EXHAUST GAS-PURIFICATION CATALYST HAVING MULTI-LAYER STRUCTURE INCLUDING PRECIOUS METAL THIN LAYER AS TOP LAYER, AND METHOD FOR PRODUCING SAME

Abstract

Disclosed is an exhaust gas purification catalyst with a multilayered structure including an ultra-thin layer with a thickness of 20 micrometers or less and containing Rh, Pd, or both as at least one precious metal component, and to a method of manufacturing the same. The method includes a step of forming an ultra-thin layer having a thickness of 20 micrometers or less as the top layer of the catalyst by applying a polymer coating solution containing a polymer having a functional group capable of chelating with the precious metal component(s) on the surface of the multilayer structure of the catalyst. The disclosed catalyst exhibits improved removal efficiency for THC, CO, and NOx contained compared to an existing thin film-type catalyst. Since the disclosed catalyst is coated with a thin coating layer containing at least a portion of precious metal components, the disclosed catalyst exhibits improved performance while using the same amount of precious metal components as in conventional catalysts.

Claims

1. A method of producing an exhaust gas purification catalyst having a multilayered structure, the method comprising: forming a pre-catalyst body having a multilayered structure on a substrate using a catalyst slurry; and applying a coating solution comprising a precious metal component onto a surface of the pre-catalyst body, thereby producing an exhaust gas purification catalyst having a multilayered structure.

2. The method of claim 1, wherein the coating solution comprising the precious metal component is a polymer solution comprising a polymer that forms a composite with the precious metal component.

3. The method of claim 2, wherein the polymer forming the composite with the precious metal component has a functional group capable of chelating with the precious metal component.

4. The method of claim 3, wherein the functional group is a hydroxyl group or an ether group.

5. The method of claim 2, wherein the polymer is hydroxyethyl cellulose (HEC) or polypropylene glycol.

6. An exhaust gas purification catalyst having a multilayer structure, the catalyst being produced by the method of claim 1, wherein an uppermost layer thereof has a thickness of 20 micrometers or less and contains the precious metal.

7. The method of claim 1, wherein the precious metal component comprises Pd.

Description

DESCRIPTION OF DRAWINGS

[0010] FIG. 1 is a conceptual diagram illustrating a catalyst having a thin layer containing palladium, according to one embodiment of the present invention;

[0011] FIG. 2A is a diagram illustrating an upper layer that is formed by a conventional coating method, in which the upper layer is not even due to a capillary phenomenon, and FIG. 2B is a photograph taken by an electron probe micro-analyzer (EPMA) and showing a uniform precious metal thin film upper layer formed by the coating method according to the present invention;

[0012] FIG. 3 is a result of comparison between performance a Pd/Rh bilayer three-way catalyst and performance of a Pd(90%)/Rh(100%) multilayer three-way catalyst with a Pd thin layer (10%) according to the present invention; and

[0013] FIG. 4 is a summary of the EMPA photographs and thicknesses of catalysts according to examples of the present invention.

BEST MODE

Definition

[0014] The term “catalyst” as used herein refers to a powder form in which active components such as Pd and Rh are supported alumina particles serving as a catalyst support, and the term “catalyst body” refers to a structure in which the catalyst is supported on a substrate or carrier such as cordierite. The term “washcoat” refers to a slurry in which the catalyst and other components are mixed. The washcoat is applied to the substrate to form the catalyst body. However, as will be understood by those skilled in the art, the terms “catalyst” and “catalyst body” may be interchangeably used. Herein, the term “upper layer” is used in the same sense as the uppermost layer or the top layer, the term “lower layer” refers to a layer close to the substrate, and the term “middle layer” refers to a layer disposed on the lower layer. In addition, an arbitrary layer other than the upper layer will also be collectively referred to as a lower layer.

[0015] The term “heat treatment step” refers to a heating step for inducing raw material components in a precursor state into a stable structure and specifically refers to a heating process performed in an exhaust gas atmosphere. The term “exhaust gas atmosphere” refers to an environment in which exhaust gas components emitted from gasoline engines, including O.sub.2, CO.sub.2, CO, H.sub.2, hydrocarbon (i.e., aromatic hydrocarbon (AHC), propane/propene, etc.), NO.sub.x, and H.sub.2O are present. In the related art, the exhaust gas atmosphere refers to an environment in which H.sub.2O exists in an amount of 5% to 10% by weight, and the content of each of O.sub.2, CO.sub.2, CO, H.sub.2, HC (aromatic hydrocarbon (AHC), propane/propene, etc.), NO.sub.x, and N.sub.2 components varies in a range of 0% to 15% by weight. As used herein, the term “pre-catalyst” refers to an unheated-state catalyst and also means a structural state in which it is not yet alloyed. Specifically, it refers to a state in which precursors are simply supported on a support.

[0016] The term “precious metal (for example, palladium) thin layer” used herein refers to a thin layer that contains not only palladium but also potentially presentable components that can be understood in the art, including inorganic oxides such as alumina and oxygen storage materials, etc. Although, many other components are included aside from palladium, the thin layer is referred to as a Pd thin layer for convenient description.

[0017] With respect to the arrangement of Pd and Rh among the three-way catalytic precious metal components, Pd and Rh are present as separate components in an art-accepted composition. That is, Pd and Rh are arranged not to be close or adjacent to each other when constituting a catalyst. For example, Pd is supported on a catalyst support and thermally fixed, and Rh is supported on another catalyst support and thermally supported. Each of the precious metal components is prepared as a washcoat, the washcoats are mixed with cordierite or coated as a multilayer structure on cordierite to produce a three-way catalyst body. The catalyst body is mounted on a vehicle exhaust system through canning.

[0018] The concept of a thin precious-metal layer introduced herein can be applied to the configuration of a conventional three-way catalyst. Namely, regardless of the configuration of an underlying layer disposed under the precious metal thin layer, a portion of Pd required for a catalyst is used to form an upper thin layer, the performance of a three-way catalyst is improved. In this case, the proportion of the total Pd used to form the upper thin layer with respect to the overall amount of Pd used to constitute the catalyst may be in a range of 10% to 50% by weight, and the thickness of the thin upper layer needs to be 20 μm or less.

[0019] In addition, the inventors of the present application have found that in forming a thin Pd layer as the uppermost layer of the catalyst, the target coating amount and coating shape cannot be achieved by the conventional coating method. For example, the Pd content distribution exceeded the reference value, or the coating shape could not be maintained uniformly. Accordingly, an exhaust gas purification catalyst with a thin layer was prepared by using a new coating method referred to as Post PGM Thin-layer Coat (PPTC). Briefly, after preparing a double-layer pre-catalyst using a conventional method, a portion of the precious metal component constituting the catalyst, such as a portion of the Pd component forming the lower layer, is included in the polymer coating solution and then coated on the top of the double-layer pre-catalyst by a conventional method. The coating solution may permeate into a surface layer (20 μm or less) of the three-way catalyst to form a precious metal thin layer.

[0020] Hereinafter, the present invention will be described in detail with reference to examples, but it is clear that the spirit of the present invention is not limited thereto. For example, in a three-way catalyst manufactured according to the present invention, a Pt component may be included as the precious metal component of the lower layer. To simply and concisely describe the thin film properties of the upper layer in the present application, only Pd and Rh components are described. Pd and Rh components in the lower layer may be present in the form of non-alloy or alloy. However, in the embodiments described below, a Pd/Rh double layer structure will be described. In addition, the coating solution containing Pd is a polymer solution that forms a composite with palladium (Pd). Although not bound by theory, the coating solution may be hydroxyethyl cellulose (HEC) or polypropylene glycol having a functional group, such as a hydroxyl group or an ether group, capable of chelating with Pd. However, the coating solution is not limited thereto.

[0021] Pre-catalyst

[0022] The catalyst support Al.sub.2O.sub.3 powder was impregnated with aqueous Pd nitrate and aqueous Rh nitrate. The alumina powder was dried in an oven at 150° C. for 5 hours and calcinated at a temperature in the range from 400° C. to 650° C. for 5 hours to prepare a pre-catalyst powder. Slurry was prepared using the obtained pre-catalyst powder. The slurry was applied on the substrate using a conventional coating method (secondary coating step) and the substrate was heat treated in a reduction gas environment (i.e., exhaust gas ambient) at a temperature in the range from 500° C. to 1100° C., preferably, for 12 hours to obtain a pre-catalyst body.

Comparative Example

[0023] Alumina was impregnated with a Pd aqueous solution, dispersed in a solvent, and milled to prepare Pd slurry. The Pd slurry was coated on the pre-catalyst body by a conventional coating method to form a thin layer, dried, and calcinated to obtain a catalyst body. In this comparative example, the amount of Pd used to form the thin layer was 10% by weight with respect to the total amount of Pd used to form the catalyst body. Specifically, 90% by weight of the Pd component was used to form the lower layer of the pre-catalyst, and the remaining 10% by weight of the Pd component was used to form the thin layer (i.e., upper layer). Here, the thickness of the upper layer made of Pd was 28 μm, and the coating amount was 10 g/L. The deviation in the thickness of the upper coating layer exceeded a reference value, and the coating shape was not uniform (refer to FIG. 2A).

EXAMPLE 1

[0024] A Pd aqueous solution was dispersed in a commercially available polypropylene glycol solution, and the solution mixture was applied on the pre-catalyst body to form a thin coating layer, dried, and calcinated to form a catalyst body (see FIG. 2B, the thickness of the upper Pd coating layer was 8.61 μm, and the amount of Pd contained in the upper coating layer was 10% by weight with respect to the total amount of Pd used for the catalyst body). In this case, the

[0025] Pd content in the thin layer was the same method as in Comparative Example.

[0026] EXAMPLE 2

[0027] A catalyst body was prepared in the same manner as in Example 1 except that the Pd content used in the thin layer was 20% by weight with respect to the total amount of Pd used for the catalyst body.

[0028] EXAMPLE 3

[0029] A catalyst body was prepared in the same manner as in Example 1 except that the Pd content in the thin layer was 30% by weight with respect to the total amount of Pd used for the catalyst body.

[0030] EXAMPLE 4

[0031] A catalyst body was prepared in the same manner as in Example 1 except that the Pd content in the thin layer was 50% by weight with respect to the total amount of Pd used for the catalyst body.

[0032] The constructions of the thin layers (i.e., upper layers) of Comparative Example and Examples are summarized in Table 1 below.

TABLE-US-00001 TABLE 1 Thickness (μm) and Upper layer Amount of Pd in upper layer shape of upper layer (thin layer) (thin layer) (% by weight) (thin layer) Comparative 10 28, not-uniform example Example 1 10 8.61, uniform Example 2 20 7.55, uniform Example 3 30 12.99 uniform Example 4 50 16.43 uniform

[0033] The photographs and thickness observed at 400-fold magnification using an electron probe microanalyzer (SPMA) are shown in FIG. 4. The vehicle evaluation results for the catalyst body prepared in Example 1 are shown in FIG. 3. The catalyst body of Example 1 showed the better results than Comparative Example in terms of the concentrations of HC, CO, and NOR. Therefore, it was confirmed that the performance of the three-way catalyst was greatly improved when a portion of the total amount of a precious metal used for the three-way catalyst was used to form a thin film serving as the uppermost layer of the three-way catalyst while using the same amount of the precious metal for the three-way catalyst.