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    • 专利摘要:
    catalyst, method for generating heat for the removal of soot and reducing the exhaust of nh? in an exhaust system, and, exhaust treatment system. a catalyst comprising: (a) a first layer comprising an oxidation catalyst having an effective pgm charge such that oxidation of hydrocarbons generates sufficient heat to regenerate soot, wherein said effective amount of pgm is greater than about 10 g [α] D 25 (357.14 g / m <3>); and (b) a second layer adjacent said first layer and comprising a reduction catalyst for selectively reducing nox.
    公开号:BR112013005816B1
    申请号:R112013005816-1
    申请日:2011-09-15
    公开日:2019-04-30
    发明作者:Julian Peter Cox
    申请人:Johnson Matthey Public Limited Company；
    IPC主号:
    专利说明:

    “CATALYST, METHOD TO GENERATE HEAT TO REMOVE SOOT AND REDUCE NH3 EXHAUST IN AN EXHAUST SYSTEM AND EXHAUST TREATMENT SYSTEM”
    REFERENCE TO RELATED ORDER
    This application claims priority to US Provisional Application No. 61 / 383,112, filed September 15, 2010, which is hereby incorporated by reference in its entirety.
    FIELD OF THE INVENTION
    The invention generally relates to the emission control of poorly burned engines, and, more specifically, to a catalyst that facilitates both the exothermic oxidation of hydrocarbons and the removal of polluting gases containing nitrogen from the exhaust gas.
    FUNDAMENTALS
    Due to environmental concerns, there is a continuing need to reduce emissions from internal combustion engines. Of particular interest here are the internal combustion engines operated using a poor air / fuel mixture, known as “poor combustion engines.” A common poor combustion engine is a diesel engine. Exhaust gas emissions from a low-burn engine can be divided into two groups - primary and secondary emissions. Primary emissions involve polluting gases that are formed directly by the fuel combustion process in the engine and are present in the gross emission before passing through exhaust gas purification devices. The exhaust gas from low-burning engines comprises the usual primary emissions of carbon monoxide (CO), hydrocarbons (HCs), nitrogen oxides (NOx), and soot (also known as particulate matter or PM), along with a content relatively high oxygen content of up to 15% by volume. Secondary emissions are polluting gases that can be formed as by-products in
    Petition 870180155768, of 11/27/2018, p. 6/29 exhaust gas purification units. Such secondary emissions may include, for example, “exhaust” ammonia (nh 3 ) and NOx as discussed below.
    Emission control systems have several configurations. For example, referring to Fig. 1, a typical emission control system 100 for a diesel engine is shown. Immediately after the exhaust gas leaves the engine (not shown), a diesel oxidation catalyst (DOC) 101 oxidizes primary pollutants such as unconsumed fuel (hydrocarbons) and carbon monoxide to render them harmless. Other primary pollutants such as NOx cannot be oxidized, but must instead be reduced to nitrogen. Reducing NOx, however, tends to be more difficult because of the high oxygen content in the exhaust stream.
    A known method of removing NOx from exhaust gases in the presence of oxygen is the selective catalytic reduction (SCR) process. SCR uses ammonia as a reducing agent over a suitable catalyst, SCR 103 catalyst as shown in Fig. 1. The reducing agent is introduced into the exhaust gas system using an injection nozzle 102. Instead of ammonia, a compound which can be easily broken down into ammonia, for example, urea can be used for this purpose.
    To ensure a complete reduction of NOx, ammonia has to be added to the exhaust gas in at least one stoichiometric ratio to nitrogen oxides, and excess ammonia is preferred to improve NOx conversion. Excess ammonia, however, significantly increases the risk of ammonia escaping out of the SCR catalyst, and becoming a secondary emission. Ammonia that paves the way or escapes from the SCR catalyst is referred to as “escape ammonia.” Since ammonia is a gas that has a penetrating odor even at low concentrations, it is desirable to minimize the escape ammonia. However, accurate measurement of ammonia is difficult in
    Petition 870180155768, of 11/27/2018, p. 7/29 internal combustion engines in motor vehicles because of the fluctuating operating conditions of motor vehicles (eg acceleration / deceleration). Therefore, inevitably excess ammonia will be injected into the system, resulting in significant ammonia escaping downstream of the SCR catalyst.
    System 100 also comprises a Diesel Exotherm Catalyst (DEC) 105 behind SCR 103 to facilitate periodic exothermic reactions to generate enough heat to regenerate soot from a Catalytic Soot Filter (CSF) 106. For this purpose, an injector 10 hydrocarbon 104 is located just upstream of the DEC. Injector 104 injects fuel or HCs into the exhaust vapor when the exhaust temperature is above the DEC start temperature. The DEC then oxidizes the HCs to generate an exotherm, which, in turn, heats the filter to clean its soot. Because the DEC is located behind the SCR, the SCR does not experience the damaging high temperatures associated with soot removal.
    Although DEC is good at oxidation, it has the potential to also non-selectively oxidize any escaping ammonia from the SCR catalyst and convert it to NOx, thereby increasing NOx emissions. To counter this, one method involves using a Catalyst 20 Ammonia Escape (ASC) 201 as shown in Fig. 2. The ASC is selective to remove NH3 with minimal NOx oxidation after the SCR 103 catalyst, but in front of the HC 104 injector. Typically the ASC has a charge low platinum group metals (PGM) (eg 0.5 to 10 g / ft 3 (357.14 g / m 3 ) (17.86 to 357.14 g / m 3 )) to maximize selectivity for N2. 25 The disadvantage of this system is the volume of additional catalyst required for the NH3 exhaust catalyst in an already large 200 emission control system.
    Therefore, the need for a simplified exhaust system that eliminates ammonia leakage while
    Petition 870180155768, of 11/27/2018, p. 8/29 exhaust current periodically to regenerate soot from the soot filter. The present invention satisfies this need, among others.
    SUMMARY OF THE INVENTION
    The following presents a simplified summary of the invention in order to provide a basic understanding of some aspects of the invention. This summary is not an extensive overview of the invention. It is not intended to identify key / critical elements of the invention or to outline the scope of the invention. Its sole purpose is to present some concepts of the invention in a simplified form as a prelude to the more detailed description that is presented later.
    The present invention provides a combination catalyst that works, not only to oxidize the exhaust ammonia and hydrocarbons in an exothermic reaction sufficient to generate enough heat to regenerate soot, but also to reduce NOx resulting from such oxidation. More specifically, it was surprisingly found that the high charge concentration in the oxidation catalyst needed to generate enough heat for soot regeneration was neutralized by an SCR catalyst in close proximity to the oxidation catalyst. This facilitates the integration of a traditional DOC and ASC, thereby simplifying an exhaust system that eliminates ammonia leakage while periodically heating the exhaust stream to regenerate soot from the soot filter.
    Consequently, one aspect of the invention relates to a combination DOC / ASC catalyst that eliminates NH3 leakage and heats the exhaust stream periodically to regenerate soot from the soot filter, while reducing secondary NOx emissions. In one embodiment, the combination catalyst comprises: (a) a substrate; (b) a first layer on the substrate, the first layer comprising an oxidation catalyst having an effective PGM charge such that the oxidation of
    Petition 870180155768, of 11/27/2018, p. 9/29 hydrocarbons generate enough heat to regenerate soot, in which, in one embodiment, the effective amount of PGM is greater than about 10 g / ft 3 (357.14 g / m 3 ); and (c) a second layer adjacent to the first layer and comprising a reduction catalyst to selectively reduce NOx.
    Another aspect of the invention relates to a method of using a combined catalyst to periodically heat the exhaust stream to regenerate soot while eliminating exhaust ammonia and NOx emissions. In one embodiment, the method comprises: (a ) inject a nitrogen-reducing agent into an exhaust stream having NOx; (b) reduce NOx using the nitrogen reducing agent in the presence of an SCR catalyst to form a reduced NOx gas stream, which, at least intermittently, contains exhaust nitrogen reducing agent; (c) injecting HC into the reduced NOx gas stream to form a HC-enriched gas stream; and (d) contacting the HC-enriched gas stream with a combined catalyst to form a heated gas stream, the combined catalyst comprising a first layer having an oxidation catalyst to oxidize the exhaust nitrogen reducing agent and HC to heat the gas stream is heated, and a second layer having an SCR catalyst to reduce the NOx formed in the first layer.
    Yet another aspect of the invention is an exhaust system that eliminates ammonia leakage while periodically heating the exhaust stream to regenerate soot from the soot filter 25 using a combination catalyst. In one embodiment, the system comprises: (a) a conduit for transmitting an exhaust gas having NOx from an engine to the atmosphere; (b) an injector to inject the nitrogen reducing agent into the exhaust gas; (c) an SCR catalyst located to contact the exhaust gas and reduce NOx using the
    Petition 870180155768, of 11/27/2018, p. 10/29 nitrogen reducing agent to form a reduced NOx gas stream, which, at least intermittently, contains exhaust nitrogen reducing agent; (d) an HC injector to inject HC into the reduced NOx gas stream to form an HC-enriched gas stream; (e) a combined catalyst located to contact the HC-enriched gas stream to form a heated gas stream, the combined catalyst comprising a first layer having an oxidation catalyst to oxidize the exhaust nitrogen reducing agent and HC to heat the heated gas stream, and a second layer having an SCR catalyst to reduce NOx in the heated gas stream; and (f) a filter arranged to contact the heated gas stream to regenerate the soot contained in the filter.
    BRIEF SUMMARY OF DRAWINGS
    Fig. 1 shows a typical urea SCR system configuration with a downstream fuel injector.
    Fig. 2 shows the SCR system of Fig. 1 with an ammonia exhaust catalyst (ASC) after SCR to minimize non-selective NH3 oxidation by the diesel exotherm catalyst (DEC).
    Fig. 3 shows an embodiment of the present invention in which the urea SCR system configuration with downstream fuel injector comprises a combined ammonia exhaust catalyst and diesel exotherm catalyst.
    Fig. 4 shows the conversion of HC to a start-up test under high hydrocarbon (exotherm) conditions to a standard DEC, a standard ASC, and combined DEC / SCR catalysts of the present invention.
    Fig. 5 shows the performance for the conversion of NH3 to the same catalysts as tested with respect to Fig. 4 under conditions with low hydrocarbon content.
    Fig. 6 shows the performance for the selective conversion of
    Petition 870180155768, of 11/27/2018, p. 11/29
    NH3 to N2 for the same catalysts as tested with respect to Figs. 4 & 5 under low hydrocarbon conditions.
    Fig. 7 shows a schematic diagram of an embodiment of the combination catalyst of the present invention.
    DETAILED DESCRIPTION
    Referring to Fig. 3, an exhaust system 300 of the present invention is shown schematically. As shown, system 300 comprises a conduit 301 for transmitting an exhaust gas from an engine 307 to the atmosphere. Such exhaust streams are known to contain NOx. Downstream of the engine 307 is an injector 302 for injecting the nitrogen reducing agent into the exhaust flow. Next to injector 302 is a selective catalytic reduction (SCR) catalyst 303. It is located to contact the exhaust gas and reduce NOx using a nitrogen reducing agent to form N2 and result in a reduced NOx gas stream. Because the amount of NOx in the exhaust current tends to vary considerably depending, for example, on engine acceleration / deceleration, operating temperatures, ambient temperature, etc., it is difficult to maintain a precise stoichiometric balance between nitrogen reducing agent and NOx. Consequently, an abundance of nitrogen reducing agent will be injected into the exhaust stream, resulting in a portion of it passing through the SCR and entering the reduced NOx gas stream. This is referred to as the exhaust nitrogen reducing agent or, more particularly, escape ammonia.
    Downstream of the SCR is a hydrocarbon injector (HC) 304 to inject HC into the reduced NOx gas stream to form an HC-enriched stream. A combined catalyst 305 is located to contact the HC-enriched stream to form a heated gas stream of sufficient temperature (eg 400 ° C) to regenerate the soot contained in the catalyst soot filter (CSF) 306. The required temperature for
    Petition 870180155768, of 11/27/2018, p. 12/29 regenerating soot can vary depending on the application. For example, typically the heated gas stream should be 550 to 650 ° C, however, additives can be added to the gas stream to reduce the required temperature to around 450 ° C and perhaps lower.
    Referring to Fig. 7, a schematic representation of an embodiment of the combined catalyst 700 is shown. The combined catalyst 700 comprises a substrate 701 on which a first layer 702 having an oxidation catalyst is arranged. The oxidation catalyst oxidizes the nitrogenous exhaust reducing agent and the HC injected into the HC-enriched steam. The oxidation catalyst has an effective amount of PGM (for example, greater than 10 g / ft 3 (357.14 g / m 3 )) to make the oxidation reaction sufficiently exothermic to heat the heated gas stream at an appropriate regeneration temperature (eg 400 to 550 ° C). The catalyst 700 also comprises a second layer 703, which, in this embodiment, covers the first layer 702. The second layer comprises an SCR catalyst to reduce NOx in the stream enriched or generated from the oxidation of HC and nitrogen reducing agent in the first layer 702.
    The system, the combined catalyst, and its use are described in more detail below with respect to certain non-limiting embodiments.
    Referring again to Fig. 3, engine 307 can be any type of low-burn engine, including, for example, a diesel engine, a low-burn gasoline engine or an engine powered by liquefied petroleum gas or gas Natural.
    In the embodiment shown in Fig. 3, system 300 also has a diesel oxidation catalyst (DOC) 308. DOC 308 is a well-known device that uses a chemical process to break down pollutants in the exhaust stream into less harmful components . More specifically, DOCs typically use
    Petition 870180155768, of 11/27/2018, p. 13/29 precious metal catalysts to reduce particulate matter (PM), soluble organic fraction (SOF) based on hydrocarbons, and carbon monoxide content of the diesel exhaust by simple oxidation. A typical DOC is a direct flow device comprising a tube containing a honeycomb-like structure or substrate. The substrate has a large surface area that is coated with an active catalyst layer. This active layer contains a small, well-dispersed amount of precious metals. As the exhaust gases pass through the catalyst, carbon monoxide, gaseous hydrocarbons and liquid hydrocarbon particles (unburned fuel and oil) are oxidized, thereby reducing harmful emissions.
    Downstream of DOC 308 is the nitrogen reducing agent injector 302, which is also well known. It is used to measure an appropriate amount of nitrogen reducing agent in the exhaust system. Various reducing agents used in SCR applications include ammonia per se, hydrazine, anhydrous ammonia, aqueous ammonia or an ammonia precursor selected from the group consisting of urea ((NH2) 2CO), ammonium carbonate, ammonium carbamate, hydrogen carbonate ammonium and ammonium formate. Pure anhydrous ammonia is toxic and difficult to store safely, but 20 does not need any further conversion to react with an SCR catalyst. Aqueous ammonia must be hydrolyzed in order to be used, but it is safer to store and transport than anhydrous ammonia. Urea is the safest to store, but requires conversion to ammonia through thermal decomposition in order to be used as an effective reducing agent.
    As is known, injector 302 is controlled by a controller (not shown), which monitors various engine and exhaust parameters and determines the appropriate amount of nitrogen reducing agent to be injected. Such parameters include, for example, NOx concentration of the exhaust gas, exhaust gas temperature,
    Petition 870180155768, of 11/27/2018, p. 14/29 catalyst, throttle position, mass flow of the exhaust gas in the system, multiple vacuum, ignition regulation, engine speed, exhaust gas lambda value, the amount of fuel injected into the engine and the position of the exhaust valve exhaust gas recirculation (EGR) and thus the amount of EGR and supply pressure.
    The SCR catalyst is also well known and typically comprises a microporous material containing one or more transition metals. SCR catalysts are manufactured from various ceramic materials used as a carrier, such as titanium oxide, and active catalytic components are usually oxides of base metals (such as vanadium and tungsten), molecular sieves, such as zeolites, and various metals precious. The two most common designs of SCR catalyst geometry used are honeycomb and plate. The honeycomb shape is usually an extruded ceramic applied homogeneously throughout the ceramic carrier 15 or coated on the substrate. Plate-type catalysts have lower pressure drops and are less susceptible to clogging and clogging than honeycomb types, but plate configurations are much larger and more expensive. Honeycomb configurations are smaller than plate types, but have higher pressure drops and clog much more easily. SCR catalysts suitable for use in the present invention are described, for example, in catalysts based on molecular sieve / zeolite. In one embodiment, the SCR catalyst is a zeolite exchanged for transition metal.
    In the embodiment shown in Fig. 3, the 25 SCR catalyst is upstream of the combined catalyst 305. Such an arrangement is generally preferred (although not necessary) for engines that operate intermittently such that the SCR 303 heats up quickly and thus reaches peak efficiency quickly. In addition, in this configuration, it is not exposed to the heated gas stream which can be detrimental to the SCR catalyst.
    Petition 870180155768, of 11/27/2018, p. 15/29
    Downstream of the SCR catalyst but before the combined catalyst 305, an HC injector injects HC (typically engine fuel) into the low NOx gas stream to form the HC-enriched gas stream. Like the nitrogen reducing agent 5 injector, the HC injector is controlled by a controller (not shown) that is configured to periodically cause a certain amount of HC to be injected into the stream to periodically regenerate the soot that is captured in the CSF 306. The frequency at which the soot needs to be regenerated and thus the frequency and amount of HC that needs to be injected is an optimization of the system that is well known to a person of skill in the art.
    An important aspect of the invention is the combined catalyst 305. It combines the functionality of an ASC 201 and a DEC 105. As mentioned above, it has been found that although a relatively high PGM-charged oxidation catalyst improves the oxidation of HCs and nitrogen-reducing agent, the SCR catalyst coating was surprisingly capable of limiting NOx formation. The catalyst of the invention is thus capable of generating sufficient heat for soot regeneration through exothermic oxidation while selectively oxidizing the exhaust ammonia.
    The multifunctionality of the combined catalyst is presumably due to various reactions and interactions within the combined catalyst. Without being bound by any particular theory, it is assumed that, first, NOx from oxidation and exhaust ammonia from the exhaust gas are absorbed into the second layer which is an SCR active coating and react in a selective catalytic reaction to form water and nitrogen they desorb after completion of the reaction. Here, ammonia is present in a super-stoichiometric amount. Second, the escape ammonia, which was not used or absorbed in the SCR layer, and the HCs pass through
    Petition 870180155768, of 11/27/2018, p. 16/29 from the second layer to the first layer. The second layer has a powerful oxidizing action and nitrogen and nitrogen oxides produced from exhaust ammonia and water, carbon dioxide and exothermic heat produced from HCs. The formed nitrogen diffuses / passes unchanged through the second layer and enters the atmosphere. Third, after nitrogen oxides are formed in the first layer, they pass through or through the SCR catalyst of the second layer, where they are reacted with previously stored / escaped ammonia in an SCR reaction to form N 2 . Therefore, the SCR / oxidation / SCR process that occurs as the gas enriched with 10 HC passes through the combined catalyst serves as a self-regulating system in which oxidation is promoted, but excessive oxidation is controlled.
    Referring to Fig. 7, an embodiment of catalyst 700 is shown. The catalyst comprises a substrate 701, 15 which can comprise any known substrate material used in this application, including, for example, alumina. Alternatively, the catalyst can be an extruded catalyst as is well known in the art. In addition, the substrate can be configured in any known configuration, including, for example, honeycomb or monolith. In a particular embodiment, the substrate is a honeycomb alumina.
    As shown in Fig. 7, the first and second layers 702,
    703 are configured such that the second layer 703 covers the first layer 702. It should be understood, however, that other configurations are within the scope of the invention. For example, the first and second layers can be deposited along the substrate such that the first layer is upstream of the second layer. Alternatively, a series of alternating first and second layers can be used. Still other configurations will be obvious to a person of skill in the art in light of this description.
    Petition 870180155768, of 11/27/2018, p. 17/29
    As mentioned above, the first layer comprises the oxidation catalyst. The catalyst must be selected to ensure oxidation of HCs and nitrogen-reducing agent as a significant exothermic reaction is obtained. Specifically, the exothermic reaction 5 needs to be sufficient to heat the heated gas stream to the point that it is capable of regenerating soot in CSF 306. Generally, this will require heating the gas to at least about 400 ° C. Ideal regeneration occurs at around 550 to about 650 ° C. For this purpose, the catalyst must comprise a microporous material, such as a zeolite or non-zeolite 10 (for example alumina, ceria, zirconia, titania, or similar materials individually or in combination), sufficiently charged with PGM to provide the desired exotherm. Generally, the higher the PGM load, the more reactive the catalyst.
    In addition to having sufficient PGM charge to guarantee 15 suitable regeneration temperatures as described above, the PGM charge must be sufficient such that the start temperature for the exothermic HC heat generation is less than about 350 ° C. Generally, lower starting temperatures are desirable. If the start-up temperature is higher than about 350 ° C, then an auxiliary system may be required to heat up the exhaust gas upstream. Such systems increase the complexity of the exhaust system and reduce fuel efficiency, and thus are generally undesirable. It has been found that the temperature of the exhaust gas reaching the DEC is generally (though not necessarily) less than 350 ° C. Therefore, in one embodiment, the catalyst of the present invention has sufficient PGM type and charge such that the starting temperature of the catalyst is less than 350 ° C, and, in a more particular embodiment, it is less than 325 ° C. The preparation of the oxidation layer to provide this desired performance would be known to those of skill in the art in light of this description.
    Given the need for high regeneration temperatures and a
    Petition 870180155768, of 11/27/2018, p. 18/29 relatively low starting temperature, the required PGM load is typically greater than that used in traditional ASC catalysts, which tend to be less than 10 g / ft 3 (357.14 g / m 3 ). (The charge on an ASC catalyst is typically kept relatively low to prevent excessive oxidation of the exhaust ammonia and NOx generation.) Consequently, in one embodiment, the PGM charge is greater than that of the ASC catalyst traditional. In one embodiment, the load is greater than about 10 g / ft 3 (357.14 g / m 3 ). In another embodiment, the load is greater than about 10 g / ft 3 (357.14 g / m 3 ) and less than about 100 g / ft 3 (3571.43 g / m 3 ). In another embodiment, the load is about 15 g / ft 3 (535.71 g / m 3 ) to about 70 g / ft 3 (2500 g / m 3 ). In yet another embodiment, the load is about 20 g / ft 3 (714.29 g / m 3 ).
    In one embodiment, the PGM comprises palladium (Pd) and / or platinum (Pt). In another embodiment, PGM comprises a combination of Pd and Pt. Generally, Pd promotes exothermic oxidation, and Pt tends to generate NOx from NH3. Consequently, the relative concentrations in a mixture of Pd and Pt will tend to depend on the amount of oxidation versus desired NOx generation. The relative charge from Pd to Pt can vary from a ratio of 1:10 to 10: 1. In a particular embodiment, PGM comprises a combination of essentially equal portions of Pt and Pd for a total load of about 15 to 70 g / ft 3 (535.71 to 2500 g / m 3 ).
    The second layer comprises the SCR catalyst. Such catalysts are well known and described above with respect to the SCR catalyst 303. Generally, the SCR catalyst comprises the SCR catalyst comprising at least (i) a microporous crystalline molecular sieve comprising; and (ii) a transition metal impregnated in the molecular sieve.
    The molecular sieve can be any known or later developed microporous structure suitable for use as a
    Petition 870180155768, of 11/27/2018, p. 19/29 catalyst, including sieves and zeolite other than zeolite (as defined by US Patent No. 4,913,799 (incorporated herein by reference)). In one embodiment, the molecular sieve comprises at least silicon, aluminum and phosphorus and has an 8 ring pore opening structure. In one embodiment, the molecular sieve is a silicoaluminophosphate (SAPO) molecular sieve. In one embodiment, SAPO molecular sieves have one or more of the following structure types as defined by the Structure Commission of the International Zeolite Association: AEI, AFX, CHA, LEV, LTA. In one embodiment, the type of structure is CHA, or CHA in combination with one or more different types of structure, such as, for example, AEI-CHA intergrowths.
    Examples of suitable CHA SAPOs include SAPO-34 and KYT-6. In a particular embodiment, the molecular sieve is SAPO-34. In another embodiment, the catalyst comprises two or more 15 different SAPO molecular sieves selected from the group consisting of AEI,
    AFX, CHA, LEV, and LTA. In one embodiment, the zeolite has a type of structure selected from AEI, AFX, CHA, LEV, LTA, BEA, MFI, FER, MOR and KFI. An example of a suitable BEA zeolite is beta zeolite.
    In addition to the molecular sieve, the SCR catalyst comprises a transition metal embedded in the sieve. Suitable transition metals include, for example, Cr, Mn, Fe, Co, Ce, Ni, Cu, Zn, Ga, Mo, Ru, Rh, Pd, Ag, In, Sn, Re, Ir, Au, Pr, Nd , W, Bi, Os, and Pt. In one embodiment, the transition metal is Cu or Fe or combinations thereof. In one embodiment, the charge of the transition metal is about 0.3% by weight to about 25% by weight of the catalyst. The type and concentration of the transmission metal may vary according to the sieve and the application. For example, suitable results were obtained with SAPO-34 loaded with about 2% by weight of Cu, and beta zeolite loaded with about 3% by weight of Fe. Still other combinations of sieves, transition metals and
    Petition 870180155768, of 11/27/2018, p. 20/29 charge concentrations will be obvious to those of skill in the art in light of this description.
    SCR catalysts can comprise a substrate made of a ceramic material, such as cordierite, mullite, silica, alumina, titania, or combinations thereof. Alternatively, the substrate can be metallic. The two most common substrate designs are monolith or plate and honeycomb. Plate type catalysts have lower pressure drops and are less susceptible to clogging and clogging than honeycomb types, but plate configurations are much larger and more expensive. Honeycomb configurations are smaller than plate types, but have higher pressure drops and clog much more easily. Alternatively, the catalyst can be an extrudate with or without a substrate. In the last embodiment, the catalyst has no separate substrate. In yet another embodiment, the catalyst is not supported at all, but is supplied in bulk.
    The combination catalyst 305 can be prepared using known techniques. For example, the Canadian Application No. 2652837 (based on PCT Publication No. 2007/137675), hereby incorporated by reference, discloses a suitable preparation procedure, although the load PGM oxidation layer of the present invention need to be higher than that described in this reference.
    The heated gas leaves the combined catalyst 305 and contacts the CSF 306 at which point the soot is regenerated. Such a process is well known and will not be discussed in detail here.
    EXAMPLES
    The following non-limiting examples compare five embodiments of the combined catalyst of the present invention (samples 2 to 6) to a conventional DEC catalyst (sample 1) and a conventional ASC (sample 7) as shown in Table 1 below.
    Petition 870180155768, of 11/27/2018, p. 21/29
    Table 1
    Sample description 1 DEC only (no SCR layer) 35g / ft 3 (1250 g / m 3 ) of Pt; 35g / ft 3 (1250 g / m 3 ) of Pd 2 Combined catalyst - Pt oxidation layer 35g / ft 3 (1250 g / m 3 ); 35g / ft 3 (1250 g / m 3 ) of Pd; beta zeolite from SCR layer loaded with 3 wt% Fe 3 Combined catalyst - Oxidation layer 40 g / ft 3 (1428.57 g / m 3 ) of Pt; SCO layer SAPO-34 loaded with 2% Cu by weight. 4 Combined catalyst - Pt oxidation layer 35g / ft 3 (1250 g / m 3 ); beta zeolite from SCR layer loaded with 3 wt% Fe. 5 Combined catalyst - Oxidation layer 20 g / ft 3 (714.29 g / m 3 ) of Pt; SCO layer SAPO-34 loaded with 2% Cu by weight. 6 Combined catalyst - Oxidation layer 10 g / ft 3 (357.14 g / m 3 ) of Pt; SCO layer SAPO-34 loaded with 2% Cu by weight. 7 ASC only (no oxidizing layer) 1 g / ft 3 (35.71 g / m 3 ) of SAPO-34 Pt loaded with 2 wt% Cu.
    In these samples, the oxidation layer was prepared by preparing a moist alumina slurry loaded with the indicated PGM at the indicated concentration, and then coating a standard honeycomb ceramic substrate with the slurry. The SCR layer was prepared by preparing a mixture of the indicated microporous material (SAPO-34 or beta zeolite) loaded with the indicated amount of Cu or Fe through ion exchange, adding a binder to the mixture, and then coating it with oxidation layer with the mixture.
    Starting temperature
    Fig. 4 shows the results of a start-up test (HC oxidation) at high HC concentrations (typical for a DEC to generate an exotherm to clean a filter). This was a steady-state start-up test in an atmosphere of 12% O 2 , 200 ppm NH 3 , 200 ppm CO, 15 1000 ppm C 10 H 22 , 4.5% H 2 O, 4, 5% CO 2 , and equilibrium with N 2 .
    Although Sample 1, the conventional DEC, had the lowest starting temperature (<200 ° C), Sample 2, the combined Pt / Pd catalyst, and Samples 3 to 5, the combined Pt catalysts with 20 to 35% in
    Petition 870180155768, of 11/27/2018, p. 22/29 Pt weight, also demonstrated adequate starting temperatures (ie <350 ° C). Sample 6, the combined 10 g / ft 3 Pt catalyst (357.14 g / m 3 ) had a start-up temperature of about 350 ° C, which is generally (though not necessarily) very high. Likewise, Sample 7, the standard NH 3 exhaust catalyst loaded with low PGM content (1 g / ft 3 (35.71 g / m 3 ) of
    Pt) also had a start-up temperature of about 350 ° C. Therefore, these results indicate that a combination catalyst with an adequate starting temperature is obtained with an oxidation layer having a PGM concentration above 10 g / ft 3 (357.14 g / m 3 ).
    NH3 conversion
    Fig. 5 shows the conversion of NH3 under standard diesel operating conditions with low hydrocarbon concentrations (generation other than exotherm) in an atmosphere of 12% O2, 200 ppm NH3, 200 ppm CO, 100 ppm C3H6, 4.5% H2O, 4.5% CO2, 15 with N2 equilibrium. Here, all samples show acceptable NH3 conversion - that is, almost 100% NH3 conversion at around 325 ° C. Selectivity
    Fig. 6 shows the performance of each sample in selectively converting NH3 to N2. This experiment was a start-up test in steady state 20 under the same atmospheric conditions as in the conversion of NH3 in Fig. 5. Sample 1, the standard DEC had the lowest selectivity with a 40% peak at relatively low temperatures and decreasing to less than 10% at higher temperatures. Samples 2 to 6, the combined catalysts, had significantly better selectivity 25 having a peak of about 55 to 70% between about 325 and 425 ° C, which is a common operating temperature range. Samples 4 and 5, the combined catalysts of 35 g / ft 3 and 20 g / ft 3 (1250 and 714.29 g / m 3 ) of Pt, show a particularly high selectivity of about 70% between 325 and 425 ° C. Such selectivity is comparable to Sample 7, a traditional ASC.
    Petition 870180155768, of 11/27/2018, p. 23/29
    Therefore, these examples show that the combination catalyst of the present invention offers the benefit of good selectivity for the escape control of the nitrogen reducing agent, which can be maintained even with the highest PGM load in the oxidation catalyst for the oxidation of 5 HC improved for the generation of exotherm. Adding Pd to the bottom layer containing Pt also improves the HC oxidation capacity of the catalyst while also improving the selectivity of NH3 to N2.
    权利要求:
    Claims (20)
    [1]
    1. Catalyst, characterized by the fact that it comprises:
    a first layer comprising an oxidation catalyst, the oxidation catalyst comprising a PGM consisting of Pd and / or Pt having an effective PGM charge such that hydrocarbon oxidation generates sufficient heat to regenerate the soot, where the PGM charge it is greater than 10 g / ft 3 (357.14 g / m 3 ) and less than 100 g / ft 3 (3571.4 g / m 3); and a second layer adjacent to said first layer and comprising a selective catalytic reduction (SCR) to selectively reduce NOx, wherein said SCR catalyst comprises at least (i) a microporous crystalline molecular sieve; and (ii) a metal transition impregnated in the molecular sieve, in which the microporous crystalline molecular sieve comprises at least silicon, aluminum and phosphorus and has an 8 ring pore opening structure, in which the transition metal is Cr, Mn, Fe, Co, Ce, Ni, Cu, Zn, Ga, Mo, Ru, Rh, Pd, Ag, In, Sn, Re, Ir, Au, Pr, Nd, W, Bi, Os or Pt or their combinations, of preferably Cu or Fe or combinations thereof, and wherein the transition metal charge is 0.3% by weight to 10% by weight of the catalyst.
    [2]
    2. Catalyst according to claim 1, characterized by the fact that the effective amount of PGM is greater than 15 g / ft 3 (535.71 g / m 3 ).
    [3]
    3. Catalyst according to claim 2, characterized by the fact that the effective amount of PGM is in the range of 15 g / ft 3 (535.71 g / m 3 ) to 70 g / ft 3 (2500 g / m 3 ).
    [4]
    4. Catalyst according to claim 3, characterized by the fact that the effective amount of PGM is greater than 20 g / ft 3 (714.29 g / m 3 ).
    Petition 870180155768, of 11/27/2018, p. 25/29
    [5]
    5. Catalyst according to claim 1, characterized by the fact that PGM is selected from the group consisting of Pt and Pd and combinations thereof.
    [6]
    6. Catalyst according to claim 5, characterized by the fact that PGM is a combination of Pt and Pd.
    [7]
    7. Catalyst according to claim 1, characterized by the fact that the catalyst has an HC start-up temperature of less than 350 ° C in an atmosphere of 12% O2, 200 ppm NH3, 200 ppm CO, 1000 ppm C10H22, 4.5% H2O, 4.5% CO2, and the N2 balance.
    [8]
    8. Catalyst according to claim 7, characterized in that the starting temperature of HC is not greater than 325 ° C.
    [9]
    9. Catalyst according to claim 1, characterized by the fact that the SCR catalyst is a molecular sieve charged with a transition metal.
    [10]
    10. Catalyst according to claim 9, characterized by the fact that the transition metal is selected from Cu, Fe and combinations thereof.
    [11]
    11. Catalyst according to claim 10, characterized by the fact that the molecular sieve is a SAPO, CHA or a beta zeolite.
    [12]
    12. Catalyst according to claim 1, characterized in that it additionally comprises a substrate on which the first layer is arranged.
    [13]
    13. Catalyst according to claim 12, characterized in that the second layer covers the first layer.
    [14]
    14. Catalyst according to claim 12, characterized by the fact that the first layer is upstream of the second layer.
    Petition 870180155768, of 11/27/2018, p. 26/29
    [15]
    15. Method for generating heat to remove soot and reduce the escape of NH3 in an exhaust system, characterized by the fact that it comprises:
    injecting the nitrogen reducing agent in an exhaust stream having NOx reduce NOx using the nitrogen reducing agent in the presence of an SCR catalyst to form a reduced NOx gas stream, which, at least intermittently, contains nitrogen reducing agent exhaust;
    injecting HC into the reduced NOx gas stream to form an HC-enriched gas stream; and contacting the HC-enriched gas stream with a combined catalyst to form a heated gas stream, the combined catalyst comprising a first layer having an oxidation catalyst to oxidize at least a portion of the HC to heat the heated gas stream, and a second layer having an SCR catalyst to reduce at least a portion of NOx in the heated gas stream.
    [16]
    16. Method according to claim 15, characterized in that the heated gas stream is heated to at least 400 ° C.
    [17]
    17. Method according to claim 15, characterized in that the temperature of the HC-enriched gas stream is less than 350 ° C.
    [18]
    18. Method according to claim 15, characterized in that the first layer is loaded with more than 15 g / ft 3 (535.71 g / m 3 ) of PGM.
    [19]
    19. Method according to claim 15, characterized
    Petition 870180155768, of 11/27/2018, p. 27/29 by the fact that it additionally comprises:
    contact the heated gas stream with a soot filter to regenerate the soot in the filter.
    [20]
    20. Exhaust treatment system, characterized by the fact that it comprises:
    a conduit for transmitting an exhaust gas having NOx from an engine to the atmosphere;
    an injector to inject the nitrogen reducing agent into the exhaust gas;
    an SCR catalyst located to contact the exhaust gas and reduce NOx using the nitrogen reducing agent to form a reduced NOx gas stream, which, at least intermittently, contains the exhaust nitrogen reducing agent;
    an HC injector for injecting HC into the reduced NOx gas stream to form a HC-enriched gas stream;
    a combined catalyst located to contact the HC-enriched gas stream to form a heated gas stream, the combined catalyst comprising a first layer having an oxidation catalyst to oxidize the exhaust nitrogen reducing agent and HC to heat the exhaust stream heated gas, and a second layer having an SCR catalyst to reduce NOx in the heated gas stream; and a filter arranged to contact the heated gas stream to regenerate the soot contained in the filter.
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    同族专利:
    公开号 | 公开日
    RU2013116902A|2014-10-20|
    KR20180058842A|2018-06-01|
    KR101996196B1|2019-07-03|
    EP2616175B1|2021-01-27|
    RU2583374C2|2016-05-10|
    EP2616175A1|2013-07-24|
    US8329127B2|2012-12-11|
    JP2013542847A|2013-11-28|
    BR112013005816A2|2016-05-10|
    CN103118780A|2013-05-22|
    WO2012037342A1|2012-03-22|
    JP2016147258A|2016-08-18|
    JP6228179B2|2017-11-08|
    CN103118780B|2016-06-01|
    US20120107204A1|2012-05-03|
    KR20130103502A|2013-09-23|
    JP5882333B2|2016-03-09|
    US20130078173A1|2013-03-28|
    KR101860741B1|2018-05-24|
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    法律状态:
    2018-09-04| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2019-03-12| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-04-30| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/09/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/09/2011, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    US38311210P| true| 2010-09-15|2010-09-15|
    US61/383112|2010-09-15|
    PCT/US2011/051750|WO2012037342A1|2010-09-15|2011-09-15|Combined slip catalyst and hydrocarbon exotherm catalyst|
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