 ). Higher loads are preferred, e.g. eg for ΝΟχ adsorbing catalysts. However, it is possible to make PGM less “accessible” in the first reactive coating to mass transfer, using a lower reactive coating charge in the second reactive coating than in the first reactive coating. That is, in embodiments, a reactive coating charge on the first reactive coating is greater than a reactive coating charge on the second reactive coating charge.
    [00081] In the second aspect of the present invention, the at least one support material (or reactive coating material) can include one or more molecular sieves, e.g. aluminosilicate zeolites. The primary duty of the molecular sieve on the catalyzed substrate of the first aspect of the invention is to improve the conversion of hydrocarbons through a duty cycle, storing hydrocarbons after the cold start or during cold phases of a work cycle and releasing hydrocarbons stored at higher temperatures, when the associated platinum group metal catalyst components are most active for HC conversion. See, for example, EP 0830201. Molecular sieves are typically used in catalyst compositions according to the invention for light-duty diesel vehicles, while they are rarely used in catalyst compositions for heavy-duty diesel applications, because temperatures Exhaust gas in heavy-duty diesel engines means that hydrocarbon trapping functionality is not generally required. However, where molecular sieves are present in the
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    28/63 substrate monolith catalyzed according to the present invention, it is highly preferred that at least one of the first reactive coating and the second reactive coating include molecular sieve. Most preferably, both the first reactive coating and the second reactive coating include molecular sieves.
    [00082] However, molecular sieves, such as aluminosilicate zeolites, are not particularly good supports for platinum group metals, because they are mainly silica molecular sieves, particularly and relatively higher silica-to-alumina, which are favored by their high thermal durability: they can thermally degrade during aging, so that a molecular sieve structure can collapse and / or PGM can sinter, providing less dispersion and, consequently, lower H / C and / or CO. Therefore, in a preferred embodiment, the first reactive coating and the second reactive coating comprise a molecular sieve at <30/5 by weight (such as <25% by weight, <20% by weight, e.g. <15% by weight) of the individual reactive coating layer. The at least one support material remaining from the first reactive coating 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 and, optionally, stabilized mixed ceria-zirconia oxide and mixture of any two or more of them.
    [00083] Preferred molecular sieves, for use as support materials / hydrocarbon adsorbents are medium-pore zeolites, preferably aluminosilicate zeolites, that is, those having a maximum ring size of eight tetrahedral atoms, and a large pore zeolites ( maximum of ten tetrahedral atoms), preferably aluminum silicate zeolites, include natural or synthetic zeolites, such as faujasite,
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    29/63 clinoptilolite, mordenite, silicalite, ferrierite, zeolite X, zeolite Y, ultrastable zeolite Y, zeolite ZSM-5, zeolite ZSM-12, zeolite SSZ-3, zeoliteSAPO5, offretite or to a zeolite beta, preferably zeolite 5, preferably zeolite beta, preferably zeolite 5 , beta and Y. Preferred zeolite adsorbent materials have a high ratio of silica to alumina, for improved hydrothermal stability. The zeolite can have a silica / alumina molar ratio of at least about 25/1, preferably at least about 50/1, with useful 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.
    [00084] The oxidation catalyst of the first aspect of the invention or the catalytic substrate monolith oxidation catalyst of the second aspect of the present invention can be a diesel oxidation catalyst or a umχ adsorbent catalyst, having obligations as described in the foundations of the invention above . A NAC contains significant amounts of alkaline earth metals and / or alkali metals relative to an oxidation catalyst. NAC typically also includes ceria or a mixed oxide containing ceria, e.g. eg a mixed cerium or zirconium oxide, mixed oxide optionally including one or more additional lanthanide or rare earth elements.
    [00085] Methods of producing catalyzed substrate monoliths, including single layer reactive coatings and double layer arrangements (one layer of reactive coating on top of another layer of reactive coating), are known in the art and include WO 99/47260, that is, comprising the steps of (a) locating a containment medium at the top, first end of a substrate monolith, (b) dosing a predetermined amount of a first reactive coating component within said containment medium, in order ( a), then (b) or (b) then (a), and (c), applying pressure or vacuum, pulling said first reactive coating component into at least part of the
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    30/63 substrate monolith, and retain substantially all said amount within the substrate monolith. In a first step, a coating of a first application end can be dried and the dry substrate monolith can be moved quickly through 180 degrees and the same procedure can be applied on a top, second end of the substrate monolith, with substantially no layer overlap between applications of the first and second ends of the substrate monolith. The resulting coating product is then dried, then calcined. The process is repeated with a second reactive coating component, to provide a catalyzed (bilayer) substrate monolith, according to the present invention.
    [00086] The filter substrate monolith for use in the first or second aspects of the invention is preferably a wall flow filter, i.e., 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 -version. In other words, the wall flow filter is a honeycomb arrangement defining a plurality of first channels plugged in without an upstream end and a plurality of second channels not plugged in the upstream end, but plugged in a downstream end. The channels vertically and laterally adjacent to a first 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 chessboard. [00087] Catalyzed filters, preferably wall flow filters, can be coated using the method described in WO 2011/080525. That is, a method of coating a monolith substrate
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    31/63 alveolar, comprising a plurality of channels with a liquid comprising a catalyst component, this method comprising the steps of: (i) retaining a substantially vertical alveolar monolith substrate; (ii) introducing a predetermined volume of the liquid into the substrate via open ends of the channels at a lower end of the substrate; (iii) sealingly retain the liquid introduced into the substrate;
    (iv) inverting the substrate containing the retained liquid; and (v) applying a vacuum to open the ends of the substrate channels at the inverted bottom end of the substrate to pull the liquid along the substrate channels. The catalyst composition can be coated on the filter channels from a first end, after which the coated filter can be dried. The use of such a method can be controlled using, e.g. eg, vacuum strength, vacuum duration, wash layer viscosity, wash layer solids, particle coating or agglomerate size and surface tension, so that the catalyst is coated predominantly on the inlet surfaces, however also, optionally, within the porous structure, but close to the entrance surfaces. Alternatively, reactive coating components can be ground to a size, e.g. eg, D90 <5 pm, so that they “permeate” the porous structure of the filter (see WO 2005/016497). The SCR catalyst of the second substrate monolith may comprise a filter substrate monolith, preferably a wall flow monolith, or a flow substrate monolith. Flow substrate monoliths can be extruded SCR catalysts or SCR catalysts covered by washing over inert substrate monoliths. It is also possible to produce a wall flow filter of an extruded SCR catalyst (see WO 1009/093071 and WO 2011/092521). SCR catalysts can be selected from the group consisting of at least one of Cu, Hf, La, Au, In, V, lanthanides and Group VIII transition metals, such as Fe, supported by a refractory oxide
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    32/63 or molecular sieve. Suitable refractory oxides include AI2O3, T1O2, S1O2, ZrÜ2 and mixed oxides containing two or more of them. The non-zeolite catalyst may also include tungsten oxide, e.g. e.g., V2O5 / WO3 / T1O2. Preferred metals of particular interest are selected from the group consisting of Ce, Fe and Cu. The molecular sieves can be ion-exchanged with any of the above metals.
    [00088] In particular embodiments, the at least one molecular sieve is an aluminosilicate zeolite or a SAPO. The at least one molecular sieve can be a medium or large pore molecular sieve, for example. By "small pore molecular sieve" here is meant a molecular sieve containing a maximum ring size of 8 tetrahedral atoms, such as CHA; by "medium pore molecular sieve" here we mean 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-vide catalysts, for example, WO 2008/132452. Molecular sieves for use in SCR catalysts, according to the invention, include one or more metals incorporated within a molecular sieve structure, e.g. ex. Fe "in-structure" Beta and Cu "in-structure" CHA.
    [00089] 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 currently preferred CHA molecular sieves, particularly in combination with Cu as a promoter, e.g. ion exchanged.
    [00090] In an embodiment of the first aspect of the invention, there is no active metal, such as PGM, in a catalyst layer or second
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    33/63 reactive coating. When there is no active metal in the other catalyst layer or the second reactive coating, then there may be no hydrocarbon adsorbent in one or more other layers of catalyst or first reactive coating, or the hydrocarbon adsorbent may be present in a concentration or ratio as defined above.
    [00091] In another embodiment of the first aspect of the invention, the first reactive coating comprises a catalyst composition comprising platinum and at least one support material for platinum, and the second reactive coating comprises a catalyst composition comprising both platinum as palladium and at least one support material for platinum and palladium and wherein a weight ratio of platinum to palladium of the second reactive coating is <2, such as 1.5: 1 or about 1: 1, e.g. e.g., <1: 1.
    [00092] In an embodiment of the second aspect of the invention, the amount of hydrocarbon adsorbent or adsorbent (e.g., zeolite) in the second reactive coating is greater than the amount of hydrocarbon adsorbent or adsorbent in the first reactive coating . Preferably, the concentration of active metal (eg, platinum and palladium) of the second reactive coating is the same as or less than, preferably less than, the concentration of the active metal (eg, platinum) in the first reactive coating. The amount of hydrocarbon adsorbent is as defined above.
    [00093] In another embodiment of the second aspect of the invention, the amount of hydrocarbon adsorbent or adsorbent (e.g., zeolite) in the second reactive coating is the same as the amount of hydrocarbon adsorbent or adsorbent in the first coating reactive. Preferably, the concentration of the active metal (eg, platinum and palladium) in the second reactive coating is less than the concentration of
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    34/63 active metal (eg platinum) from the first reactive coating.
    EXHAUST SYSTEM [00094] In accordance with the third and sixth aspects, the invention provides an exhaust system for a low-firing lower contact module, a system comprising a first catalyzed substrate monolith according to the present invention.
    [00095] In a preferred embodiment, the exhaust system according to the present invention, particularly the third aspect of the invention, comprises a second catalyzed substrate monolith, comprising a selective catalytic reduction (SCR) catalyst, second catalyzed substrate this being disposed downstream of the first catalyzed substrate monolith. In preferred embodiments, the exhaust system of the invention, particularly the third aspect 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, without means to inject 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 the means for injecting ammonia or a precursor thereof, in another embodiment, a means of engine control is provided to enrich the exhaust gas, so that ammonia gas is generated in situ by reducing ΝΟχ in the catalyst composition of the first catalyzed substrate monolith.
    [00096] Nitrogen reducers and precursors for use in the present invention include any of those mentioned above, with respect to the fundamentals section of the invention, p. eg, ammonia and urea.
    [00097] In combination with a properly designed and controlled diesel compression ignition engine, enriched exhaust gas, ie exhaust gas containing increased amounts of carbon monoxide.
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    35/63 carbon and hydrocarbons relating to normal poor operating mode, contact the catalyst composition of the first catalyzed substrate monolith. Components within a NAC, such as ceramics or promoted ceriazirconia-PGM, can promote the changed water-gas reaction, ie CO ( g ) + H 2 O (v) -> CO 2 (g) + H 2 ( g) giving off H 2 . From secondary reaction notes to reactions (3) and (4) exposed above, p. Ba (NO 3 ) 2 + 8H 2 -> BaO + 2NH 3 + 5H 2 O, NH 3 can be generated in situ and stored for ΝΟχ reduction in the downstream SCR catalyst.
    [00098] In a more preferred embodiment, the exhaust system of the invention, particularly the third aspect of the invention, comprises a third catalyzed substrate monolith, wherein the substrate monolith of the first catalyzed substrate monolith is a substrate monolith flow, in which the third catalyzed substrate monolith is a filtering substrate monolith, having inlet surfaces and outlet surfaces and in which the inlet surfaces are separated from the outlet surfaces by a porous structure, said third catalyzed substrate monolith. comprising an oxidation catalyst and is disposed between the first catalyzed substrate monolith and the second catalyzed substrate monolith and, preferably, between the first catalyzed substrate monolith and any injector for injecting a nitrogenous reducer into the exhaust gas, between the first catalyzed substrate monolith and the second substrate monolith catalyzed act.
    [00099] In a second, more preferred embodiment, the second catalyzed substrate monolith of the exhaust system of the invention, particularly the third aspect of the invention, is a filtering substrate monolith, having inlet and outlet surfaces, where the entrance surfaces are separated from the exit surfaces by a porous structure.
    [000100] In a third most preferred embodiment, the system
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    The exhaust system of the invention, particularly the third aspect of the invention, comprises a third substrate monolith, wherein the third substrate monolith is a filtering substrate monolith, having inlet and outlet surfaces, in which the inlet are separated from the outlet surfaces by a porous structure, the third substrate monolith being disposed downstream of the second catalyzed substrate monolith. In a particular embodiment, the third substrate monolith comprises an oxidation catalyst. That is, in one embodiment, the third substrate monolith is devoid of any coating.
    [000101] In the first, second and third most preferred embodiments of the exhaust system of the invention, particularly in the third aspect of the invention, the or each filter substrate monolith is preferably a wall flow filter.
    [000102] The preferred function of the first catalyzed substrate of the second and third most preferred embodiments of the invention, particularly the third aspect of the present invention, is different from that of its first most preferred embodiment. In the second and third most preferred embodiments, the catalyzed substrate monolith which immediately follows downstream of the first catalyzed substrate monolith is the second substrate monolith, comprising the SCR catalyst. In order to promote the reaction (6), it is preferable that the first catalyzed substrate monolith promotes NO oxidation, while at the same time avoiding PGM volatilization and its subsequent migration to the SCR catalyst directly downstream, thereby reducing the conversion activity of NOxtotal.
    [000103] For this function it is preferable that a weight ratio Pt: Pd of both the first reactive coating and the second reactive coating is> 2: 1. In order to avoid volatilization problems, it is preferred that the weight ratio of Pt: Pd of both the first reactive coating and the second reactive coating combined is <10: 1, p. e.g.> 8: 1, <6: 1 or <
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    4: 1. In particular embodiments, preferably the PGM of the first reactive coating is Pt only, that is, it is substantially palladium free. In order to trap any platinum that may volatilize from the first reactive coating, it is preferred that the weight ratio of platinum to palladium in the second reactive coating is <2, such as 1.5: 1 or about 1: 1, P. e.g., <1: 1.
    [000104] By "substantially palladium-free" is meant that palladium is not intentionally provided in a relevant layer. It is recognized, however, that the material can migrate or diffuse from the second reactive coating to the first reactive coating in small amounts considered to be non-substantial (ie <10% of methanol, <9%, <8%, <7% , <6%, <5%, <4%, <3%, <2%, or even <1%).
    [000105] The preferred function of the first catalyzed substrate of the first most preferred embodiment of the invention of the third and sixth aspect of the invention, particularly the third aspect of the present invention, is different from that of the second and third most preferred embodiments, because there are a catalyzed soot filter (the third catalyzed substrate monolith) disposed between the first substrate monolith and the second substrate monolith. As a result, although it is possible to reduce or prevent PGM volatilization of the first catalyzed substrate monolith and its subsequent migration to downstream components, the fact that there is a catalyzed soot filter, located downstream of the first substrate monolith, whose soot filter catalyzed preferably promotes NO oxidation upstream of the second substrate monolith comprising SCR catalyst for the purpose of promoting reaction (6) and, therefore, will likely contain a relatively high platinum content, measures to collect volatilized PGM can be more effectively applied to downstream of the first catalyzed substrate monolith. For example, measures to trap volatile PGM can be applied to
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    38/63 aspects of catalyzed soot filter design, p. e.g., a protective bed can be disposed between the catalyzed soot filter and the second catalyzed substrate monolith or in an entry zone for the second catalyzed substrate monolith itself. Such measures are described in the Applicant / Assignee's sister applications, entitled “Catalysed Substrate Monolith”; Exhaust System for a Lean Bum IC Engine comprising a PGM Component and a SCR Catalyst ”; and Exhaust System for a Lean-Bum Internal Combustion Engine including SCR Catalyst ”, deposited under reference numbers 70050, 70051 and 70053, respectively.
    [000106] Thus, in the situation of the first most preferred embodiment of the third and sixth aspects of the invention, particularly the third aspect of the present invention, the preferred function of the first catalyzed substrate monolith is to oxidize carbon monoxide and unburned hydrocarbons (fraction volatile organic (VOF) also known as the soluble organic fraction (SOF) and does not necessarily oxidize NO to NO2 to promote reaction (6).
    [000107] Preferably, in the catalyzed substrate monolith for use in the first most preferred embodiment of the third and sixth aspects of the invention, particularly the third aspect of the present invention, the second reactive coating comprises both platinum and palladium and the first reactive coating comprises both platinum and palladium in a higher Pt: Pd weight ratio than in the second reactive coating. That is, where the weight ratio of platinum to palladium in the second reactive coating is <2, such as 1.5: 1 or certain 1: 1, p. e.g., <1: 1, the weight ratio of the first reactive coating is preferably <1: 2, most preferably about 2: 1. In particular embodiments, a weight ratio of Pt: Pd of both the first reactive coating and the second reactive coating combined is> 1: 1.
    [000108] Figure 5 is a schematic drawing of a system of
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    39/63 exhaust 10 according to the second most preferred embodiment, according to the third aspect of the present invention, comprising, in a series arrangement upstream, a flow substrate 2 monolith coated with a DOC composition of two layers, according to the present invention; a wall flow filtering substrate monolith 4, coated in 100% of its input channels with 5 gft 3 (166.5 g / m 3 ) of platinum supported by particulate alumina and 35% of a total length of its channels output of 1.75 gft ' 3 (58.3 g / m 3 ) of palladium supported by particulate alumina; an ammonia source 6 comprising an injector for an ammonia precursor urea; and a flow substrate monolith 8, coated with an SCR Beta / Fe catalyst. Each substrate monolith 2, 4, 8 is arranged in a metallic container or "can", including cone-shaped diffusers and is connected by a series of ducts 3 with a smaller cross-sectional area than a cross-sectional area of either of substrate monoliths 2, 4, 8. Cone-shaped diffusers act to spread the flow of exhaust gas entering an enclosure of a “canned” substrate monolith, so that the exhaust gas as a whole it is driven through substantially the entire "face" of the front of each substrate monolith. The substrate monolith 8 leaving the exhaust gas is emitted into the atmosphere in the “discharge pipe” 5.
    [000109] Flow substrate monolith 2, coated with two-layer DOC, is designed to promote oxidation of hydrocarbons, carbon monoxide and nitrogen oxide and has a weight ratio Pt: Pd in the top layer of 2 : 1 and total Pt: Pd weight ratio of 6: 1. The catalyzed wall flow substrate monolith 4 is described in the Applicant / Assignee's sister patent application, filed on the same date as the present application, entitled “Catalysed Substrate Monolith” under reference number 70050, in which it was found that palladium disposed at one end downstream of the outlet channels of a wall flow filter can reduce or prevent platinum that has volatilized upstream of the flow channels
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    40/63 inlet of the wall flow filter and / or a substrate monolith comprising platinum-containing catalysts, such as a DOC, upstream of the wall flow filter, to pass downstream to the SCR catalyst, thereby poisoning the conversion ΝΟχ in the SCR catalyst, possibly through the formation of a volatile Pt alloy with palladium. As such, the total Pt: Pd weight ratio of the two-layer DOC can be relatively high, without fear of platinum volatizing from DOC and passing directly to the SCR catalyst. However, the <2: 1 limit for the second reactive coating limits the amounts of platinum that can volatize from DOC as much as possible.
    [000110] With reference to Figure 6, there is shown an exhaust system 20 according to the second most preferred embodiment, according to the third aspect of the present invention, comprising, in serial order from upstream to a substrate monolith flow 22 homogeneously coated with a red NAC composition; and a wall flow filter substrate monolith 24 coated in its inlet and outlet channels with an SCR CuCHA catalyst. Each substrate monolith 22, 24 is arranged in a metallic container or “can”, including cone-shaped diffusers and are connected by a series of ducts 3 with a smaller cross-sectional area than a cross-sectional area of one or the other substrate monolith 22, 24.
    [000111] In combination with a properly designed and controlled diesel compression ignition engine (upstream of the substrate monolith, not shown), enriched exhaust gas, that is, exhaust gas containing increased amounts of carbon monoxide and relative hydrocarbons to normal poor operating mode, contact NAC. Components within a NAC, such as ceria or PGM-promoted ceria-zirconia, can promote the water-gas displacement reaction, ie CO (g) + H 2 O ( v ) -> CO 2 (g) + Hz ( g) emitting H 2 . From the footnote to the
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    41/63 secondary reaction to reactions (3) and (4) set out below, p. Ba (NO3) 2 + 8H 2 -> BaO + 2NH3 + 5H 2 O, NH3 can be generated in situ and stored for ΝΟχ reduction in the SCR catalyst downstream of the flow substrate monolith 24. Exhaust gas leaving the substrate monolith 24 is exhausted to the atmosphere in the “discharge tube” 5. An upper layer of the red NAC composition comprises both platinum and palladium in a 2: 1 weight ratio, but the total Pt: Pd weight ratio of the NAC composition as a whole is 4: 1, in order to promote NO oxidation upstream of the SCR catalyst.
    [000112] Fig. 7 is a schematic drawing of an exhaust system 30 according to the third most preferred embodiment, according to the third aspect of the present invention, comprising, in serial order from upstream to downstream, a monolith flow substrate 32 homogeneously coated with a two-layer DOC composition; an ammonia source 6, comprising an injector for an ammonia precursor urea; a downstream flow monolith substrate 34, coated with an SCR CuCHA catalyst; and a downstream catalyzed soot filter, based on a wall flow filter substrate 36. The substrate monoliths 32, 34, 36 are arranged in a metallic container or “can”, including conical diffusers and are connected by a series of conduits 3 with a smaller cross-sectional area than a cross-sectional area of each substrate monolith 32, 34, 36.
    [000113] In this embodiment, the flow substrate monolith 34, coated with the SCR catalyst, is in direct fluid communication with the flow substrate monolith 32 comprising DOC. In order to reduce or prevent platinum group metals from volatizing from DOC and migrating to the SCR catalyst, the two-layer DOC composition is designed to include both platinum and palladium in the second reactive coating in a Pt: Pd weight ratio of 2 :1. To promote NO oxidation in this way
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    42/63 promoting reactions (1) and (6), the weight ratio Pt: Pd is 4: 1.
    [000114] As explained above, the system in Figure is a preferred system arrangement for light duty diesel, because an important consideration is to achieve ΝΟχ conversion to an exhaust system as quickly as possible after a vehicle engine is started, to enable (i) the precursors of nitrogenous reducers, such as ammonia, to be injected / decomposed in order to release ammonia for ΝΟχ conversion; and (ii) as high ΝΟχ conversion as possible.
    VEHICLES [000115] The invention is for use in the exhaust systems of vehicles equipped with an internal combustion engine. Specific examples of vehicles using an internal combustion engine can be listed as: cars, buses, trucks, locomotives, motorcycles, motorized bicycles and heavy construction machines, etc .; carriers such as aircraft; forestry and agricultural machinery, such as plows, tractors, combined, chainsaw trucks and raw timber transporters; vessels such as ships, fishing vessels and motor boats; civil engineering machinery, such as cranes, compactors and excavators; and generators. However, the application is not limited to that.
    DEFINITIONS [000116] The term "oxidation catalyst", as used herein, particularly with reference to the first aspect of the invention, generally refers to the combination of a substrate and an oxidation catalyst, such as the oxidation catalyst of the second aspect of invention.
    [000117] The term "plurality of catalyst layers", as used herein, particularly with reference to the first aspect of the invention, includes "a catalyst layer" and one or more "other catalyst layers". The “one catalyst layer” can be located directly on top of or be arranged on top of one or more “other catalyst layers”
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    43/63 (eg, the uppermost of the “other catalyst layers”) or one or more intervening layers (eg, layers that are not “catalyst layers”) can be arranged between “a catalyst layer” and one or more of “other catalyst layers”.
    [000118] The term "catalyst surface layer side", as used herein, particularly with reference to the first aspect of the invention, refers to the side of the oxidation catalyst that is first exposed to an exhaust gas, which is usually the outermost catalytic layer.
    [000119] The term "underside that does not dictate a catalyst layer", as used herein, particularly with reference to the first aspect of the invention, refers to the part or area of the oxidation catalyst that is between "a catalyst layer" and the “support substrate”.
    [000120] The term "plurality of catalyst layers comprises a reactive coating material, an active metal and a hydrocarbon adsorbent" as used herein, particularly with reference to the first aspect of the invention, refers to two or more catalyst layers in which the The combination of all catalyst layers (i.e., all layers) comprises the reactive coating material, the active metal and the hydrocarbon adsorbent. Thus, the reactive coating material. Thus, the reactive coating material, the active metal and the hydrocarbon adsorbent do not have to be present in every catalyst layer. Typically, however, each catalyst layer comprises, consists essentially of, or consists of, a reactive coating material and at least one of an active metal or a hydrocarbon adsorbent. Thus, the "catalyst layer" may comprise, consist essentially of, or consist of, a reactive coating material and a hydrocarbon adsorbent and the "one or more other catalyst layers" may comprise, consist essentially of, or consist of a material of reactive coating and at least one of an active metal.
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    However, in general, each catalyst layer comprises, consists essentially of, or consists of a reactive coating material, an active metal and a hydrocarbon adsorbent.
    [000121] The term "amount of hydrocarbon adsorbent" as used herein, particularly with reference to the first aspect of the invention, refers to the total amount of hydrocarbon adsorbent that is present. Thus, the "amount of hydrocarbon adsorbent in the catalyst layer" refers to the total amount of hydrocarbon adsorbent in the "catalyst layer". The "amount of hydrocarbon adsorbent in one or more other catalyst layers" refers to the total amount of hydrocarbon adsorbent that is present in all "other catalyst layers". Typically, the “amount of hydrocarbon adsorbent” is measured as the “mass of hydrocarbon adsorbent” (eg, the weight of the hydrocarbon adsorbent). If more than one type of hydrocarbon adsorbent is present, then the “amount” refers to the total amount of all types of hydrocarbons present.
    [000122] The term "active metal concentration" as used herein, particularly in relation to the first aspect of the invention, refers to the ratio of the weight of active metal to the total weight of the respective catalyst layer expressed as a percentage by weight. The “concentration of the active metal in a catalyst layer” refers to the total concentration of the active metal or metals in “a layer of catalyst” The “concentration of active metal in one or more other layers of catalyst” refers to total concentration of the metal or active metals in all “other catalyst layers”.
    [000123] The expression "the concentration of active metal in said catalyst layer is the same as ... the concentration of active metal in said one or more other catalyst layers", as used here, particularly in relation to the first aspect of invention, covers concentrations that differ by only 1% of its average value,
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    45/63 preferably 0.1% of its average value or, more preferably, 0.01% of its average value. Typically, concentrations are, for all intents and purposes, the same when measured by standard conventional methods for measuring concentration.
    [000124] The expression "the amount of hydrocarbon adsorbent in said catalyst layer is the same as the amount of hydrocarbon adsorbent in said one or more other catalyst layers", as used herein, particularly in relation to the first aspect of the invention , covers quantities that differ by only 1% of their average value, preferably 0.1% of their average value or, more preferably, 0.01% of their average value. Typically, quantities are, for all intents and purposes, the same when measured by standard conventional methods for measuring quantity.
    [000125] The expression "the weight of the active metal in said catalyst layer is approximately the same as the weight of the active metal in said one or more other catalyst layers" as used herein, particularly in relation to the first aspect of the invention, encompasses weights which differ by only 1% of their average value, preferably 0.1% of their average value, or more preferably 0.01% of their average value. Typically, weights are, for all intents and purposes, the same when measured by standard, conventional methods for measuring weight.
    [000126] Any reference to a "catalyst weight" as used herein, particularly with reference to the first aspect of the invention, refers to the weight of the reactive coating material (e.g., the reactive coating comprising the active, adsorbent metal hydrocarbon and reactive coating material) that is applied to a supporting substrate. Typically, the term "a catalyst layer" as used herein, particularly with reference to the first aspect of the invention, is synonymous with the term "second reactive coating" which is used in other respects
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    46/63 of the invention. Similarly, the term "other catalyst layer" as used herein, particularly with reference to the first aspect of the invention, is typically synonymous with the term "first reactive coating" which is used in other aspects of the invention.
    [000127] For the avoidance of doubt, the expression “a second reactive coating is arranged on a layer above the first reactive coating” means that the second reactive coating can be located directly on top of the first reactive coating or that one or more intervening layers can be be arranged between the first reactive coating and the second reactive coating. Three three-layer catalyst compositions are known in the art from both DOC and NAC (see UK patent application No. 1021649.7, filed December 21, 2010 in the name of the Claimant / Assignee, respectively).
    [000128] The term "consisting essentially of" as used herein limits the scope of a claim or a detail of a claim to include the specified materials or steps and any other materials or steps that do not materially affect the basic features of the claimed invention. It has a meaning that it is intermediate between the expressions "consisting of" and "comprising".
    EXAMPLES [000129] The invention will now be illustrated by the following non-limiting examples.
    Reference Example 1
    1) Preparation of a catalyst layer (surface layer side) [000130] Pt and Pd (2: 1) as active metals were mixed with alumina (AI2O3) as the reactive coating material and zeolite as the hydrocarbon adsorbent, and a "catalyst layer" sludge was prepared. The amount of hydrocarbon adsorbent present was 12 g per liter of support and the concentration of the active metal was 0.4% by weight. O
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    47/63 weight of the catalyst per liter of support was 50 g (active metal 0.2 g).
    2) Preparation of another catalyst layer (support side) [000131] Pt and Pd (2: 1) as active metals were mixed with alumina (AI2O3) as reactive coating material and zeolite as a hydrocarbon adsorbent, and a “ another catalyst layer ”was prepared. The amount of hydrocarbon adsorbent present was 30 g per liter of support and the concentration of active metal was 1.7% by weight. The weight of the catalyst per liter of support was set at 105 g (active metal 1,785 g).
    3) Coating on support substrate [000132] Firstly, a 1.3 liter NGK honeycomb substrate was coated with the mud for the “other catalyst layer”. Calcination was then performed. Then, the sludge for "one catalyst layer" was coated on the "other catalyst layer". Calcination was then carried out, providing Reference Example 1.
    Reference Example 2
    1) Preparation of a catalyst layer (surface layer side) [000133] Pt and Pd (2: 1) as active metals mixed with alumina (AI2O3) as reactive coating material and zeolite as a hydrocarbon adsorbent, and a sludge from “A catalyst layer” was prepared. The amount of hydrocarbon adsorbent present was 12 g per liter of support and the concentration of the active metal was 2% by weight. The weight of the catalyst per liter of support was set at 90 g (1.8 g active metal).
    2) Preparation of another catalyst layer (support side) [000134] Pt and Pd (2: 1) as active metals were mixed with alumina (AI2O3) as reactive coating material and zeolite as a hydrocarbon adsorbent, and a “ a catalyst layer ”was prepared. The amount of hydrocarbon adsorbent present was 1230 g per liter of support and the concentration of the active metal was 0.3% by weight. The weight of
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    48/63 catalyst per liter of support was set at 65 g (active metal 0.195 g).
    3) Coating on support substrate [000135] Reference Example 2 was obtained as in Reference Example 1.
    Evaluation Test 1 [000136] The finished catalyst was heat treated in an oven at 800 ° C for 20 hours and then mounted on the exhaust pipe of a diesel engine 4 in Unha. Using commercial diesel oil (JIS 2), a transient activity test was performed with the actual exhaust gas and the performance of the catalyst was evaluated.
    Test Results 1 [000137] The results are given in Table 1. The T50 (the inlet temperature of the catalyst when the conversion reaches 50% - a higher catalyst performance is indicated the lowest numerical value of T50) was low for Reference Example 2, suggesting that the catalytic activity of Reference Example 1 was higher than in Reference Example 2.
    Table 1
    COT 50 0: ° C Example Reference 1 188 Example Reference 2 202
    Reference Example 3
    1) Preparation of a catalyst layer (surface layer side) [000138] Pt and Pd (2: 1) as active metals were mixed with alumina (AI2O3) as reactive coating material and zeolite as a hydrocarbon adsorbent, and a sludge from “A catalyst layer” was prepared. The amount of hydrocarbon adsorbent present was 30 g per liter of support and the concentration of the active metal was 1.7% by weight. The weight of the catalyst per liter of support was set at 105 g (active metal 1,785 g).
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    2) Preparation of another catalyst layer (support side) [000139] Pt and Pd (2: 1) as active metals were mixed with alumina (AI2O3) as reactive coating material and zeolite as a hydrocarbon adsorbent, and a “ a catalyst layer ”was prepared. The amount of hydrocarbon adsorbent present was 12 g per liter of support and the concentration of the active metal was 0.4% by weight. The weight of the catalyst per liter of support was set at 50 g (active metal 0.2 g).
    3) Coating on the support substrate [000140] Reference Example 3 was obtained as in Reference Example 1.
    Evaluation test 2 [000141] The finished catalyst was heat treated in an oven at 800 ° C for 20 h and then mounted on the exhaust pipe of a diesel engine 4 in Unha. Using commercial diesel oil (JIS 2) a provisional activity test was performed with the actual exhaust gas and the performance of the catalyst was evaluated.
    Test results 2 [000142] The results are given in Table 2 and suggested that the catalyst activity of Reference Example 3 was higher than that of Reference Example 2.
    Table 2
    COT 50 0: ° C Example Reference 1 193 Example Reference 2 202
    Example 1
    1) Preparation of a catalyst layer (layer side of the surface) [000143] Pt as an active metal was mixed with alumina (AI2O3) as reactive coating material and zeolite as a hydrocarbon adsorbent, and a “catalyst layer” sludge was ready. The amount of hydrocarbon adsorbent present was 24 g per liter of
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    50/63 support and the concentration of the active metal was 0.2% by weight. The weight of the catalyst per liter of support was set at 90 g (active metal 0.18 g).
    2) Preparation of another catalyst layer (support side) [000144] Pt as an active metal was mixed with alumina (AI2O3) as a reactive coating material and zeolite as a hydrocarbon adsorbent, and a slurry from the “other catalyst layer” was prepared . The amount of hydrocarbon adsorbent present was 6 g per liter of support and the concentration of the active metal was 2.2% by weight. The weight of the catalyst per liter of support was set at 90 g (active metal 1.98 g).
    3) Coating on the support substrate [000145] Example 1 was obtained using the same method described in Reference Example 1.
    Reference Example 4
    1) Preparation of a catalyst layer (surface layer side) [000146] Pt as an active metal was mixed with alumina (AI2O3) as a reactive coating material and zeolite as a hydrocarbon adsorbent, and a “catalyst layer” sludge was ready. The amount of hydrocarbon adsorbent present was 15 g per liter of support and the concentration of the active metal was 1.2% by weight. The weight of the catalyst per liter of support was set at 90 g (active metal 1.08 g).
    2) Preparation of another catalyst layer (support side) [000147] Pt as an active metal was mixed with alumina (AI2O3) as a reactive coating material and zeolite as a hydrocarbon adsorbent, and a slurry from the “other catalyst layer” was prepared . The amount of hydrocarbon adsorbent present was 15 g per liter of support and the concentration of the active metal was 1.2% by weight. The weight of the catalyst per liter of support was set at 90 g (active metal 1.08 g).
    3) Coating on the support substrate [000148] Reference Example 4 was obtained as in the Example of
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    Reference 1
    Reference Example 5
    1) Preparation of a catalyst layer (surface layer side) [000149] Pt as an active metal was mixed with alumina (AI2O3) as a reactive coating material and zeolite as a hydrocarbon adsorbent, and a “catalyst layer” sludge was ready. The amount of hydrocarbon adsorbent present was 6 g per liter of support and the concentration of the active metal was 2.2% by weight. The weight of the catalyst per liter of support was set at 90 g (active metal 1.98 g).
    2) Preparation of another catalyst layer (support side) [000150] Pt as an active metal was mixed with alumina (AI2O3) as a reactive coating material and zeolite as a hydrocarbon adsorbent, and a “catalyst layer” sludge was prepared. The amount of hydrocarbon adsorbent present was 24 g per liter of support and the concentration of the active metal was 0.2% by weight. The weight of the catalyst per liter of support was set at 90 g (active metal 0.18 g).
    3) Coating on the support substrate [000151] Reference Example 5 was obtained as in Reference Example 1.
    Evaluation test 3 [000152] The finished catalyst was heat treated in an oven at 800 ° C for 20 h and then mounted on the exhaust pipe of a diesel engine 4 in Unha. Using commercial diesel oil (JIS 2), a transient activity test was performed with the actual exhaust gas and the performance of the catalyst was evaluated.
    Test Results 3 [000153] The results are given in Table 3 and suggest that the catalytic activity is distinctly higher in Example 1 than in Reference Examples 4 and 5. The results then indicated that, in a comparison
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    52/63 by weight of uniform catalyst from one catalyst layer and the other catalyst layer, the CO oxidation activity improved because of a catalyst structure in which the amount of hydrocarbon adsorbent present in the catalyst layer was greater than the concentration present in the other catalyst layer, and the concentration of the active metal present in one catalyst layer was less than the concentration of the aforementioned active metal, present in the other catalyst layer.
    Table 3
    COT50: ° C Example 1 180 Example Reference 4 199 Example Reference 5 198
    Example 2
    Preparation of 3 wt% Coated Substrate Monolith Zeolite CHA / Cu [000154] Commercially available ahiminosilicate zeolite CHA was added to an aqueous Cu (NO 3 ) solution with stirring. The sludge was filtered, then washed and dried. The procedure can be repeated to obtain a desired metal charge. The final product was calcined. After mixing, binders and rheology modifiers were added to form a reactive coating composition.
    [000155] A 400 cpsi cordierite flow substrate monolith was coated with an aqueous sludge from the CHA / Cu zeolite sample, using the method described in Applicant / Assignee 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 liquid component within said containment medium, in the order (a) next (b) or (b) next (a ), and (c) applying pressure or vacuum, pulling said liquid component into at least part of the support and retaining substantially all said amount within the support. This one
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    53/63 coated product (coated on one end only) is dried and then calcined and this process is repeated on the other end, so that substantially the entire substrate monolith is coated, with less overlap in the axial direction at the joint between the two coatings. The coated substrate monolith was aged in an air oven at 500 ° C for 5 hours. A core of 1 inch (2.54 cm) in diameter x 3 inches in length (7.62 cm) was cut from the finished article.
    Example 3
    Preparation of Diesel Oxidation Catalyst A [000156] Platinum nitrate and palladium nitrate were added to an aqueous slurry of particulate silica-alumina. Beta zeolite was added to the sludge, so that it comprised <30% of the solids content as zeolite by mass to create a reactive coating sludge. The reactive coating slurry was dosed on a 400 cpsi flow substrate monolith using the method described in WO 99/47260. The dosed part was dried and then calcined at 500 ° C. The Pt: Pd weight ratio of the first layer of reactive coating was 2: 1.
    [000157] A second aqueous reactive coating sludge was prepared as described above, but with different amounts of platinum nitrate and palladium nitrate. This second reactive coating cover slurry was dosed on top of the first previously coated layer, using the same methods used to apply the first reactive coating cover. The second cover was dried and then calcined at 500 ° C. The weight ratio of Pt: Pd in the second reactive coating cover layer was 1: 1.6 and the total PGM load of the first reactive coating cover and the second reactive coating cover was 1: 1. The total reactive coating charge of the first and second combined reactive coating coatings was 3.0 gin ' 3 (0.18 g / cm 3 ) and the total platinum group metal charge in the first
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    54/63 combined reactive coating coverage and the second reactive coating coverage was 120 gin 3 (7.32 g / cm 3 ).
    [000158] 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 "fresh", that is, not aged.
    Reference Example 6
    Preparation of Diesel B Oxidation Catalyst [000159] Platinum nitrate and palladium nitrate were added to an aqueous slurry of particulate stabilized alumina. Beta zeolite was added to the mud, so that it comprised <30% of the solids content as zeolite by mass. The sludge from the reactive coating was dosed on a 400 cpsi flow substrate monolith, using the same method as in Example 3. The coated part was dried and then calcined at 500 ° C. The weight ratio of Pt: Pd in the first reactive coating was 2: 1.
    [000160] A second aqueous reactive coating sludge was prepared by adding platinum nitrate to a particulate alumina sludge. Beta zeolite was added to the mud, so that it comprised <30% of the solids content as zeolite by mass. This reactive coating was dosed on top of the first layer previously coated, using the same method as above. The second layer of reactive coating was then dried and the part was calcined at 500 ° C. The Pt: Pd weight ratio of the second reactive coating cover was 1: 0 and the total reactive coating charge of the first reactive coating cover and the second reactive coating cover combined was 3.0 gin 3 (0.18 g / cm 3 ), with most of the reactive coating charge in the bottom layer. The total platinum group metal load of the first and second reactive coating coatings was 85 gft ' 3 (5.18 g / cm 3 ). The weight ratio of Pt: Pd of both the first reactive coating cover and the second reactive coating cover
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    55/63 combined was 4: 1. A core 1 inch (2.54 cm) in diameter x 3 inches (7.62 cm) in length was cut from the finished article. The resulting part can be described as "fresh", that is, not aged.
    Example 4
    Preparation of Diesel Oxidation Catalyst C [000161] Platinum nitrate was added to an aqueous platinum slurry. Beta zeolite was added to the mud, so that it comprised <30% of the solids content as zeolite by mass. The reactive coating slurry was dosed on a 400 cpsi flow substrate monolith, using the same method as in Example 2. The dosed part was dried and then calcined at 500 ° C. This first coating had a 1: 0 Pt: Pd weight ratio.
    [000162] A second aqueous reactive coating sludge was prepared by adding platinum nitrate and palladium nitrate to the particulate alumina sludge. Beta zeolite was added to the mud, so that it comprised <30% of the solids content as zeolite by mass. This second reactive coating slurry was dosed on top of the first layer previously coated. The second coating of the reactive coating was dried and calcined at 500 ° C. The second reactive coating had a Pt: Pd ratio of 2: 1. The Pt: Pd weight ratio of both the first reactive coating and the second reactive coating combined was 4: 1 and the total metal load of the platinum group of both combined layers was 85 gft ' 3 (5.18 g / cm 3 ). The total reactive coating load of both the first and second combined layers was 3.0 gin ' 3 (0.18 g / cm 3 ), with most of the reactive coating load being on the second reactive coating.
    [000163] 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 can be described as "fresh", that is, not aged.
    Example 5
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    System Tests [000164] The tests were performed in a first synthetic catalytic activity test (SCAT) laboratory reactor illustrated in Figure 1, in which an aged core of the coated CHA / Cu zeolite SCR catalyst of Example 1 was arranged in a conduit downstream of a diesel oxidation catalyst (DOC) B (according to Reference Example 6) or C (according to Example 4) core. 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 at a constant 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 kept in a catalyst temperature of 300 ° C during the aging process, adjusting the length of the tube between the oven outlet and the SCR inlet, although a water-cooled heat exchanger jacket could also be used as appropriate. determined using appropriately positioned thermocouples (Ti and T 2 ). The gas mixture used during aging was 50% air, 50% N 2 , 10% H 2 O.
    [000165] Following DOC aging, 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 SCR catalysts were then tested for SCR activity at 500 ° C, using a mixture of synthetic gas (O 2 = 10%; H 2 O = 5%; CO 2 = 7.5%; CO = 330 ppm; NH3 = 400 ppm; NO = 500 ppm; NO 2 = 0 ppm; N 2 = the rest, that is, an alpha value of 0.8 was used (NH3: NO X ratio), so that the maximum NO X conversion possible was 80%) and the resulting ΝΟχ conversion was plotted in relation to the temperature of the accompanying bar graph in Figure 2. This plot essentially measures the competition between reaction (9) and reaction (5) and thus how much reaction (9 ) affects ΝΟχ conversion by consumption of
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    Available NH 3 , required for the SCR reaction (reaction (5)).
    [000166] It can be seen from the results shown in Figure 2 that DOC C (according to Example 6) retains a higher proportion of ΝΟχ conversion activity than DOC B (according to Reference Example 6). This result is interpreted as indicating that, under the conditions used for the rest, Pt is more readily volatilized from the external layer of DOC B, which has a weight ratio of Pt: Pd of 1: 0, than from the reverse arrangement of DOC C, where the outer layer has a weight ratio of Pt: Pd of 2: 1, although the combined weight ratio of total Pt: Pd of both layers in both cases was the same, that is, 4: 1.
    Example 6
    Preparation of Substrate Monolith Coated with 5% by weight of Zeolite Beta / Fe [000167] Commercially available Zeolite Beta was added to an aqueous solution of Fe (NO 3 ) 3 with stirring. After mixing, binders and viscosity modifiers were added to form a reactive coating composition.
    [000168] A 400 cpsi cordierite flow substrate monolith was coated with a 5% by weight aqueous Beta / Fe zeolite sample using the method described in Applicant / Assignee WO 99/47260, as described in Example 2 above. This coated product (coated on one end only) is dried and then calcined and this process is repeated on the other end, so that substantially the entire substrate monolith is coated, with a small overlap in the axial direction at the junction between the two coatings. A core of 1 inch (2.54 cm) in diameter x 3 inches in length (7.62 cm) was cut from the finished article.
    Reference Example 7
    Preparation of Pt-Catalyzed Wall Flow Filter
    Petition 870190074061, of 08/01/2019, p. 67/155
    58/63 [000169] A reactive coating composition, comprising a mixture of alumina particles ground 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 in a reactive coating load of 0.2 g / in 3 (0.122 g / m 3 ) at a final total Pt load of 5 g / foot ' 3 (166.5 g / m 3 ), using the method and apparatus described in WO 2011/00525, in which channels at a first end, intended for orientation to an upstream side, were covered in 75% of their full length with a reactive coating comprising platinum nitrate and particulate alumina from its intended upstream end; and channels at an opposite end and intended to be oriented to a downstream side are coated over 25% of their total length, with the same reactive coating as the inlet channels. That is, the method consisted of the steps of (i) retaining a substantially vertical alveolar monolith substrate; (ii) introducing a predetermined volume of the liquid into the substrate via open ends of the channels at a lower end of the substrate; (iii) sealingly retain the liquid introduced into the substrate; (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 pull the liquid along the substrate channels. The catalyst composition was coated over the filter channels of a first end, after the coated filter had dried. The dried filter coated on the first end was then turned over and the method repeated to coat the same catalyst for the filter channels on the second end, followed by drying and calcination.
    [000170] A core 1 inch (2.54 cm) in diameter x 3 inches (7.62 cm) in length was cut from the finished article. The resulting part can be described as "fresh", that is, not aged.
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    Example 7
    Preparation of wt% 1: 1 Pt: Pd Containing Wall Flow Filter [000171] A coated filter was prepared using the same method as in Reference Example 7, except that the reactive coating applied to both the inlet and outlet channels of the filter included palladium nitrate, in addition to platinum nitrate. The reactive coating load in the inlet and outlet channels was conducted in such a way as to reach a load of Pt of 5 g / ft 3 (166.5 g / m 3 ), of Pd of 5 g / ft 3 (166 , 5 g / m 3 ), both on the inlet and outlet surfaces, ie a PGM load of 10 g / ft 3 (333 g / m 3 ).
    [000172] A core of 1 inch (2.54 cm) in diameter x 3 inches in length has been cut from the finished article. The resulting part can be described as "free", that is, not aged.
    Example 8
    Preparation of 5: 1 Pt: Pd by weight Containing Catalyzed Wall Flow Filter [000173] A coated filter was prepared using the same method as in Reference Example 7, except that the reactive coating applied to both Inlet channels as well as the filter outlet channels included palladium nitrate, in addition to platinum nitrate. The reactive coating load in the inlet and outlet channels was conducted in such a way as to reach a Pt load of 5 g / ft 3 (166.5 g / m 3 ), Pd of 1 g / ft 3 (33 , 3 g / m 3 ) on both the inlet and outlet surfaces, ie a PGM load of 6 g / ft 3 (199.8 g / m 3 ).
    [000174] A core of 1 inch (2.54 cm) in diameter x 3 inches in length has been cut from the finished article. The resulting part can be described as "fresh", that is, not aged.
    Example 9
    System Tests
    Petition 870190074061, of 08/01/2019, p. 69/155
    60/63 [000175] The tests were performed in a first synthetic catalytic activity test (SCAT) laboratory reactor illustrated in Figure 1, in which a fresh core of the Beta / Fe zeolite SCR catalyst of Example 2 is arranged in a downstream conduit of a catalyzed wall flow filter core of Reference Example 7 or Example 7 or
    8. A mixture of synthetic gas was passed through the flue in a swept catalyst volume of 30,000 h 1 . An oven was used to heat (or "age") the catalyzed wall flow filter sample at a constant state temperature at a filter inlet temperature of 900 ° C for 60 minutes, during which time the temperature of the SCR catalyst inlet was 300 ° C. An air cooling mechanism (heat exchanger) or water was used to achieve 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 Cl, the rest N2.
    [000176] Following aging, 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 (O2 = 14%; H2O = 7%; CO2 = 5 %; NH3 = 250 ppm; NO = 250 ppm; NO2 = 0 ppm; N2 = 0 rest) and the resulting conversion of NO2 was plotted in relation to the temperatures for each temperature data point in Figure 2. This plot essentially measures the competition between reaction (9) and reaction (5) and, thus, how much reaction (9) affects the conversion of NO X by the consumption of available NH3, necessary for the SCR reaction (reaction (5)).
    [000177] The results are plotted graphically in Figure 3. With reference to Figure 3, it can be seen that the Beta / Fe zeolite SCR catalyst, aged behind the catalyzed soot filter, having a weight ratio
    Petition 870190074061, of 08/01/2019, p. 70/155
    61/63 Pt: Pd of 1: 0 (ie Reference Example 7), has significantly reduced total ΝΟχ conversion activity compared to the fresh sample. The catalyzed soot filter of Example 8, which has a Pt: Pd weight ratio of 5: 1, improved the conversion activity of emχ, compared to Reference Example 7. However, Example 7, which has a relationship in weight Pt: Pd of 1: 1, it demonstrably has performance similar to that of the SCR catalyst not aged. Substantially no loss of activity was seen between a fresh Beta / Fe catalyst and a Beta / Fe catalyst aged at 300 ° C for 1 hour, with no catalyst present upstream (results not shown).
    Example 10
    More Pt: Pd Weight Ratio States [000178] Two more diesel oxidation catalysts were prepared as follows:
    Diesel Oxidation Catalyst D [000179] 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 mud, so that it comprised <30% of the solids content as zeolite by mass. The reactive coating slurry was dosed on a 400 cpsi flow substrate, using the method of Example 3. The metered part was dried and then calcined at 500 ° C. The total platinum group metal load in the reactive coating layer was 60 gft 3 (1998 g / m 3 ) and the total Pt: Pd weight ratio was 4: 1.
    [000180] A core 1 inch (2.54 cm) in diameter x 3 inches (7.62 cm) in length was cut from the finished article. The resulting part can be described as "fresh", that is, not aged.
    Diesel Oxidation Catalyst E [000181] A single layer DOC was prepared as follows. Platinum nitrate and palladium nitrate were added to a silica-alumina slurry.
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    Beta zeolite was added to the mud, so that it comprised <30% of the solids content as zeolite by mass. The reactive coating slurry was dosed on a 400 cpsi flow substrate, using the same method used for DOC D. The dosed part was dried and then calcined at 500 ° C. The total PGM load of the single-layer DOC was 120 gft ' 3 (3996 g / m 3 ) and the weight ratio of Pt: Pd was 2: 1. A core 1 inch (2.54 cm) in diameter, 3 inches (7.62 cm) in length was cut from the finished article. The resulting part can be described as "fresh", that is, not aged.
    [000182] Both catalysts were tested according to the protocols set out in Example 5. The results are given in Figure 4 with reference to a control (aged SCR catalyst, which was no longer aged downstream of DOC D or SWEET).
    CONCLUSIONS [000183] Taken as a whole, the results of Example 9, shown in Figure 3 with respect to Examples 7 and 8, and Reference Example 7, indicate that a Pt: Pd weight ratio between 1: 1 and 5: 1 it is beneficial in reducing the problem of loss of ΝΟχ conversion activity, through the volatilization of the platinum group metal, mainly platinum, from a catalyst containing platinum group metal to a downstream SCR catalyst; and [000184] The results of Examples 5 and 10 shown in Figure 4, in connection with Diesel Oxidation Catalysts D and E, show that, for an aged SCR catalyst downstream of a DOC having a weight ratio of Pt: Pd 2 : 1 total, the loss of ΝΟχ conversion activity is relatively slight to 67% of ΝΟχ conversion activity, compared to the control of 72% of ΝΟχ conversion activity (an aged SCR catalyst behind a total DOC of weight ratio Pt: Pd (not described here) using the same protocol, had a atividadeχ conversion activity of 69%). However, when the total Pt: Pd weight ratio was increased to 4: 1, SCR activity was significantly reduced to 48%.
    Petition 870190074061, of 08/01/2019, p. 72/155
    63/63 [000185] It is concluded, therefore, that there is a limit of weight ratio of Pt: Pd of 2: 1 generally, above which Pt volatilization is more likely to occur. As a result, limiting to a total weight ratio of Pt: Pd of 2: 1 in the DOC as a whole, and a weight ratio of Pt: Pd <2: 1 in the second layer of reactive coating, Pt in DOC is less likely to volatilize and migrate to a downstream SCR catalyst.
    [000186] For the avoidance of doubt, the entire content of any and all of the documents cited here is incorporated by reference into this application.
    权利要求:
    Claims (21)
    [1]
    1. Catalyzed substrate monolith, characterized by the fact that it comprises an oxidation catalyst in a through-flow substrate monolith for use in the treatment of the exhaust gas emitted by a low-combustion internal combustion engine, the flow-substrate monolith through having a first end and a second end and comprising a metal or ceramic honeycomb monolith having an elongated channel formation extending through it, the channels being opened at both ends, this catalyzed substrate monolith comprising a first reactive coating having a length L extending the entire length of the substrate monolith channels and a second reactive coating, wherein the second reactive coating is arranged in a layer above, and covering, the first reactive coating for at least part of the length L and arranged in a zone of substantially uniform length at the second end age of the throughflow substrate monolith, zone being defined at one end at the second end of the throughflow substrate monolith itself and at a first end at a point less than the total length of the first reactive coating, the first reactive coating comprises a catalyst composition comprising platinum and at least one support material for platinum, the second reactive coating comprises a catalyst composition comprising both platinum and palladium and at least one support material for platinum and palladium and a weight ratio of platinum for palladium the second reactive coating is <2.
    [2]
    2. Catalyzed substrate monolith according to claim 1, characterized by the fact that the second reactive coating comprises both platinum and palladium and the first reactive coating comprises both platinum and palladium in a weight ratio of Pt: Pd higher than than in the second reactive coating.
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    2/5
    [3]
    3. Catalyzed substrate monolith according to claim 1 or 2, characterized by the fact that a weight ratio of Pt: Pd of both the first reactive coating and the second reactive coating combined is> 1: 1.
    [4]
    4. Catalyzed substrate monolith according to claim 3, characterized by the fact that a weight ratio of Pt: Pd of both the first reactive coating and the second reactive coating combined is> 2: 1.
    [5]
    Catalyzed substrate monolith according to any one of claims 1 to 4, characterized in that a weight ratio of Pt: Pd of both the first reactive coating and the second reactive coating combined is <10: 1.
    [6]
    6. Catalyzed substrate monolith according to any one of claims 1 to 5, characterized in that the first reactive coating comprises 25-75% by weight of the metal of the total platinum group present in the first reactive coating and the second reactive coating combined.
    [7]
    Catalyzed substrate monolith according to any one of claims 1 to 6, characterized in that the at least one support material of the first reactive coating or the second reactive coating comprises a metal oxide selected from the group consisting of optionally alumina stabilized, amorphous silica-alumina, optionally stabilized zirconia, ceria and zirconia, ceria, titania and an optionally stabilized mixed ceriazirconium oxide or a molecular sieve or a mixture of any two or more of them.
    [8]
    Catalyzed substrate monolith according to any one of claims 1 to 7, characterized in that at least one of the first reactive coating and the second reactive coating comprises a molecular sieve <30% by weight of the top coat layer. coating
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    3/5 reactive.
    [9]
    9. Catalyzed substrate monolith according to any of claims 1 to 8, characterized in that the reactive coating charge of each of the first reactive coating and the second reactive coating is individually selected from the range of 0.1- 3.5 gin 3 (0.061 g / cm 3 to 0.21 g / cm 3 ).
    [10]
    10. Catalyzed substrate monolith according to any one of claims 1 to 9, characterized in that the oxidation catalyst is a diesel oxidation catalyst or ΝΟχ adsorbent catalyst.
    [11]
    11. Exhaust system for a low-combustion internal combustion engine, characterized in that it comprises a first catalyzed substrate monolith, as defined in any one of claims 1 to 10, wherein a first end of the flow substrate monolith through is facing the upstream side.
    [12]
    Exhaust system according to claim 11, characterized by the fact that it comprises a second catalyzed substrate monolith, comprising a selective catalytic reduction catalyst (SCR), a second catalyzed substrate monolith being arranged downstream of the first monolith of catalyzed substrate.
    [13]
    13. Exhaust system according to claim 12, characterized by the fact that it comprises an injector to inject a nitrogenous reducer into the exhaust gas, between the first catalyzed substrate monolith and the second catalyzed substrate monolith.
    [14]
    Exhaust system according to claim 12 or 13, characterized by the fact that it comprises a third catalyzed substrate monolith, wherein the third catalyzed substrate monolith is a filtering substrate monolith, having entrance surfaces and surfaces of the exit surfaces and the entrance surfaces are separated from the exit surfaces by a porous structure, a third catalyzed substrate monolith comprising a
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    4/5 oxidation catalyst and is disposed between the first catalyzed substrate monolith and the second catalyzed substrate monolith.
    [15]
    15. Exhaust system, according to claim 14, characterized by the fact that it comprises an injector to inject a nitrogenous reducer into the exhaust gas, between the first catalyzed substrate monolith and the second catalyzed substrate monolith, in which the injector to inject a nitrogenous reducer into the exhaust gas is arranged to inject nitrogenous reducer into the exhaust gas between the third catalyzed substrate monolith and the second catalyzed substrate monolith.
    [16]
    16. Exhaust system according to claim 12 or 13, characterized in that it comprises a third substrate monolith, in which the third substrate monolith is a filtering substrate monolith, having inlet and outlet surfaces, wherein the inlet surfaces are separated from the outlet surfaces by a porous structure, the third substrate monolith being disposed downstream of the second catalyzed substrate monolith.
    [17]
    17. Exhaust system according to claim 16, characterized in that the third substrate monolith comprises an oxidation catalyst.
    [18]
    18. Exhaust system according to any one of claims 12 to 17, characterized in that the second catalyzed substrate monolith is a filtering substrate monolith, having inlet and outlet surfaces, in which the inlet surfaces are separated from the outlet surfaces by a porous structure.
    [19]
    19. Exhaust system according to any of claims 14 to 18, characterized in that the filter substrate monolith is a wall flow filter.
    [20]
    20. Low combustion internal combustion engine, particularly for a vehicle, characterized by the fact that it comprises a
    Petition 870190074061, of 08/01/2019, p. 77/155
    Exhaust system as defined in any one of claims 11 to 19.
    [21]
    21. Method to reduce or prevent a selective catalytic reduction (SCR) catalyst from poisoning with platinum, from an exhaust system from a low-combustion internal combustion engine, which can volatize from a first reactive coating, comprising a catalyst composition comprising platinum and at least one platinum support material, arranged on a substrate monolith upstream of the SCR catalyst, when the catalyst composition, comprising platinum, is exposed to relatively extreme conditions, including relatively high temperatures, where the monolith of substrate is a throughflow substrate monolith having a first upstream end and a second upstream end and comprising a metal or ceramic honeycomb monolith having an elongated channel formation extending through it, channels being opened at both ends , where the first reactive coating has a length L if it is tending for the entire length of the throughflow substrate monolith channels, the method characterized by the fact that it comprises trapping volatilized platinum in a second reactive coating, arranged in a layer above, and covering the, first reactive coating for at least part of the length L, the second reactive coating is arranged in a zone of substantially uniform length at the second end downstream of the throughflow substrate monolith, this zone being defined at one end at the second end just past the throughflow substrate monolith itself and at a first end at a point less than the total length of the first reactive coating, the second reactive coating comprising a catalyst composition comprising both platinum and palladium and at least one support material for platinum and palladium and in which a ratio in platinum weight for palladium of the second re reactive clothing is <2.
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    同族专利:
    公开号 | 公开日
    GB2495404A|2013-04-10|
    US8652429B2|2014-02-18|
    BR112014008228A2|2017-04-18|
    IN2014CN03303A|2015-07-03|
    US20190358616A1|2019-11-28|
    JP2013081878A|2013-05-09|
    US9005559B2|2015-04-14|
    CN103874541A|2014-06-18|
    JP5938819B2|2016-06-22|
    US20130089481A1|2013-04-11|
    CN103874541B|2017-02-15|
    EP3363525A1|2018-08-22|
    EP2763791A2|2014-08-13|
    US10773251B2|2020-09-15|
    KR20140077950A|2014-06-24|
    WO2013050784A3|2013-05-30|
    US20180104677A1|2018-04-19|
    US9868115B2|2018-01-16|
    CN106622352B|2020-10-23|
    US20140130760A1|2014-05-15|
    EP2962744B1|2019-11-27|
    CN106622352A|2017-05-10|
    US20150202604A1|2015-07-23|
    EP2962744A1|2016-01-06|
    BR112014008228B8|2020-01-14|
    KR101634203B1|2016-06-28|
    GB2495404B|2015-10-07|
    US10376867B2|2019-08-13|
    DE102012218254A1|2013-04-11|
    RU2014117966A|2015-11-20|
    GB201217884D0|2012-11-21|
    EP2763791B1|2015-09-30|
    RU2623218C1|2017-06-23|
    RU2570197C1|2015-12-10|
    WO2013050784A2|2013-04-11|
    EP3363526A1|2018-08-22|
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    法律状态:
    2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-06-04| B06T| Formal requirements before examination|
    2019-11-12| B09A| Decision: intention to grant|
    2019-12-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    2020-01-14| B16C| Correction of notification of the grant|Free format text: REFERENTE A RPI 2555 DE 24/12/2019, QUANTO AO ITEM (72) NOME DO INVENTOR. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011221896A|JP5938819B2|2011-10-06|2011-10-06|Oxidation catalyst for exhaust gas treatment|
    US201161569542P| true| 2011-12-12|2011-12-12|
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    US201261623736P| true| 2012-04-13|2012-04-13|
    PCT/GB2012/052482|WO2013050784A2|2011-10-06|2012-10-05|Oxidation catalyst for internal combustion engine exhaust gas treatment|
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