• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    catalytic article, emission treatment system, and method for manufacturing a catalytic article. diesel oxidation catalysts, catalytic articles, methods for making catalytic articles, emission treatment systems and methods for treating an exhaust gas stream using catalytic articles for treating exhaust gas emissions, such as hydrocarbon oxidation (hc) unburned and carbon monoxide (co) are described. specific catalytic articles comprising a substrate having a first washable coating layer comprising more than or equal to about 2% by weight palladium dispersed on a ceria support and a second washable coating layer comprising a platinum group metal and a refractory metal oxide are described.
    公开号:BR112013013008B1
    申请号:R112013013008-3
    申请日:2011-11-22
    公开日:2019-08-13
    发明作者:Xinyi Wei；Stanley Roth
    申请人:Basf Corporation；
    IPC主号:
    专利说明:

    “CATALYTIC ARTICLE, EMISSIONS TREATMENT SYSTEM, AND, METHOD FOR MANUFACTURING A CATALYTIC ARTICLE” FUNDAMENTALS [0001] The modalities of the present invention are addressed to diesel oxidation catalysts and methods of doing the same.
    [0002] The operation of poorly burning engines, for example, diesel engines and poorly burning petrol engines, provides the user with excellent fuel economy and has very low emissions of gas phase hydrocarbons and carbon monoxide due to their operation in high air / fuel ratios under poor fuel conditions. Diesel engines, in particular, also offer significant advantages over gasoline engines in terms of their fuel economy, durability and their ability to generate high torque at low speed.
    [0003] From an emissions standpoint, however, diesel engines have more severe problems than their spark ignition replicas. Emission problems refer to particulate matter (PM), nitrogen oxides (NOx), unburned hydrocarbons (HC), and carbon monoxide (CO). NOx is a term used to describe several species of nitrogen oxides, including nitrogen monoxide (NO) and nitrogen dioxide (NO2), among others. NO is worrisome because it is believed to be subjected to a process known as photochemical fog formation, through a series of reactions in the presence of sunlight and hydrocarbons, and is a significant contributor to acid rain. NO2, on the other hand, has a high potential as an oxidizer and is a strong lung irritant. Particulate matter (PM) is also linked to respiratory problems. As engine operation modifications are made to reduce particulate materials and unburned hydrocarbons in diesel engines, NOx emissions tend to increase.
    [0004] Oxidation catalysts comprising a precious metal
    Petition 870180168667, of 12/28/2018, p. 12/34 / 19 dispersed in a refractory metal oxide support are known for use in the exhaust treatment of diesel engines to convert gaseous pollutants from both hydrocarbon and carbon monoxide by catalyzing the oxidation of these pollutants into carbon dioxide and water. Such catalysts are generally contained in units called diesel oxidation catalysts (DOC), or more simply catalytic converters, which are placed in the exhaust flow path from a diesel driven engine to treat the exhaust before bleeding into the atmosphere. Typically, diesel oxidation catalysts are formed in metallic or ceramic substrate carriers (such as the monolithic direct flow carrier, as described below) on which one or more catalyst coating compositions are deposited. In addition to the conversion of gaseous HC, CO and the SOF fraction of particulate matter, oxidation catalysts containing platinum group metals (which are typically dispersed in a refractory oxide support) promote the oxidation of nitric oxide (NO) to NO2 .
    [0005] Catalysts used to treat exhaust from internal combustion engines are less effective during periods of relatively low temperature operation, such as operating the engine's initial cold start period, because the engine exhaust is not at a sufficiently high temperature for efficient catalytic conversion of harmful components in the exhaust. For this purpose, an adsorbent material, which can be a zeolite, can be supplied as part of a catalytic treatment system to adsorb gaseous pollutants, usually hydrocarbons, and retain them during the initial cold start-up period. As the temperature of the exhaust gas increases, the adsorbed hydrocarbons are moved from the adsorbent and subjected to catalytic treatment at the highest temperature.
    [0006] As discussed above, oxidation catalysts
    Petition 870180168667, of 12/28/2018, p. 13/34 / 19 comprising a platinum group metal dispersed in a refractory metal oxide support are known for use in the treatment of exhaust gas emissions from diesel engines. Platinum (Pt) remains the most effective platinum group metal for oxidizing CO and HC in a DOC, after aging at elevated temperature under poor conditions and in the presence of fuel sulfur. Nevertheless, catalysts incorporated in Pd offer advantages in stabilizing Pt in higher temperature aging (> 700 ° C) and reducing catalyst cost. However, Pd-based DOCs typically show higher catalyst melt temperatures for CO and HC oxidation, especially when used with HC storage materials, potentially causing a delay in the melting of CO or HC catalyst. DOCs containing Pd can poison the Pt activity in converting paraffins and / or oxidizing NO and can also make the catalyst more susceptible to sulfur poisoning. These characteristics have typically avoided the use of Pd as an oxidation catalyst in low-burn operations especially for light-load diesel applications where engine temperatures remain below 250 ° C for most driving conditions. It would be desirable to improve one or more of the aforementioned limitations. SUMMARY [0007] One or more embodiments of the invention are directed to catalytic articles to treat an exhaust gas stream containing hydrocarbons, CO and particulate matter. The articles comprise a substrate having an inlet end and an outlet end defining an axial length. A first wash coating layer on the substrate comprises more than or equal to approximately 2% by weight of palladium dispersed in a ceria support. A second wash coating layer on the first wash coating layer. The second wash coating layer comprises a
    Petition 870180168667, of 12/28/2018, p. 14/34 / 19 platinum group metal and a refractory metal oxide.
    [0008] Additional modalities of the invention are addressed to emission treatment systems comprising a diesel engine that emits an exhaust stream including hydrocarbons, CO and particulate matter. The catalytic article comprising a substrate with a first wash coating layer and a second wash coating layer is downstream of and in flow communication with the diesel engine. The first layer of wash coating on the substrate comprises more than or equal to approximately 2% by weight of palladium dispersed in a ceria support. The second wash coating layer is on the first wash coating layer. The second wash coating layer comprises a platinum group metal and a refractory metal oxide.
    [0009] Additional embodiments of the invention are directed to methods of making a catalytic article. A substrate surface is coated with a first wash coating layer comprising palladium supported on ceria. Palladium has a charge greater than or equal to approximately 2% by weight. The substrate is dried and calcined and then coated with a second wash coating layer comprising a platinum group metal and a refractory metal oxide. The substrate is then dried and calcined again.
    [00010] In detailed embodiments, the first wash coating layer comprises palladium in the range of approximately 2% to approximately 10% by weight. in specific embodiments, the first wash coating layer comprises approximately 4% palladium by weight. In some embodiments, the first wash coating layer does not substantially comprise alumina. In one or more embodiments, the first wash coating does not substantially comprise dopants. In detailed embodiments, the refractory metal oxide in the second wash coating layer comprises
    Petition 870180168667, of 12/28/2018, p. 15/34 / 19 alumina.
    [00011] In detailed embodiments, the platinum group metal in the second wash coating layer comprises one or more of platinum and palladium supported in the refractory metal oxide. In specific embodiments, the platinum group metal in the second wash coating layer is present in the range of approximately 1% to approximately 5% by weight. In some embodiments, the second wash coating layer further comprises a zeolite. In detailed embodiments, the zeolite comprises one or more of beta-zeolite, zeolite Y and ZSM-5.
    [00012] The substrate of specific modalities is a direct flow substrate having a plurality of longitudinally extended passages formed by longitudinally extended walls limiting and defining the passages. In one or more embodiments, the substrate is a wall flow filter having gas-permeable walls formed in a plurality of axially extended channels, each channel having an obstructed end with any pair of adjacent channels fitted at opposite ends thereof.
    BRIEF DESCRIPTION OF THE DRAWINGS [00013] Figure 1 is a graph of the crystallite size of ceria and the surface ratio of Pd to ceria as a function of the charge of Pd according to one or more embodiments of the invention.
    [00014] Figure 2 is a schematic view of a channel of a catalytic article according to one or more embodiments of the invention.
    [00015] Figure 3 is a perspective view of a wall flow monolith according to one or more embodiments of the invention.
    [00016] Figure 4 is a partial cross-sectional view of a wall flow monolith for use with one or more embodiments of the invention.
    Petition 870180168667, of 12/28/2018, p. 16/34 / 19 [00017] Figure 5 is a partial cross-sectional view enlarged in relation to figure 3 and taken along a plane parallel to the extreme faces of the figure 4 monolith, which shows an enlarged view of the current passages shown in figure 4.
    [00018] Figure 6 shows a schematic view of the preparation of a catalytic article according to one or more embodiments of the invention; and [00019] Figure 7 shows an emission treatment system according to one or more embodiments of the invention.
    [00020] Figure 8 is a graph of the melting temperature of carbon monoxide catalyst for catalysts according to embodiments of the invention.
    [00021] Figure 9 is a graph of the conversion of carbon monoxide to various catalysts according to embodiments of the invention; and [00022] Figure 10 is a graph of the conversions of carbon monoxide and propane for various catalysts according to embodiments of the invention.
    DETAILED DESCRIPTION [00023] Before describing several exemplary embodiments of the invention, it should be understood that the invention is not limited to the details of construction or process steps set out in the following description. The invention is capable of other modalities and can be put into practice or carried out in various ways.
    [00024] Where they appear here, the terms "exhaust current" and "engine exhaust current" refer to the effluent out of the engine as well as the effluent downstream of one or more other components of the catalyst system including, but not limited to to a diesel oxidation catalyst and / or soot filter.
    [00025] The following terms will, for the purposes of this application, have the respective meanings set out below.
    Petition 870180168667, of 12/28/2018, p. 17/34 / 19 s
    [00026] "Refractory metal oxides" refer to alumina, silica, zirconia, titania, ceria and physical mixtures or chemical combinations thereof, including atomically doped combinations.
    [00027] "Platinum group metal components" refer to platinum group metals in the Periodic Table of Elements or one of their oxides.
    [00028] "Rare earth metal components" refer to one or more oxides of the lanthanum series defined in the Periodic Table of Elements, including lanthanum, cerium, praseodymium and neodymium.
    [00029] "Flow communication" means that the components and / or ducts are contiguous in such a way that the exhaust gases or other fluids can flow between the components and / or ducts.
    X [00030] "Downstream" refers to the position of a component in an exhaust gas stream in a path further away from the engine than the component that precedes the component. For example, when a diesel particulate filter is mentioned as downstream of a diesel oxidation catalyst, the exhaust gas that emanates from the engine in an exhaust duct flows through the diesel oxidation catalyst before flowing through of the diesel particulate filter. Thus, "upstream" refers to a component that is located closer to the engine refers to another component.
    [00031] One aspect of the invention relates to a catalyst. According to one or more embodiments, the catalyst can be arranged on a monolithic substrate such as a wash coating layer. “Wash coating” has no normal significance in the art of an adherent, thin coating of a catalytic or other material applied to a refractory substrate, such as a honeycomb flow through the monolith substrate or a filter substrate, which is sufficiently porous to allow the gas stream being treated to pass through. As used here and as described in Ronald M. Heck and Robert J. Ferrauto,
    Petition 870180168667, of 12/28/2018, p. 18/34 / 19
    Catalytic Air Pollution Control, New York: Wiley-Interscience, 2002, p. 18-19, a wash coating layer includes a compositionally distinct layer of material disposed on the surface of the monolithic substrate or an underlying wash coating layer. A catalyst can contain one or more layers of wash coating, and each layer of wash coating can have unique chemical catalytic functions.
    [00032] A primary function of diesel oxidation catalysts (DOC) is to convert carbon monoxide and hydrocarbons at relatively low temperature, particularly during cold engine start-up. The incorporation of palladium with an oxygen storage component (OSC) in the DOC has been shown to significantly improve the melting activity of CO / HC catalyst. The modalities of the invention describe superior activity at low temperature of a catalyst of high concentration of palladium, supported on pure ceria and its significant improvement over other OSC-palladium catalysts. The high cerium-palladium catalyst can be used individually or as a separate layer from a fully formulated catalyst to increase performance at low temperature.
    [00033] A pure ceria support is less stable than zirconia or other rare earth doped ceria after hydrothermal aging at a higher temperature (> 700 ° C). as a result, after such aging, Pd-CeO2 in relatively low Pd charge (<1%) shows much lower activity than Pd-OSC for oxidation of CO / HC. However, the inventors have found that when the Pd concentration is increased to more than or equal to approximately 3% by weight, a dramatic mutual stabilization effect begins to occur that results in extremely high CO / HC catalyst melting activity, and the activity improves even after hydrothermal aging.
    Petition 870180168667, of 12/28/2018, p. 19/34 / 19 [00034] Without being limited by any specific theory of operation, it is believed that the high activity probably comes from a combination of several factors: (1) almost atomic dispersion of Pd on the surface of CeO2 and Pd 0 easily available; (2) strong stabilization of CeO2 crystallite by Pd (at> 4% load), sintering at a higher temperature; and (3) steam activation that is exclusive to the Pd-OSC component and is enhanced by the synergy of Pd-CeO2. The evidence for strong Pd-CeO2 synergy is shown in Figure 1. The size of CeO2 crystallite and concentration of Pd on the surface as a function of Pd loading on CeO2 were measured in samples that were aged at 750 ° C / 20 h in 10% steam air. The systematic decrease in size of CeO2 crystallite and increase in superficial Pd / CeO2 with increased Pd charge suggests a mutual stabilization effect between CeO2 and Pd after hydrothermal aging. On the other hand, such behavior is not observed in any doped CeO2-supported Pd catalysts, that is, the surface Pd concentration does not increase with the increased Pd load. Unlike Pd catalysts supported on zirconia, Pd-CeO2 catalyst appears stable under catalyst melt conditions and does not suffer from course-to-course deactivations. A 3-8% advantage of Pd-CeO2 for Pd / OSC remained after engine aging, an improvement at 24 ° C in melting of CO catalyst was observed. The high activity of 3-8% Pd-CeO2 catalyst decreases dramatically when other dopants, such as zirconium or lanthanum are present. This is believed to be due to the loss of Pd-CeO2 interaction which may be important for low temperature activity.
    [00035] The high Pd-CeO2 component can be used in a separate layer from the Pt-Pd / Al2O3 component to avoid negative interaction between Pt and CeO2. In specific modalities, Pd-CeO2 is located below the Pt-Pd / AUO3 layer, so that the HC species, which could inhibit Pd-CeO2 function, can be oxidized and removed before
    Petition 870180168667, of 12/28/2018, p. 20/34 / 19 reach the Pd-CeO2.
    [00036] Accordingly, one or more embodiments of the invention refer to catalytic articles for treating an exhaust gas stream containing hydrocarbons, CO and particulate matter. With reference to figure 2, a catalytic article 10 can comprise a substrate 12 having an inlet end 14 and an outlet end 16 that define an axial length L. A single channel 18 of the substrate 12 is shown. A first wash coating layer 20 is on substrate 12. The first wash coating layer 20 comprises more than or equal to approximately 3% by weight of palladium dispersed in a ceria support. A second wash coating layer 22 is on the first wash coating layer 20. The second wash coating layer 22 comprises a platinum group metal and a refractory metal oxide. The amount of palladium in the first wash coating layer 20 can vary depending on the desired application and specific uses. in one or more embodiments, the first wash coating layer 20 comprises palladium in the range of approximately 2% to approximately 10% by weight. In some embodiments, the first wash coating layer 20 comprises palladium in the range of approximately 3% to approximately 6% by weight. In various embodiments, the first wash coating layer comprises approximately 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% palladium by weight. In specific embodiments, the first wash coating layer 20 comprises approximately 4% palladium by weight. In various embodiments, the first wash coating layer 20 comprises palladium in an amount greater than approximately 2%, 4%, 5%, 6%, 7%, 8%, 9% or 10% by weight.
    [00037] In specific embodiments, the first wash coating layer 20 does not substantially comprise alumina. As used
    Petition 870180168667, of 12/28/2018, p. 21/34 / 19 in that specification and in the attached claims. The term "substantially without alumina" means that alumina was not intentionally added to the first wash coating layer. It is to be understood that alumina can migrate from layers above or below the first wash coating layer 20 without deviating from the meaning of substantially no alumina.
    [00038] As previously described, the high% activity of Pd-CeO2 catalyst can decrease when other dopants are present. In detailed embodiments, the first wash coating layer 20 does not substantially comprise dopants. According to specific embodiments, the first wash coating layer 20 does not substantially comprise dopants, individually or in combination, such as zirconium, lanthanum, praseodymium, samarium, neodymium, yttrium, titanium and / or silicon.
    [00039] In one or more embodiments, the composition of the second wash coating layer 22 differs from that of the first wash coating layer 20. For example, in some embodiments, the second wash coating layer 22 has a metal oxide refractory comprising alumina. In these embodiments, a small portion of the alumina is expected to migrate into the first wash coating layer 20.
    [00040] The platinum group metal in the second wash coating layer 22 of detailed embodiments comprises one or more of platinum and palladium supported on refractory metal oxide. In specific embodiments, the platinum group metal of the second wash coating layer 22 is platinum and palladium.
    [00041] The refractory metal oxide of the second wash coating layer 22 can be any suitable material known to those skilled in the art. In specific modalities, refractory metal oxide
    Petition 870180168667, of 12/28/2018, p. 22/34 / 19 of the second wash coating layer 22 comprises alumina. [00042] The amount of the platinum group metal in the second wash coating layer 22 may vary depending on the desired characteristics of the resulting catalytic article. In detailed embodiments, the platinum group metal in the second wash coating layer 22 is present in the range of approximately 1% to approximately 5% by weight.
    [00043] The second wash layer 22 of detailed embodiments further comprises a zeolite. Any suitable zeolite can be added and are known to those skilled in the art. In specific embodiments, the zeolite comprises one or more of beta-zeolite, zeolite Y and ZSM-5.
    The Substrate [00044] Any suitable substrate can be employed, as a monolithic direct flow substrate and having a plurality of parallel, thin gas flow passages extending from an inlet to an outlet face of the substrate, such that passages are opened for fluid flow. The passages, which are essentially straight paths from its fluid inlet to its fluid outlet, are defined by walls on which the catalytic material is coated as a “wash liner” so that gases flowing through the passages contact the catalytic material. The flow passages of the monolithic substrate are thin-walled channels that can be of any shape in appropriate cross-section such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc. such structures may contain approximately 60 to approximately 1200 or more gas inlet openings (ie, “cells”) per square inch (1 in 2 = 6.54 cm 2 ) in cross section (cpsi). However, it will be understood that the invention is not limited to a specific substrate type, material or geometry.
    [00045] Ceramic substrates can be made of any material
    Petition 870180168667, of 12/28/2018, p. 23/34 / 19 suitable metallic or ceramic. Exemplary ceramic materials include, but are not limited to: cordierite, cordierite-α alumina, silicon nitride, zirconium mullite, spodumene, silica alumina-magnesia, zirconium silicate, silimanite, magnesium silicates, zirconium, petalite, α alumina , aluminosilicates and the like. Exemplary metal supports include heat-resistant metals and metal alloys such as titanium and stainless steel as well as other alloys in which iron is a substantial or major component. [00046] Figures 3 and 4 illustrate a wall flow filter substrate 50 that has a plurality of alternately blocked channels 52 and can serve as a particulate material filter. The passages are tubularly enclosed by the inner walls 53 of the filter substrate. The plurality of axially extended channels are formed of gas permeable internal walls 53. The substrate has an inlet end 54 and an outlet end 56. Alternating passages are obstructed at the inlet end 54 with inlet caps 58 and the outlet end 56 with output tops 60 to form opposing chessboard patterns at input 54 and output 56. Thus, each channel 52 has an obstructed end with any pair of adjacent channels fitted at opposite ends of it. A gas stream enters through unobstructed channel inlet 64, is stopped by outlet plug 60 and diffuses through channel walls 53 (which are porous) to outlet end 56. Gas cannot pass back to the entrance side of walls due to entrance tops 58. If such a substrate is used, the resulting system will be able to remove particulate materials together with gaseous pollutants.
    [00047] Figure 5 shows a partial cross-sectional view of the wall flow filter in Figures 2 and 3. The cross-sectional view is shown along a plane parallel to the edge of the substrate 50. It can be seen from the Figure 5 shows that the flow passages, or channels 52, are formed by the inner walls 53 and extend through the substrate 50 from the end
    Petition 870180168667, of 12/28/2018, p. 24/34 / 19 inlet 54 to outlet end 56. Inlet covers 58 and outlet covers 60 are not shown. The walls 53 are so dimensioned and configured that gas flow channels 52 have a substantially rectangular polygonal shape, substantially square in the illustrated mode, but with rounded corners in accordance with US patent 4,335,023, issued on June 15, 1982 for JC Dettling et al. The first wash coating layer 20, which in the art and is sometimes referred to here as a "wash coating" is adhered to or coated on the walls 53 of the substrate 12. The second wash coating layer 22 is coated on the first wash coating layer 20 as described herein. In some embodiments, a lower layer (not shown) can be applied to the substrate 12 below the first wash coating layer 20.
    [00048] As shown in figure 5, the carrier element includes empty spaces provided by the gas flow channels 52, and the cross-sectional area of the channels 52 and the thickness of the walls 53 defining the channels 52 will vary from one type of carrier element to another. Similarly, the weight of the wash coating applied to such carriers will vary from case to case. Consequently, when describing the amount of wash coating or catalytic metal component or other component of the composition, it is convenient to use units of component weight per unit volume of catalyst carrier. Therefore, the units of grams per cubic inch (“g / in 3 ”, (1 g / in 3 = 0.061 g / cm 3 )) and grams per cubic foot (“g / foot 3 ”, (1 g / foot 3 = 35.71 g / m 3 )) are used here to mean the weight of a component per volume of the carrier element, including the volume of voids in the carrier element.
    [00049] When the composition is arranged on a refractory oxide substrate, for example, a direct flow honeycomb substrate, the metal concentration of the platinum group is typically approximately
    Petition 870180168667, of 12/28/2018, p. 25/34 / 19 to 200 g / foot 3 (357.14 to 7142.86 g / m 3 ), 30 to 150 g / foot 3 (1071.43 to 5357.14 g / m 3 ) or even 50 to 120 g / foot 3 (1785.71 to 4285.71 g / m 3 ).
    Method of Preparing a Catalyst [00050] With reference to figure 6, one or more embodiments of the invention are directed to methods of making a catalytic article. A substrate surface 12 is coated with a first wash coating layer 20 comprising cerium-supported palladium. The substrate 12 having an input end 14 and an output end 16 defining an axial length L. A single channel 18 of the substrate 12 is shown for illustrative purposes. It is to be understood that the substrate 12 can comprise a plurality of channels. In detailed embodiments, substrate 12 has a plurality of channels 18 formed by axially extended gas permeable walls. Palladium has a charge greater than or equal to approximately 2% by weight. The coated substrate 12 is then dried and calcined to fix the first wash coating layer 20 onto the substrate 12. Some embodiments of the first wash coating layer 20 have been described here.
    [00051] The coated substrate 12 is then coated with a second wash coating layer 22. The second wash coating layer 22 comprises a platinum group metal and a refractory metal oxide. The coated substrate 12 is then dried and calcined again to fix the second wash coating layer 22 onto the substrate 12. Some embodiments of the second wash coating layer 22 have been described here.
    Emission Treatment System [00052] Referring to figure 7, additional modalities of the invention are addressed to emission treatment systems 70. One or more modalities of system 70 comprise a diesel engine 71 that emits an exhaust stream including hydrocarbons, CO and material in
    Petition 870180168667, of 12/28/2018, p. 26/34 / 19 particles. A catalytic diesel oxidation article 10, as described from start to finish, is positioned downstream of and in flow communication with the diesel engine 71. Catalytic article 10 has an inlet and an outlet end that define an axial length . The exhaust gas stream leaving the diesel engine 71 passes through the catalytic article 10 where NOx, CO and hydrocarbons are oxidized. The exhaust stream leaving the catalytic article 10 can then leave the treatment system 70 via, for example, the discharge pipe 73 and be expelled into the atmosphere.
    EXAMPLES
    Example 1 [00053] A series of CeO 2 , OSC (45% CeO 2 - 55% ZrO 2 ) or ZrO2 samples loaded with different Pd concentrations was prepared by impregnating incipient moisture from support materials with a solution of Pd (NH 3 ) 4 (NO3) 2. The samples were dried at 110 ° C and calcined at 450 ° C in air. After hydrothermal aging at 750 ° C for 20 hours, the samples were evaluated for melting activity of HC and CO catalyst in a laboratory reactor. The catalyst melt gas mixture consisted of 2000 ppm CO, 100 ppm C3H6, 100 ppm C3H8, 50 ppm Toluene, 100 ppm NO, 12% O2 and 5% H2O.
    [00054] Figure 8 shows T50, that is, the temperature at which 50% conversion is obtained (lower T50 ® higher activity) for the various samples. Although a 0.5% sample of Pd / CeO2 showed a higher T50 (215 ° C), the activity of the Pd / CeO2 series increases dramatically with Pd load, and the highest activity is observed when the% Pd is> 4% (<86 ° C). This observation was compatible with the synergy of Pd-CeO2 shown in figure 1. On the other hand, in the OSC (45% CeO255% ZrO2) or ZrO2 supports, the melting T50 of CO catalyst (110
    Petition 870180168667, of 12/28/2018, p. 27/34 / 19
    130 ° C) did not respond to the Pd load and appeared much higher than the 4-8% Pd / CeO2 samples at equivalent Pd load.
    Example 2 [00055] A series of CeO2 and OSC samples (45% CeO2-55% ZrO2) loaded with 2-4% Pd was prepared by incipient moisture impregnation of support materials with Pd solution (NH3) 4 (NO3) 2. The samples were dried at 110 ° C and calcined at 450 ° C in air. Each powder sample was made into a paste and ground to a particle size D90 <12 μ m, then mixed with a pre-ground γ-alumina paste at 50:50 dry gain ratio, then coated over a substrate of direct flow monolith. Γ-alumina served as a binding material for better adhesion of the wash coating. The total wash coating was 1.5 g / in 3 (0.091 g / cm 3 ), and the Pd load was 26 g / foot 3 (928.57 g / m 3 ) for 2% Pd / support or 52 g / foot 3 (1857.14 g / m 3 ) to 4% Pd / support respectively.
    [00056] The 5% Y-CeO2 support was prepared by impregnating Y (NO3) 3 solution over CeO2 followed with drying and calcination. A reference Pt-Pd / Al2O3 catalyst at 70 g / ft 3 (2500 g / m 3 ) of PGM load and 2/1 Pt / Pd ratio was also prepared for comparison. In this case, the precursor solutions of Pd and Pt were co-impregnated on the alumina support followed by drying and calcination. The subsequent paste and coating procedures were similar to those for Pd / CeO2 catalysts. The coated catalysts were aged in a diesel engine at 750 ° C for 20 hours, and measured in relation to the melting activities of O / HC catalyst in a laboratory reactor. The catalyst melt gas mixture consisted of 1400 ppm CO, 100 ppm C3H6, 50 ppm toluene, 100 ppm NO, 5% CO2, 10% O2 and 7% H2O. The space speed was 50,000 h -1 .
    [00057] Figure 9 shows a comparison of the melting data of
    Petition 870180168667, of 12/28/2018, p. 28/34 / 19 CO catalyst. compared to the 2% Pd / OSC catalyst, the 2% Pd / CeO2 catalyst showed improvement> 50 ° C at T50, the 4% Pd / CeO2 showed further improvement than the Pd / CeO2 catalyst at 2%, particularly in the highest temperature region (ie, T80). The T50 of CO of 2% Pd / CeO2 increased by ~ 20 ° C when 5% Y were introduced into CeO2. A similar decrease in activity was seen when other elements such as Zr or La were introduced. Compared to the much higher PGM Pt-Pd / AHE reference catalyst, 2-4% Pd / CeO2 catalysts also showed higher activity in the lower temperature region up to 140 ° C, confirming the Advantages of high Pd / CeO2 component for conversion of CO / HC at low temperature, which could significantly benefit the reduction of emission during cold start.
    Example 3 [00058] Layered catalysts were prepared using 2-6% Pd / CeO2 in the lower layer and PtPd / AEO3 + zeolite β in the upper layer. Given the ratio and load of fixed PGM, the distribution of PGM in the lower and upper layers was adjusted to obtain maximum overall activity. As described in example 2, 2-6% Pd / CeO2 in the lower layer made a greater contribution during cold start emission, whereas the Pt-Pd / Al2O3 component in the upper layer was more effective for converting emission at temperatures higher. Zeolites were separated from the Pd / CeO2 component at all times to avoid a negative impact on Pd. In the examples, the catalyst consisted of 8% Pd / CeO2 or 8% Pd / OSC (45% CeO2-55% ZrO2) in the bottom layer (wash coating load was 1 g / in 3 (0.061 g / cm 3 ), Pd load was 138 g / ft 3 (4928.57 g / m 3 )) and Pt / AHE + β zeolite in the upper layer (wash coating load was 0.75 g / in 3 (0.046 g / cm 3 ), Pt load was 8 g / foot 3 (285.71 g / m 3 )). The catalysts were aged and tested under the
    Petition 870180168667, of 12/28/2018, p. 29/34 / 19 same condition as in example 2. The melting data of C3H6 and CO catalyst are shown in figure 10. The catalyst with the lower layer of 8% Pd / CeO2 showed a T50 below 20-30 ° C .
    [00059] Reference in every specification to “a modality”, “certain modalities”, “one or more modalities” or “a modality” means that at least one aspect, structure, material or characteristic described in relation to the modality is included in an embodiment of the invention. In this way, the appearances of phrases such as "in one or more modalities", "in certain modalities", "in a modality" in various places from the beginning to the end of this specification are not necessarily referring to the same modality of the invention. In addition, specific aspects, structures, materials or characteristics can be combined in any appropriate way in one or more modalities. The order of description of the method above should not be considered limiting, and methods may use the described operations were of order or with omissions or additions.
    [00060] It should be understood that the description above is intended to be illustrative and not restrictive. Many other modalities will be evident to those of ordinary skill in the art after examining the above description. The scope of the invention must therefore be determined with reference to the appended claims, together with the total scope of equivalents to which such claims are entitled.
    权利要求:
    Claims (14)
    [1]
    1. Catalytic article (10) to treat an exhaust gas stream containing hydrocarbons, CO and particulate matter, characterized by the fact that the article comprises:
    a substrate (12) having an inlet end (14) and an outlet end (16) defining an axial length;
    a first washable coating layer (20) on the substrate (12) comprising more than or equal to 2% by weight of palladium dispersed in a ceria support; and a second washable coating layer (22) on the first washable coating layer (20), the second washable coating layer (22) comprising a platinum group metal and a refractory metal oxide.
    [2]
    2. Catalytic article (10) according to claim 1, characterized in that the first washable coating layer (20) comprises palladium in the range of 2% to 10% by weight.
    [3]
    Catalytic article (10) according to claim 1, characterized in that the first washable coating layer (20) comprises 4% palladium by weight.
    [4]
    Catalytic article (10) according to any one of claims 1 to 3, characterized in that the first washable coating layer (20) is free of alumina.
    [5]
    Catalytic article (10) according to any one of claims 1 to 4, characterized in that the first washable coating layer (20) is free of doping.
    [6]
    Catalytic article (10) according to any one of claims 1 to 5, characterized in that the refractory metal oxide in the second washable coating layer (22) comprises alumina.
    [7]
    7. Catalytic article (10) according to any of the
    Petition 870180168667, of 12/28/2018, p. 31/34
    2/3 claims 1 to 6, characterized by the fact that the platinum group metal in the second washable coating layer (22) comprises one or more of platinum and palladium supported on refractory metal oxide.
    [8]
    Catalytic article (10) according to any one of claims 1 to 7, characterized in that the metal of the platinum group in the second washable coating layer (22) is present in the range of 1% to 5% by weight .
    [9]
    Catalytic article (10) according to any one of claims 1 to 8, characterized in that the second washable coating layer (22) further comprises a zeolite.
    [10]
    10. Catalytic article (10) according to claim 9, characterized by the fact that the zeolite is selected from beta zeolite, zeolite Y and ZSM-5.
    [11]
    11. Catalytic article (10) according to claim 1, characterized in that the substrate (12) is a direct flow substrate having a plurality of passages extending longitudinally formed by walls extending longitudinally delimiting and defining said passages .
    [12]
    12. Catalytic article according to claim 1, characterized by the fact that the substrate is a wall flow filter (50) having gas permeable walls (53) formed in a plurality of channels extending axially, each channel (52 ) having one end obstructed with any pair of adjacent channels obstructed at opposite ends thereof.
    [13]
    13. Emissions treatment system (70), characterized by the fact that it comprises:
    a diesel engine (71) emitting an exhaust gas stream including hydrocarbons, CO and particulate matter; and the catalytic article (10) as defined in any of the
    Petition 870180168667, of 12/28/2018, p. 32/34
    3/3 claims 1 to 12.
    [14]
    14. Method for making a catalytic article (10) as defined in any one of claims 1 to 12, characterized in that it comprises:
    coating a substrate surface (12) with a first washable coating layer (20) comprising palladium supported on ceria, the palladium having a charge greater than or equal to 2% by weight;
    drying and calcining the substrate (12), to fix the first washable coating layer (20) on the substrate (12);
    coating the substrate (12) with a second washable coating layer (22) comprising a platinum group metal and a refractory metal oxide; and drying and calcining the substrate (12), to fix the second washable coating layer (22) on the substrate (12).
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    同族专利:
    公开号 | 公开日
    US8668877B2|2014-03-11|
    CN107262094A|2017-10-20|
    MX2013005886A|2013-12-06|
    JP5843880B2|2016-01-13|
    MY161590A|2017-04-28|
    JP2014504202A|2014-02-20|
    KR101862814B1|2018-05-30|
    US20120124975A1|2012-05-24|
    KR20140002678A|2014-01-08|
    WO2012071421A3|2012-07-19|
    ZA201304549B|2014-08-27|
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    CA2818860A1|2012-05-31|
    MX342674B|2016-10-07|
    CN103313787A|2013-09-18|
    BR112013013008A2|2017-03-21|
    EP2643082A4|2014-07-30|
    EP2643082A2|2013-10-02|
    EP2643082B1|2017-05-10|
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    法律状态:
    2018-10-02| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-06-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-08-13| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/11/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/11/2011, OBSERVADAS AS CONDICOES LEGAIS |
    2021-09-14| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 10A ANUIDADE. |
    2022-01-04| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2645 DE 14-09-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/954,257|US8668877B2|2010-11-24|2010-11-24|Diesel oxidation catalyst articles and methods of making and using|
    US12/954257|2010-11-24|
    PCT/US2011/061860|WO2012071421A2|2010-11-24|2011-11-22|Diesel oxidation catalyst articles and methods of making and using|
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