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    • 专利摘要:
    "Process for preparing a catalyst" The present invention relates to a process for preparing a catalyst comprising at least the steps of adding a protective agent to an aqueous solution of a metal precursor to give a mixture (m1), adding a reducing agent to the mixture (m1) to give a mixture (m2), add a support material to the mixture (m2) to give a mixture (m3), adjust the pH of the mixture (m3) and separate the solid and liquid phases from the mixture (m3). furthermore, the present invention relates to the catalyst as such and its use as a diesel oxidation catalyst.
    公开号:BR112012002614B1
    申请号:R112012002614-3
    申请日:2010-07-28
    公开日:2019-02-26
    发明作者:Attilio Siani；Torsten Muller-Stach；Torsten Neubauer；Xinyi Wei
    申请人:Basf Corporation；
    IPC主号:
    专利说明:

    "PROCESS TO PREPARE A CATALYST"
    FIELD OF THE INVENTION [1] This invention relates to a method of producing a precious metal catalyst. In addition, the present invention relates to the catalyst as such and its use as a diesel oxidation catalyst.
    BACKGROUND OF THE INVENTION [2] Exhaust gas emitted from an internal combustion engine like a car engine contains carbon monoxide (CO), hydrocarbons (HC), nitrogen oxides (NOx) and so on. These harmful substances are generally purified by an exhaust gas purification catalyst in which the catalyst component mainly consisting of a precious metal such as platinum (Pt), rhodium (Rh), palladium (Pd), iridium (Ir), etc., it is supported by an oxide support such as alumina.
    [3] To support these precious metals from the catalyst component in the oxide support, a method is generally used that involves the steps of using an optionally modified precious metal compound solution, allowing the oxide support to be impregnated with this solution so to disperse the metallic compound on the surface of the oxide support, and cooking of the oxide support. Materials having a high specific surface area such as gamma-alumina are generally employed for the oxide support, to provide a large area of contact with the catalyst component for the exhaust gas.
    [4] It is known that the performance of supported metal catalysts depends on the structure and composition of the metal nanoparticles they contain, and the nature of the support.
    [5] Although simple, conventional impregnation methods used for the preparation of support catalysts generally provide limited control over the structure of the resulting materials (ie, size
    Petition 870180143120, of 10/22/2018, p. 9/33
    2/22 particle average, particle composition and location of active components).
    [6] To overcome such disadvantages, the published literature describes the use of alternative synthetic pathways such as the use of organometallic molecular carbonyl cluster precursors as well as methods involving the use of modeling agents (eg surfactants and polymers). The potential advantages of using metallic carbonyl clusters as a source of precious metal for catalytic applications lie in high metal dispersions and homogeneity in particle size composition due to the relatively low temperature of the activation procedure and, when using heterometallic cluster precursors, at heterometallic connections made. However, the limited stability of said clusters on the surfaces of various supports, as well as difficulties in their synthesis and handling, makes use of catalysts derived from problematic clusters for large-scale applications.
    [7] On the other hand, synthetic routes based on the use of modeling agents offer the possibility to prepare colloidal metal nanoparticles with particle size and controlled composition. The synthesis steps for the preparation of supporting metal catalysts through colloidal routes commonly involve the interaction between the metal precursors and the protective agent followed by a reduction treatment that leads to the formation of a colloidal metal suspension. Said metal suspension can then be deposited on a surface of the support and finally the protective agent is removed to expose the nanoparticles to the reagents.
    [8] Some examples are reported in the literature describing the use of polymer-stabilized precious metal colloids as precursors for the preparation of support metal catalysts where improved metal dispersions over conventional methods are achieved.
    [9] Liu et al. (Polym. Adv. Technol. 1996, 7, 634) describe the
    Petition 870180143120, of 10/22/2018, p. 10/33
    3/22 deposition of Pt and Pd nanoparticles protected with polyvinylpyrrolidone (PVP) and polyvinyl alcohol- (PVA) on an S1O2 surface. However, each surface had to be pretreated by pre-adsorption of polyacrylic acid to ensure the deposition of polymer-coated nanoparticles.
    [10] Colloidal Pd suspensions were prepared by Burton et al. (Top. Catai. 2008, 49, 227-232) heating up to 300 ° C an appropriate Pd precursor in a solution of triclifosfino or octilamina. The particles obtained were then washed with hexane and deposited on an oxidic support by calcination of the support to remove the protective agent.
    [11] Higher exhaust gas purification performance is still required for an exhaust gas purification catalyst for environmental protection. Controlling the size of the precious metal cluster to an optimal size is one way. According to the prior art precious metal support method using a precious metal compound solution, the precious metal is adsorbed on the oxide support at an atomic level at which the precious metal compound is dispersed on the surface of the support of the oxide, but the precious metal atoms move and cause grain to grow in the cooking process in which the precious metal is firmly supported. It has therefore been extremely difficult to support only the precious metal of a desired cluster size on the oxide support.
    [12] Unexamined JP Patent Publication (Kokai) No. 2003181288 proposes a method for supporting a precious metal or an oxide support by introducing the precious metal into the pores of a hollow carbon material such as a carbon nanocomet or a nanotube of carbon so that the precious metal forms a grouping containing a desired size, instead of directly supporting the precious metal on the oxide support, fixing the precious metal to the carbon material, then baking them together and then burning and removing the material carbon and at the same time,
    Petition 870180143120, of 10/22/2018, p. 11/33
    4/22 supporting the precious metal in the oxide support.
    [13] According to this method, the precious metal exists within the pores of the carbon material until the carbon material is burned and removed, and when the carbon material is burned and removed, the precious metal is quickly supported on the support. of oxide. Therefore, the precious metal can be substantially supported by the oxide support in a cluster size within the pores of the carbon material. However, this method is not without problems in which the precious metal must be introduced into the pores of the hollow carbon material, which results in low productivity.
    [14] Torigoe, Esumi et al. propose in “Chemical Industry”, pp. 276-296 (1998) produce precious metal particles containing particle sizes in the order of nm by reducing a mixed solution of a polymer compound such as polyvinylpyrrolidone and precious metal ions using a reducing agent such as H2, NaBH 4 , C2H5OH, or the like.
    [15] However, when a compound is used as the reducing agent in the method described above, there is a problem that an element or elements are contained in the compound mixture as impurities in the final particles of the precious metal. When NaBH 4 is used as the reducing agent, for example, mixing Na and B. When an alcohol is used as the reducing agent, not only alcohol, but also ketones, aldehydes, carboxylic acids, etc., formed while alcohol is oxidized during the reduction of metal ions, they can mix. When hydrogen is used as the reducing agent, problems occur due to the fact that the particles resulting from the precious metal become large and the particles have a strange shape.
    [16] WO 2004/089508 provides a method for preparing an oxidation catalyst to oxidize the volatile organic fraction and a catalyzed wall flow filter for use in removing exhaust soot particles from diesel engines, including preparing a PGM salt. and a metal salt
    Petition 870180143120, of 10/22/2018, p. 12/33
    5/22 transition / alkaline with a water-soluble polymer compound and reducing agent, to obtain a first colloidal solution which is then covered by washing on a monolithic ceramic substrate coated with catalyst support, followed by a calcination process in high temperatures, to obtain an oxidation catalyst; and treating a PGM salt and a metal salt mixture including at least one selected from a first metal catalyst group to increase the oxidation activity for nitrogen monoxide (NO) and at least one selected from a second metal catalyst group for decrease the combustion temperature of soot particles by oxidizing agents, such as nitrogen dioxide and oxygen, with a water-soluble polymer compound and a reducing agent, to obtain a second colloidal solution which is then covered by washing in a filter wall flow coated with catalyst support, followed by calcination process at high temperatures, to obtain a catalyzed wall flow filter.
    [17] WO 95/32790 generally refers to the control of hydrocarbons, carbon monoxide, and nitrogen oxides in the internal combustion exhaust of engines. More particularly, the invention relates to the removal of NO when the exhaust gases substantially include oxygen in excess of that necessary for combustion of the fuel. This is for example the case with light-burning engines, diesel engines, and other engines currently under development.
    [18] US 2008/0268159 refers to the method of producing a precious metal catalyst. More specifically, the present invention relates to a method of producing a precious metal catalyst, the size of the array from which it is controlled. US 2008/0628159 provides a method of producing a precious metal catalyst including the steps of uniformly mixing a solution containing a precious metal and an aqueous solution of a polymer compound capable of coordination with the metal
    Petition 870180143120, of 10/22/2018, p. 13/33
    6/22 precious to form a complex of the precious metal and the polymer compound, added to the aqueous solution under dripping, containing the complex, to the water containing micro-bubbles containing this hydrogen, mix the solutions to reduce the precious metal, supporting the mixed solution on a stand and cooking the solution.
    [19] The processes known to the state of the art have several disadvantages, such as, for example, the use of multi-step procedures to obtain the final catalyst, limited control over the location of colloidal nanoparticles in the impregnation in a coated wall flow filter. on the support, the use of high temperature treatment for the formation of colloidal suspension or the use of an H2 micro-bubble generator, which has a limited lifetime in the solution. These disadvantages limit the method's applicability and productivity.
    [20] The present invention provides a process for preparing a catalyst avoiding the disadvantages of processes known from the state of the art.
    SUMMARY OF THE INVENTION [21] The present invention is directed to a process for preparing a catalyst. In particular, the present invention is directed to a process for preparing a catalyst, at least comprising the steps:
    (1) adding a protective agent to an aqueous solution of a precursor metal to generate a mixture (Ml), (2) adding a reducing agent to the mixture (Ml) to generate a mixture (M2), (3) adding a material mixture support (M2) to generate a mixture (M3), (4) adjust the pH of the mixture (M3), (5) separate the solid and liquid phase from the mixture (M3).
    [22] According to another aspect, the present invention is
    Petition 870180143120, of 10/22/2018, p. 14/33
    7/22 directed to a catalyst obtainable by a process according to the present invention.
    [23] Furthermore, the present invention is directed to the use of a catalyst obtainable by a process according to the present invention or of a catalyst of the present invention as a diesel oxidation catalyst.
    DETAILED DESCRIPTION OF THE INVENTION [24] The present invention is directed to a process for preparing a catalyst, In particular, the present invention is directed to a process for preparing a catalyst, at least comprising the steps:
    (1) add a protective agent to an aqueous solution of a precursor metal to generate a mixture (Ml), (2) add a reducing agent to the mixture (Ml) to generate a mixture (M2), (3) add a material mixture support (M2) to generate a mixture (M3), (4) adjust the pH of the mixture (M3), (5) separate the solid and liquid phase from the mixture (M3).
    [25] In accordance with the process of the present invention, a catalyst is obtained which contains metal particles highly dispersed in a support material.
    [26] The present invention improves the state of the art described above by reducing the number of preparation steps. This results in an improved process and reduced costs.
    [27] Furthermore, the process according to the present invention can be carried out without an inert atmosphere, thus eliminating the need for purging of gases or inert atmospheres in the dissolution and interaction of the metal salt precursor with the protective agent.
    [28] Using the process of the present invention, it is possible to obtain
    Petition 870180143120, of 10/22/2018, p. 15/33
    8/22 deposition of metallic nanocomposites on the support surface by simplified control over the physical-chemical properties (ie, pH) of the metal colloid solutions used as a precursor.
    [29] The use of additional polymers and or solvents in the aqueous solution to obtain a more homogeneous metal dispersion and composition of metal nanoparticles with respect to conventional methods can be avoided.
    [30] Finally, the need for multiple metal / protective agent interaction steps and / or reduction steps to form highly dispersed Pt / Pd nanoparticles with homogeneous composition are eliminated in accordance with the present invention. According to the present invention the composition of the resulting Pt / Pd particles is controlled by the relative amount of Pt / Pd used in the preparation.
    [31] The catalysts obtained by the process according to the present invention show improved catalytic activity of the resulting materials even after hydrothermal treatment at 800 ° C for 12h.
    [32] The process according to the present invention comprises steps (1) to (5). According to step (1), a protective agent is added to an aqueous solution of metal path to generate a mixture (Ml).
    [33] As a metal precursor, any suitable compound can be added that is soluble in water, that is, that is suitable for preparing an aqueous solution of the metal precursor. Suitable compounds are, for example, metal salts. Preferably, an appropriate compound of a metal selected from the group consisting of platinum, palladium, rhodium, gold and silver or mixtures thereof is used. For example platinum, palladium, rhodium, gold and silver metal salts or mixtures thereof are used in the process of the present invention. In particular, the metal is palladium or platinum.
    Petition 870180143120, of 10/22/2018, p. 16/33
    9/22 [34] According to one embodiment, the present invention is therefore directed to a process for preparing a catalyst as disclosed above, where the metal precursor is selected from the metal salt of platinum, palladium, rhodium, gold and silver or mixtures thereof.
    [35] An aqueous metal precursor solution is used in step (1). According to the present invention, the concentration of the metal in the aqueous metal precursor solution is in the range of 1 * 10 ' 6 to 4.6 * IO ' 5 mol of metal per mole of solution, more preferably in the range of 5 * IO' 6 to 4.3 * IO ' 5 mol of metal per mole of solution, more preferably in the range of 1 * 10' 5 to 3, 9 * 10 5 moles of metal per mole solution, more preferably in the range of 1.8 * IO "5 to 3.6 * IO '5 mol per mol of metal solution.
    [36] As a protective agent, any suitable compound can be used in the context of the present invention. Suitable protective agents are for example soluble in homo and copolymers containing one or more amino, starch, carboxylic, aldehyde, or hydroxyl groups, and organic molecules containing one or more amino, starch, carboxylic, aldehyde, or hydroxyl groups and mixtures of the themselves.
    [37] According to another embodiment, the present invention is therefore directed to a process for preparing a catalyst as disclosed above, where the protecting agent is selected from homo and copolymers containing one or more amino, starch, carboxylic, aldehyde groups, or hydroxyl, and organic molecules containing one or more amino, starch, carboxylic, aldehydic, or hydroxyl groups and mixtures thereof.
    [38] Preferred protective agents are, for example, selected from poly (vinyl alcohol), poly (vinyl pyrrolidone), poly (ethyleneimine), poly (acrylic acid), alkali metal carbohydrates or citrates. Therefore, according to a preferred embodiment, the present invention is therefore directed to a process for preparing a catalyst as disclosed above, where the protective agent is selected from poly (vinyl alcohol),
    Petition 870180143120, of 10/22/2018, p. 17/33
    10/22 poly (vinylpyrrolidone), poly (ethyleneimine), poly (acrylic acid), alkali metal carbohydrates or citrates.
    [39] According to the present invention, appropriate ratios between the metal precursor and the protective agent are in the range of 1: 1 to 1:10 when calculated as ratios between one mole of precious metal and the protective agent unit. . Preferred proportions between a mol of precursor metal and a protective agent unit are in the range of 1: 2 to 1: 4.
    [40] Preferably, the reaction is conducted at room pressure at a temperature of 15 to 35 ° C, more preferably at a temperature of 20 to 30 ° C, more preferably at room temperature. It is preferable to conduct the reaction under agitation. In accordance with the present invention, mixtures are preferably obtained by mixing two or more solutions comprising the same or different components of precious metals. However, it is still possible that the mixtures made are used.
    [41] In step (1) of the process according to the present invention, the mixture (Ml) is obtained. According to step (2), a reducing agent is added to the mixture (M1) to generate a mixture (M2).
    [42] In principle, any suitable reducing agent can be used in the process according to the present invention. Preferably, the reducing agent is selected from alkali metal borohydrides, hydrazine, formaldehyde, alkali metal citrates, amino-borane complexes, hydrogen gas and carbon monoxide.
    [43] Therefore, according to another embodiment, the present invention is therefore directed to a process for preparing a catalyst as disclosed above, where the reducing agent is selected from alkali metal borohydrides, hydrazine, formaldehyde, alkali metal citrates, complexes amino-borane, hydrogen gas and carbon monoxide
    Petition 870180143120, of 10/22/2018, p. 18/33
    11/22 carbon.
    [44] Appropriate ratios between the metal's precursor and the reducing agent are in the range of 1: 1 to 1:20 when calculated as the ratio between one mole of precious metal and one mole of the reducing agent. Preferred proportions between one mole of precursor metal and one mole of reducing agent are in the range of 1: 2 to 1: 8. Depending on the reducing agent, the reaction can be carried out at room temperature with stirring.
    [45] The mixtures then obtained can be further constituted by mixing two or more (M2) mixtures comprising the same or different components of precious metal. Said solutions can also be obtained by mixing two or more solutions (Ml), which are obtained in step (1) adding the same or different protective agent, followed by the addition of the same or different reducing agent. In addition, the mixture (M2) can be obtained by mixing one or more mixtures (M2) with one or more mixtures (Ml) followed by the addition of a reducing agent.
    [46] In step (2), the mixture (M2) is obtained. To this mixture, a support material is added to generate a mixture (M3).
    [47] In principle, any suitable support material can be used in the process according to the present invention. Preferred support materials are, for example, aluminum oxide, silicon oxide, cerium oxide, zirconium oxide, titanium oxide, isolated magnesium oxide or as mixtures and / or solid solutions of these support materials.
    [48] According to another embodiment, the present invention is therefore directed to a process for preparing a catalyst as disclosed above, where the material support material is selected from aluminum oxide, silicon oxide, cerium oxide, zirconium oxide , titanium oxide, magnesium oxide alone or as mixtures and / or solid solutions of these support materials.
    [49] Appropriate amounts of support material are chosen
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    12/22 to have a final concentration of precious metal in the support in the range of 0.01% to 10% w / w with respect to the resulting material. Preferred concentrations of the precious metal in the support material are in the range of 0.1% to 5% w / w with respect to the support material.
    [50] In accordance with the present invention, the support material is added to the mixture at room temperature while the mixture is stirred.
    [51] According to step (4) of the process of the present invention, the pH of the mixture (M3) obtained in step (3) of the process of the present invention is adjusted. The pH is preferably adjusted to a value in the range of 2 to 7. Thus, according to another embodiment, the present invention is directed to a process for preparing a catalyst as disclosed above, where in step (4) the pH is adjusted to a value in the range of 2 to 7.
    [52] According to the present invention, the pH can be adjusted by any appropriate method, for example by adding an appropriate acid, in particular a mineral acid such as HCl or HNO3.
    [53] According to the present invention, pH adjustment is preferably carried out at room temperature while the solution is stirred.
    [54] In step (5) of the process of the present invention, the solid and liquid phases of the mixture (M3) are separated. Separation can be achieved by any appropriate method, for example filtration or centrifugation or evaporation of the solvent. According to another embodiment, the present invention is therefore directed to a process for preparing a catalyst as disclosed above, where in step (5) the solid and liquid phase of the mixture (M3) are separated by filtration or evaporation of the solvent.
    [55] The process according to the present invention can further comprise additional steps, for example heating or cooling steps to change the concentration of any of the mixtures obtained
    Petition 870180143120, of 10/22/2018, p. 20/33
    13/22 in the process of the present invention. Additional steps can be conducted before or after steps (1) to (5) or between any of steps (1), (2), (3), (4), and / or (5) of the process of the present invention.
    [56] In accordance with the process of the present invention, a catalyst is obtained which has highly dispersed nanoparticles with a homogeneous composition.
    [57] The catalysts obtained by the process according to the present invention show improved catalytic activity of the resulting materials even after hydrothermal treatment at 800 ° C for 12h.
    [58] Therefore, according to another aspect, the present invention is directed to a catalyst obtainable and / or obtained by the process as disclosed above.
    [59] The catalyst according to the present invention comprises a support material and highly dispersed metal nanoparticles.
    [60] Preferably, the support material is selected from preferred support materials as mentioned above, for example aluminum oxide, silicon oxide, cerium oxide, zirconium oxide, titanium oxide, isolated magnesium oxide or as mixtures and / or solid solutions of these support materials.
    [61] The metal is preferably selected from platinum, palladium, rhodium, gold and silver or mixtures thereof, more preferably platinum and palladium or mixtures thereof.
    [62] The catalysts according to the present invention have improved properties. For example, for a catalyst comprising only platinum as a metal, after treating the catalyst at 450 ° C for a desired period of time in an oxidizing atmosphere (air), not less than 65% of the metal particles have a mean diameter below 3 nm. Also for a catalyst comprising only platinum as a metal, after treating the catalyst obtained at 800 ° C for 12h in an atmosphere
    Petition 870180143120, of 10/22/2018, p. 21/33
    14/22 oxidant (10% H2O in air), not less than 22% of the metal particles have an average diameter less than 22 nm.
    [63] For a catalyst comprising platinum and palladium as metals, after treating the catalyst obtained at 800 ° C for 12 h in an oxidizing atmosphere (10% H2O in air), no less than 36% of the metal particles have a average diameter below 22 nm. In addition, for a catalyst comprising platinum and palladium as metals, after treating the catalyst obtained at 800 ° C for 12h in an oxidizing atmosphere (100% H2O in air), no less than 90% of the metal particles are made up of both Pt and Pd.
    [64] The catalysts obtained according to the process according to the present invention or the catalysts according to the present invention are in particular suitable as a diesel oxidation catalyst, in particular due to the improved thermal resistance and particle grain growth reduced metal during simulated hydrothermal aging conditions, the aging trend conditions typically encountered during the operation of a diesel engine. Therefore, according to another aspect, the present invention is directed to the use of a catalyst obtainable and / or obtained by a process according to the present invention as a diesel oxidation catalyst. In addition, the present invention relates to a process for oxidizing diesel exhaust where the diesel exhaust is brought into contact with a catalyst obtainable and / or obtained by a process according to the present invention.
    [65] This catalytic soot filter of the present invention can be used in an integrated emission treatment system, in particular in an exhaust duct comprising one or more additional components for the treatment of diesel exhaust emissions. For example, said exhaust channel that is more preferably in fluid communication with the engine
    Petition 870180143120, of 10/22/2018, p. 22/33
    15/22 diesel may comprise a soot filter catalyzed according to the present invention and may further comprise a diesel oxidation catalyst article (DOC) and / or selective catalytic reduction article (SCR) and / or a catalytic catalyst article NOx reduction and storage (NSR). More preferably, the DOC article and / or the SCR article and / or the NSR article are in fluid communication with the catalyzed soot filter. The diesel oxidation catalyst can be located upstream or downstream of the catalyzed soot filter and / or selective catalytic reduction component. More preferably, the catalyzed soot filter of the present invention is located downstream of the DOC article. Even more preferably the catalyzed soot filter of the present invention is located either upstream or downstream of the SCR article.
    [66] Even more preferably, downstream of the inventive catalyzed soot filter, there is a NOx reduction catalytic article comprised in the system, preferably in the NOx reduction and storage catalytic article (NSR).
    [67] An SCR-appropriate article for use in the exhaust pipe is typically capable of catalyzing the reaction of O2 with any excess of NH3 to N2 and H2O, so that NH3 is not emitted into the atmosphere. Useful SCR catalytic compositions used in the exhaust pipe must still have thermal resistance at temperatures greater than 650 ° C. Said high temperatures can be found during the regeneration of an upstream catalyzed soot filter. Suitable SCR articles are described, for example, in US 4,961,917 and US 5,516,497. Suitable SCR articles include one or both of an iron and a copper promoter typically present in a zeolite in an amount of about 0.1 to 30 weight percent, preferably about 1 to 5 weight percent, of the total promoter weight plus zeolite. Typical zeolites may have a CHA skeleton structure.
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    16/22 [68] The inventive catalytic soot filter can be fitted downstream of the DOC. In said arrangement, the inventive catalyzed soot filter provides the advantage that HC and CO are reduced during soot combustion which is most preferably achieved by the zone upstream of the inventive filter. In addition, the specific design of the rear zone ensures that the zone downstream of the catalyzed soot filter, as low as possible NOx is generated. Thus, said DOC downstream, the inventive catalyzed soot filter can be very advantageous in its cleaning function for the treatment of diesel exhaust.
    [69] In addition, the present invention relates to the catalyzed soot filter as defined above for use in a diesel engine exhaust stream treatment method, the exhaust stream containing soot particles, said method comprising contacting the stream exhaust with catalyzed soot filter, preferably after being directed to the exhaust stream by a diesel oxidation catalyst (DOC), said DOC preferably comprising a flow through the substrate or a wall flow substrate. Similarly, the present invention relates to the use of the catalyzed soot filter as defined above to treat a diesel engine exhaust stream, the exhaust stream containing soot particles, where the exhaust stream is contacted with the filter catalyzed soot, preferably after directing the exhaust stream by a diesel oxidation catalyst (DOC), said DOC preferably comprising a substrate flow or a wall flow substrate.
    [70] In addition, the present invention relates to a system for treating a diesel engine exhaust chain, the system comprising an exhaust pipe in fluid communication with the diesel engine through an exhaust manifold;
    a catalyzed soot filter as defined above; and
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    17/22 one or more of the following in fluid communication with the catalyzed soot filter: a diesel oxidation catalyst (DOC), a selective catalytic reduction article (SCR), a NOx reduction and storage catalytic article (NSR) .
    [71] Preferably, the catalytic soot filter is installed in the system downstream of the DOC. Most preferably, the system does not contain a NOx reduction catalytic article, and more preferably, the system does not contain a NOx reduction and storage catalytic article (NSR).
    [72] Therefore, the present invention also relates to a method of treating a diesel engine exhaust stream, the exhaust stream containing soot particles, said method comprising contacting the exhaust stream with a catalyzed soot filter as defined above, preferably after directing the exhaust stream by a diesel oxidation catalyst (DOC), said DOC preferably comprising a flow substrate or a wall flow substrate.
    [73] According to an optional embodiment of the present invention, this method further comprises directing the exhaust current resulting from DOC or the soot filter catalyzed by a selective catalytic reduction (SCR) article.
    DETAILED DESCRIPTION OF THE FIGURES [74] Figure 1. shows the transmission electron microscopy of a Pt / Pd sample on an alumina support prepared following the procedure according to Example 3 below and detailing the particle size composition. The x-axis of the diagram shows the number of particles (#), the y-axis the Pt / Pd ratio (in mol / mol).
    [75] Figure 2. shows the XRD spectrum of 1% Pt in aluminum oxide prepared according to the process of the invention. The x-axis shows the 2 Theta scale (in °), the y-axis the intensity (in lincounts; I / LC).
    Petition 870180143120, of 10/22/2018, p. 25/33
    18/22 [76] Figure 3. shows the XRD spectrum of 1% Pt in aluminum oxide prepared according to a process according to the state of the art. The x-axis shows the 2 Theta scale (in °), the y-axis the intensity (in lincounts; I / LC).
    [77] Figure 4. shows the XRD spectrum of 0.67% and Pt 0.33% Pd in aluminum oxide prepared according to the process of the invention. The x-axis shows the 2 Theta scale (in °), the y-axis the intensity (in lincounts; I / LC).
    [78] Figure 5. shows the XRD spectrum of 0.67% Pt and 0.33% Pd in aluminum oxide prepared according to a process according to the state of the art. The x-axis shows the 2 Theta scale (in °), the y-axis the intensity (in lincounts; I / LC).
    [79] Figure 6. shows a diagram comparing the gas activity of catalysts prepared according to the process of the invention with that of catalysts in the prior art. A detailed description of Fig. 6 should be found in the context of Example 11 here below.
    [80] The present invention is further illustrated by means of the following examples:
    EXAMPLES
    Example 1 [81] 10.2 g of a PLPtCló solution containing 5.1 * 10 ' 2 moles of Pt per liter of solution were diluted in 400 ml of water and an appropriate amount of a PVP solution containing 10 mg of PVP per ml of solution was added to achieve a weight ratio of Pt / PVP equal to 1. After allowing the solution to stir at room temperature in air for 1 hour, NaBH 4 was added to the solution at room temperature. The amount of NaBH 4 was chosen to have a Pt / NaBH 4 weight ratio of 1/2. After stirring for 1 hour in air the mixture obtained, an appropriate amount of powdered alumina was added to the solution to achieve a loading
    Petition 870180143120, of 10/22/2018, p. 26/33
    19/22 total metal of 1% w / w and the pH adjusted to a value of 2.4 with an HCl solution containing 15% HCl by weight. After 30 minutes of stirring the solution was filtered and the powdered solid recovered.
    Example 2 [82] The same process and quantities of reagents were used as in Example 1 with the exception of the addition of PVP. Here, a timely amount of PVP solution containing 10 mg of PVP per mg of solution was added to achieve a weight ratio of Pt / PVP equal to 2.
    Example 3 [83] The same process and quantities were used as Example 2 with the exception that 6.6 g of a solution of H ^ PtClô containing
    5.1 * 10 ' 2 moles of Pt per liter of solution were diluted in 400 ml of water together with 110 mg of K 2 PdCl 4 .
    [84] As can be seen in Figure 1, precious metal nanoparticles comprise both platinum and palladium and the composition is the same as one would expect from the relative proportion of platinum and palladium when calculated based on that of precious metal.
    Example 4 [85] 6.6 g of a H ^ PtClô solution containing 5.1 * 10 ' 2 moles of Pt per liter of solution were diluted in 400 ml of water and an appropriate amount of a PVP solution containing 10 mg of PVP per ml of solution was added to achieve a Pt / PVP weight ratio of 1. After allowing the solution to stir at room temperature in air for 1 hour, NaBH 4 was added to the solution at room temperature. The amount of NaBH 4 was chosen to have a Pt / NaBH 4 weight ratio of 1/2. The resulting solution was stirred for 30 minutes and then 110 mg of K 2 PdCl 4 was added to the solution. After 30 minutes, NaBH 4 was added to the solution at room temperature. The amount of NaBH 4 was chosen to have a
    Petition 870180143120, of 10/22/2018, p. 27/33
    20/22 1/2 weight ratio of Pd / NaBH 4 . After stirring for 1 hour in air the mixture obtained, an appropriate amount of powdered alumina was added to the solution to achieve a total metal loading of 1% w / w and the pH adjusted to a value of 2.4 with a solution of HCl containing 15% HCl by weight. After 30 minutes of stirring, the solution was filtered and the powdered solid recovered.
    Example 5 [86] The same process and quantities of reagents were used as in Example 4 with the exception that the order of addition of H ^ PtClô and K2PdCl 4 was reversed.
    Example 6 [87] The same process and quantities of reagents were used as in Example 1 with the exception of adding PVP. Here a timely amount of PVP solution containing 10 mg of PVP per mg of solution was added to achieve a weight ratio of Pt / PVP equal to 4.
    Example 7 [88] The same process and quantities of reagents were used as in Example 1 with the exception of H ^ PtClô and amounts of support that were chosen to obtain a catalyst containing 2% w / w of precious metal with respect to the support.
    Example 8 [89] The same process and quantities of reagents were used as in Example 3 with the exception of amounts of H ^ PtClô, K 2 PdCl 4 and alumina which were chosen to obtain a catalyst containing 4% w / w of precious metal regarding support.
    Example 9 - Comparative Example [90] Referring to Figure 2, an XRD spectrum of a sample is shown comprising 1% Pt w / w with respect to the support material deposited on alumina support, prepared after the same process as
    Petition 870180143120, of 10/22/2018, p. 28/33
    21/22
    Example 1, which was thermally aged for 12 hours at 800 ° C.
    [91] Figure 3 shows an XRD spectrum of a sample comprising 1% Pt w / w with respect to the support material deposited on an alumina support, prepared from the same precursor of the precious metal according to the impregnation methods incipient humidity of the state of the art, which has been thermally aged for 12 hours at 800 ° C.
    [92] As can be seen, in Figure 2 the Pt diffraction peak is broader and less intense than in the case of the sample prepared according to the state of the art incipient moisture impregnation, thus indicating a smaller average size of particle.
    Example 10 - Comparative Example [93] Referring to Figure 4, an XRD spectrum of a sample is shown comprising 0.67% Pt w / w and 0.33% Pd w / w with respect to the support material deposited on a support alumina, prepared according to the same process as in Example 3, which was thermally aged for 12 hours at 800 ° C.
    [94] Figure 5 shows an XRD spectrum of a sample comprising 0.67% Pt w / w and 0.33% Pd w / w with respect to the support material deposited on an alumina support, prepared from the same precursors of precious metal according to the state of the art incipient moisture impregnation methods, which has been thermally aged for 12 hours at 800 ° C.
    [95] As can be seen, in Figure 4 the Pt / Pd diffraction peak is broader and less meaningful than in the case of the sample prepared according to the incipient moisture impregnation of the state of the art, thus indicating a smaller size particle average.
    Example 11 - Comparison of Examples and Examples of the State of the Art [96] Figure 6 shows the gas activity of samples tested in
    Petition 870180143120, of 10/22/2018, p. 29/33
    22/22 a laboratory reactor simulating the exhaust emissions of a conventional diesel engine. The reaction conditions used were a fixed bed tube reactor where 40 mg of powder was diluted with 100 mg of cordierite material and a mixture was crushed and sieved in the range of 250-500 micrometers. The total gas flow was 200 mL / min and the resulting spatial velocity was equivalent to 15,000-20,000 per hour that could be experienced by a monolith sample. The gas composition used in the powder reactor test comprised CO 2000 ppm, NO 100 ppm, C3H6 300 ppm, C3H6 300 ppm, toluene 350 ppm, O212%, H2O 5%. Unless otherwise specified, hydrocarbon (HC) concentrations are reported based on Cl.
    [97] At the start of the light-off test, the powder sample was equilibrated in the gas mixture for 20 minutes at 50 ° C. The temperature at which 50% conversion was observed is denoted as T50 and was used as the measure of catalytic activity: the lower ο T50, the better the performance of the catalyst. The activity after thermal aging for 12h at 800 ° C of the samples prepared according to the process of the invention as outlined in Example 2, Example 3, Example 7 and Example 8, was compared to that of samples prepared according to the methods of impregnation by state of the art (IW) incipient moisture from the same precious metal precursors, deposited on the same support material and containing the same precious metal content as in Example 2, Example 3, Example 7 and Example 8.
    [98] As can be seen, the catalytic activity of samples prepared according to the process of the invention is greater than that of samples prepared according to the prior art impregnation methods as indicated by the lower T50 value of CO in the stream of power used for the evaluation.
    权利要求:
    Claims (6)
    [1]
    1. Process for preparing a catalyst, characterized by the fact that it comprises at least the steps of:
    (1) adding a protecting agent to an aqueous solution of a metal precursor to give a mixture (Ml), (2) adding a reducing agent to the mixture (Ml) to give a mixture (M2), where the reducing agent is selected from alkali metal borohydrides, hydrazine, formaldehyde, alkali metal citrates, aminoborane complexes, hydrogen gas and carbon monoxide, (3) add a support material to the mixture (M2) to give a mixture (M3), (4 ) adjust the pH of the mixture (M3) to a value in the range of 2 to 7, (5) separate the solid and liquid phases of the mixture (M3).
    [2]
    2. Process according to claim 1, characterized by the fact that the protective agent is selected from homo and soluble copolymers having one or more amino, starch, carboxylic, aldehyde or hydroxyl groups and organic molecules having one or more amino groups , starch, carboxylic, aldehyde, hydroxyl and mixtures thereof.
    [3]
    3. Process according to claim 1 or 2, characterized by the fact that the protective agent is selected from poly (vinyl alcohol), poly (vinylpyrrolidone), poly- (ethyleneimine), poly (acrylic acid), carbohydrates or alkali metal citrates.
    [4]
    Process according to any one of claims 1 to 3, characterized in that the metal precursor is selected from the metallic salt of platinum, palladium, rhodium, gold and silver or mixtures thereof.
    [5]
    5. Process according to any one of claims 1 to 4, characterized in that the support material is selected from aluminum oxide, silicon oxide, cerium oxide, zirconium oxide, oxide
    Petition 870180143120, of 10/22/2018, p. 31/33
    2/2 of titanium, magnesium oxide alone or as mixtures and / or solid solutions of these support materials.
    [6]
    Process according to any one of claims 1 to 5, characterized in that in step (5) the solid and liquid phases of the mixture (M3) are separated by filtration or evaporation of the solvent.
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    US20140044627A1|2014-02-13|
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    EP2461905A2|2012-06-13|
    KR20180019244A|2018-02-23|
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    法律状态:
    2018-03-27| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2018-07-24| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2018-12-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-02-26| 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 28/07/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-06-01| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 11A ANUIDADE. |
    2021-09-21| 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 2630 DE 01-06-2021 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
    US23142709P| true| 2009-08-05|2009-08-05|
    US61/231,427|2009-08-05|
    US12/844,287|2010-07-27|
    US12/844,287|US20110033353A1|2009-08-05|2010-07-27|Preparation of Diesel Oxidation Catalyst Via Deposition of Colloidal Nanoparticles|
    PCT/US2010/043463|WO2011017139A2|2009-08-05|2010-07-28|Preparation of diesel oxidation catalyst via deposition of colloidal nanoparticles|
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