WO2009118593A1

WO2009118593A1 - Exhaust gas purifying catalyst

Info

Publication number: WO2009118593A1
Application number: PCT/IB2009/000433
Authority: WO
Inventors: Masamichi Kuwajima
Original assignee: Toyota Jidosha Kabushiki Kaisha
Priority date: 2008-03-25
Filing date: 2009-03-05
Publication date: 2009-10-01
Also published as: JP2009226349A

Abstract

An exhaust gas purifying catalyst is provided in which a NOx storageτeduction catalyst layer (3) is formed on a NOx adsorption layer (2) that includes a NOx adsorbent whose NOx adsorption amount when saturated at 2000C is equal to or larger than 0.1 mass%. NOx is adsorbed on the NOx adsorption layer (2) when exhaust gas is in a low temperature range equal to or lower than about 2000C, and NOx released from the NOx adsorption layer in a high temperature range exceeding about 2000C is stored and reduced (converted) on the NOx storage-reduction catalyst (3) as the upper layer. Thus, the catalyst is able to control emissions of NOx over a wide temperature range from low temperatures to high temperatures.

Description

EXHAUST GAS PURIFYING CATALYST

BACKGROUND OF THE INVENTION

1. Field of the Invention [0001] The invention relates to exhaust gas purifying catalysts capable of controlling emissions of NOx from automobiles over a wide range of temperatures from a low temperature range to a high temperature range.

2. Description of the Related Art [0002] Lean NOx catalysts, NOx storage -reduction catalysts, NH3 denitration catalysts, NOx selective reduction catalysts, and so forth are known as catalysts for reducing and converting NOx contained in exhaust gases emitted from lean-burn engines of automobiles. Of the above types of catalysts, the NOx storage-reduction catalyst uses a NOx storage material, such as alkali metal or alkaline earth metal, in addition to precious metal, such as Pt, serving as a catalyst, and causes the NOx storage material to store NOx thereon in a lean atmosphere. With exhaust gases intermittently controlled to be rich atmospheres (i.e., through rich spikes), the NOx storage-reduction catalyst causes NOx released from the NOx storage material to be reduced by a reducing component abundant in the atmosphere, so as to convert NOx into harmless substances. It is to be understood that "storage" used herein means retention of a substance (solid, liquid, gas, molecules, etc) in the form of at least one of adsorption, adhesion, absorption, trapping, occlusion, and others.

[0003] The NH3 denitration catalyst reduces NOx, using NH3 produced by adding an aqueous solution of urea, or the like, into exhaust gas, as disclosed in, for example, Japanese Patent Application Publication No. 10-146528 (JP-A-10-146528).

[0004] On the lean NOx catalyst and the NOx storage-reduction catalyst, however, it is difficult to reduce NOx in a low temperature range below about 250°C where precious metal, such as Pt, loaded on the catalyst is activated, thus presenting a problem that NOx is discharged as it is to the atmosphere. Also, NH3 and NOx react with each other at a high temperature on the NH3 denitration catalyst; therefore, a precious metal, such as Pd, is also used so as to lower the activation temperature of the catalyst. In this case, however, conversion or reduction of NOx is difficult to achieve until the temperature reaches a level at which the precious metal is activated, as is the case with the lean NOx catalyst or the NOx storage-reduction catalyst.

[0005] In view of the above problems, it has been proposed in Japanese Patent Application Publication No. 2000-230414 (JP-A-2000-230414) to locate a NOx adsorbent upstream of a NOx reduction catalyst in the form of a lean NOx catalyst or a NH3 denitration catalyst in an exhaust gas passage. In the proposed exhaust emission control system, NOx is adsorbed on the NOx adsorbent in a low temperature range, and NOx desorbed from the NOx adsorbent is reduced or converted on the NOx reduction catalyst located downstream of the NOx adsorbent in a high temperature range. It is thus possible to control (i.e., reduce) emissions of NOx over a wide temperature range from low temperatures to high temperatures.

[0006] An example of the NOx adsorbent as disclosed in JP-A-2000-230414 is composed of alumina carrying Pt, and it is stated in this publication that this NOx adsorbent absorbs NOx at temperatures up to about 230⁰C. Another example of NOx adsorbent as disclosed in Japanese Patent Application Publication No. 2007-160168 (JP-A-2007-160168) is composed of zeolite carrying at least one element selected from Fe, Cu and Co through ion exchange. A further example of NOx adsorbent as disclosed in Japanese Patent Application Publication No. 2001-198455 (JP-A-2001- 198455) is composed of an oxide of at least one element selected from Co, Fe and Ni, and adsorbs NOx at low temperatures equal to or below 40⁰C. Also, it is stated in JP-A-2007- 160168 that zeolite carrying at least one element selected from Fe, Cu and Co through ion exchange exhibits a high NOx adsorption capability at ordinary temperatures around room temperature.

[0007] While it has been proposed to mix the NOx adsorbent into the NOx storage-reduction catalyst, or locate the NOx adsorbent upstream of the NOx storage-reduction catalyst in an exhaust gas passage, these proposals are still deficient, and it has been desired to further reduce emissions of NOx over a wide temperature range from low temperatures to high temperatures.

SUMMARY OF THE INVENTION

[0008] The present invention has been developed in view of the above situations, and it is an object of the invention to provide an exhaust gas purifying catalyst capable of sufficiently controlling or reducing emissions of NOx over a wide temperature range from low temperatures to high temperatures.

[0009] According to one aspect of the invention, there is provided an exhaust gas purifying catalyst which includes^ a support substrate, a NOx adsorption layer that is formed on a surface of the support substrate, and includes a NOx adsorbent whose NOx adsorption amount when saturated at 200⁰C is equal to or larger than 0.1 mass%, and a NOx reduction catalyst layer formed on a surface of the NOx adsorption layer.

[0010] The NOx adsorbent is preferably at least one selected from alumina, ceria, zirconia and magnesia. It is particularly desirable that the NOx adsorbent is ceria.

[0011] The NOx adsorbent preferably includes one of lanthanides, and it is desirable that the lanthanides include at least one of lanthanum, praseodymium, and neodymium. Furthermore, it is desirable that the NOx adsorbent contains 3 to 80 mass% of an oxide of the lanthanide. The NOx adsorbent may be a ceria-zirconia composite oxide, in place of ceria.

[0012] The NOx adsorption layer preferably has a thickness of lOμm or larger. It is particularly desirable that the NOx adsorption layer has a thickness of 30μm or larger. [0013] The NOx adsorption layer preferably contains precious metal that serves as a catalyst for oxidizing NO, and the precious metal comprises at least one of Pt (platinum), Pd (palladium), and Rh (rhodium).

[0014] Also, the NOx reduction catalyst layer is desirably composed of a NOx storage-reduction catalyst.

[0015] In the exhaust gas purifying catalyst as described above, the NOx adsorbent of the NOx adsorption layer adsorbs NOx when the exhaust gas temperature is in a low temperature range of about 200°C or lower, so that emissions of NOx are controlled (i.e., reduced) even if the NOx reduction catalyst has not reached the activation temperature.

[0016] Then, if the exhaust gas temperature exceeds about 200⁰C, the NOx storage-reduction catalyst as an example of the NOx reduction catalyst reaches the activation temperature, and is thus able to store NOx in a lean atmosphere. Accordingly, NOx released from the NOx adsorption layer as the lower layer is trapped and stored by the NOx storage-reduction catalyst as the upper layer when it passes through the NOx storage-reduction catalyst, and the thus stored NOx is reduced and removed upon rich spikes. Also, NO contained in exhaust gases is oxidized into NO2 and stored at the same time on the NOx storage-reduction catalyst in a lean atmosphere, and is reduced and removed upon rich spikes. Thus, the use of the exhaust gas purifying catalyst of the present invention makes it possible to control (i.e., reduce) emissions of NOx even in a high temperature range.

BRIEF DESCRIPTION OF THE DRAWINGS [0017] The features, advantages, and technical and industrial significance of this invention will be described in the following detailed description of example embodiments of the invention with reference to the accompanying drawings, in which like numerals denote like elements, and wherein:

FIG. 1 is an explanatory, cross -sectional view schematically showing an exhaust gas purifying catalyst according to one embodiment of the invention;

FIG. 2 is a graph showing the relationship between the temperature of each specimen of exhaust gas purifying catalyst and the NOx adsorption amount when the catalyst is saturated with NOx.^' FIG. 3 is a graph showing the relationship between the temperature of the exhaust gas purifying catalyst and the amount of NOx stored in the catalyst after a rich spikeJ

FIG. 4 is a graph showing the relationship between the temperature of the exhaust gas purifying catalyst and the NOx conversion efficiency; FIG. 5 is a graph showing the relationship between the average thickness of the NOx adsorption layer and the NOx adsorption amount when the catalyst is saturated with NOxJ

FIG. 6 is a graph showing the relationship between the average thickness of the NOx adsorption layer and the amount of NOx stored in the catalyst after a rich spike.^' and

FIG. 7 is a graph showing the relationship between the average thickness of the NOx adsorption layer and the NOx conversion efficiency.

DETAILED DESCRIPTION OF EMBODIMENTS [0018] The exhaust gas purifying catalyst of the present invention has a support substrate, a NOx adsorption layer formed on a surface of the support substrate, and a NOx reduction catalyst layer formed on a surface of the NOx adsorption layer. The exhaust gas purifying catalyst of the invention is used in an exhaust gas atmosphere that varies alternately between a lean atmosphere and a stoichiometric or rich atmosphere.

[0019] The support substrate may be in the form of a honeycomb substrate, foam substrate, pellet substrate, or the like, which is made of a ceramic material, such as cordierite or SiC, or metal.

[0020] The NOx adsorption layer includes a NOx adsorbent whose NOx saturation adsorption amount (i.e., the amount of NOx adsorbed on the NOx adsorbent when it is saturated with NOx) is 0.1 mass % or greater at 200⁰C. The inclusion of the NOx adsorbent having such a large NOx adsorption amount at low temperatures makes it possible to prevent or restrict the entry of NOx before the NOx reduction, catalyst as an upper layer placed on the NOx adsorption layer is activated, and to reduce the amount of NOx discharged to the atmosphere in a low temperature range.

[0021] The NOx adsorbent may be selected from, for example, ceria (cerium oxide), zirconia (zirconium oxide), and magnesia (magnesium oxide), which have high degrees of basicity, and alumina (aluminium oxide) having a large specific surface area. It is desirable for the NOx adsorbent to include at least ceria, among the above-listed materials. Ceria, which has a high capability of absorbing and releasing oxygen, oxidizes NO contained in exhaust gas, using active oxygen produced during absorption and release of oxygen, and adsorbs NO2 on itself. Thus, ceria exhibits a high NOx adsorption capability in a low temperature range. Since oxygen is consumed for oxidation of NO, a reducing component of a rich atmosphere used upon rich spikes is less likely to be oxidized by oxygen contained in ceria, and otherwise possible degradation of the rich atmosphere (i.e., reduction in the richness of the rich atmosphere) is avoided. [0022] When ceria is used as the NOx adsorbent, a ceria-zirconia composite oxide, or the like, may be used in place of ceria. Also, the NOx adsorbent may contain 3 to 80 mass% of an oxide of lanthanide, such as La (lanthanum), Pr (praseodymium), or Nd (neodymium), based on the amount of ceria, for improvement of the NOx adsorption capability. The NOx adsorbent may contain an oxide of a metal selected from, for example, Fe (iron), Mn (Manganese), Bi (bismuth), Cu (copper), Cr (chromium), Co (cobalt), Ga (gallium), V (vanadium), Ba (barium), Mg (magnesium), K (potassium), Hf (hafnium), and Re (rhenium), for improvement of the NOx adsorption capability. Also, the NOx adsorbent may contain another porous oxide, such as AI2O3, ZrO2, or TiO2- In this connection, it is desirable that the oxide of an element(s) other than Ce (cerium) amounts to 80 mass% or smaller, with respect to ceria. If the amount of the oxide of the other element(s) exceeds the upper limit of this range, the content of ceria decreases relative to that of the other oxide(s), and the NOx adsorption amount of the NOx adsorbent is reduced.

[0023] The NOx adsorption layer may be formed solely of the NOx adsorbent, or may be formed such that the NOx adsorbent is loaded on a support comprised of a porous oxide different from that of the NOx adsorbent. Then, the

NOx adsorption layer may be formed on a surface of the support substrate by washcoating, for example.

[0024] Where the catalyst is honeycomb shaped, it is desirable to form the

NOx adsorption layer with the average thickness of 10μm or larger, more desirably,

30μm or larger. If the average thickness of the NOx adsorption layer is less than

10μm, the amount of NOx adsorbed when saturated is too small, and is not practical.

[0025] While the NOx adsorption layer yields its intended effect even if it does not carry precious metal, it may carry a precious metal, such as Pt, Pd or Rh in some cases. If the NOx adsorbent as described above is loaded with a small amount of precious metal, for example, NO contained in exhaust gas is oxidized at 200⁰C or higher to form NO2. As a result, adsorption of NOx onto the NOx adsorbent is promoted, and the NOx adsorption capability is improved. In this case, the amount of the precious metal loaded may be 0.01 to 2 mass% with respect to the NOx adsorbent.

[0026] The NOx reduction catalyst layer is formed as an upper layer on the NOx adsorption layer. While a known catalyst, such as a lean NOx catalyst, NOx storage-reduction catalyst, or a NH3 denitration catalyst, may be used as the NOx reduction catalyst, the NOx storage-reduction catalyst capable of effectively controlling emissions of NOx in a high temperature range is particularly desirable.

[0027] The NOx storage -reduction catalyst layer formed on a surface of the NOx adsorption layer has a porous oxide support made of, for example, alumina, zirconia, or titania (titanium dioxide), and precious metal and NOx storage material which are loaded on the support. At least one element selected from Pt, Rh, Pd, etc. may be used as the precious metal, and at least one element selected from alkali metals, such as K, Li, and Na and alkaline earth metals, such as Ba, Ca, and Mg, may be used as the NOx storage material. The support substrate is preferably loaded with the precious metal in a range of O.Olg to 2Og per liter of the support substrate, and is preferably loaded with the NOx storage material in a range of 0.05 mol to 0.5 mol per liter of the support substrate. [0028] Where the catalyst is honeycomb shaped, the NOx reduction catalyst layer is desirably formed with the average thickness of lOμm or larger, more desirably, 50μm or larger. If the average thickness of the NOx reduction catalyst layer is less than lOμm, the resulting NOx reduction catalyst layer has an insufficient NOx converting capability, and is not suited for practical use. However, since the exhaust pressure loss increases if the thickness is too large, the total thickness of the NOx reduction catalyst layer and the NOx adsorption layer should be controlled so as not to affect the exhaust pressure loss.

[0029] In the following, the invention will be more specifically described by means of example of the invention, comparative examples, and test examples. [0030] FIG. 1 shows an exhaust gas purifying catalyst according to

Example 1 of the invention. This exhaust gas purifying catalyst consists of a honeycomb substrate 1 made of cordierite, NOx adsorption layers 2 formed on surfaces of cell partition walls 10 of the honeycomb substrate 1, and NOx storage-reduction catalyst layers 3 formed on surfaces of the NOx adsorption layers 2. In the following, a method for producing the NOx adsorption layer 2 and the NOx storage -reduction catalyst layer 3 will be described, in place of detailed description of the construction of the catalyst.

[0031] Initially, a slurry (A) was prepared by mixing a powder of Ceθ2-Pr2θ3 composite oxide (mole ratio of Ce to Pr = 90 : 10), a certain amount of ceria sol, and ion-exchange water, and subjecting the mixture to milling.

[0032] Next, a honeycomb substrate 1 (of straight flow type, having a diameter of 30mm and a volume of 50L) made of cordierite was prepared, and was washcoated with the slurry or liquid mixture as described above, dried, and calcined, to form the NOx adsorption layer 2. The average thickness of the NOx adsorption layer 2 is 30 μm.

[0033] On the other hand, a slurry (B) was prepared by mixing an alumina powder, a certain amount of alumina sol, and ion-exchange water, and subjecting the mixture to milling. This slurry was applied by washcoating to the surface of the NOx adsorption layer 2, dried, and calcined, to form a coating. The average thickness of the coating is 70μm. Then, the coating was loaded with Pt, using a platinum solution, and was further loaded with K, Li and Ba, using an aqueous solution of nitrate, to form the NOx storage-reduction catalyst layer 3.

[0034] The amount of Pt loaded is 3g per liter of the honeycomb substrate 1, and the amounts of K, Li and Ba loaded are 0.1 mol, 0.2 mol, and 0.1 mol, respectively, per liter of the honeycomb substrate 1.

[0035] Next, Comparative Example 1 will be described. A honeycomb substrate 1 similar to that of Example 1 was prepared, and a coating having the average thickness of 70μm was formed on the substrate 1, using the above-described slurry (B). Further, the coating was loaded with Pt, K, Li and Ba in the same manner as in Example 1, so as to form only the NOx storage -reduction catalyst layer. This catalyst is equivalent to the conventional NOx storage-reduction catalyst.

[0036] Next, Comparative Example 2 will be described. A honeycomb substrate 1 similar to that of Example 1 was prepared, and a coating having the average thickness of lOOμm was formed on the substrate 1, using a mixture of equal amounts of the slurry (A) and slurry (B). The coating was loaded with the same amounts of Pt, K, Li and Ba as in Example 1, so as to form a NOx storage-reduction catalyst layer. [0037] Next, Comparative Example 3 will be described. A honeycomb substrate 1 similar to that of Example 1 was prepared, and a coating having the average thickness of 70μm was formed on the substrate 1, using the slurry (B).

Thereafter, the coating was loaded with the same amounts of Pt, K, Li and Ba as in Example 1, so as to form a NOx storage-reduction catalyst layer (lower layer).

[0038] Then, a NOx adsorption layer (upper layer) having the average thickness of 30μm was formed, using the slurry (A), on a surface of the NOx storage -reduction catalyst layer (lower layer), in the same manner as in Example 1. [0039] Next, Test Example 1 will be described. Each of the catalysts of

Example 1 and Comparative Examples 1 - 3 was placed in an evaluation apparatus, in which the catalyst was exposed to lean gas as indicated in TABLE 1, so that NOx was absorbed on the catalyst until it is saturated with NOx, at respective catalyst temperatures in the range of 50⁰C to 200⁰C (the catalyst temperatures being deemed equivalent to exhaust gas temperatures). The amounts of NOx adsorbed on the respective catalysts when saturated were measured, and the results of measurements are indicated in FIG. 2. TABLE 2 shows the construction of each of the catalysts tested in this test example.

TABLE l

NO (ppm) C₃H₆ (ppmC) O₂ (%) CO₂ (%) H₂O (%) N₂

Lean Gas 200 500 10 10 3 Remainder

Rich Gas 200 20000 1 10 3 Remainder

TABLE 2

[0040] Under a condition that flow of the lean gas as indicated in TABLE 1 which lasts 55 seconds and flow of the rich gas as indicated in TABLE 1 which lasts 5 seconds are repeated alternately, each of the catalysts as indicated above was subjected to rich spikes at catalyst temperatures between 300⁰C and 450⁰C, and the amount of NOx stored on the catalyst after rich spike and the NOx conversion efficiency (the average value in a 3-minite period) were measured with respect to each of the catalysts. The results of the measurements are indicated in FIG. 3 and FIG. 4.

[0041] It is understood from FIG. 2 that the NOx adsorption amount at temperatures equal to or below 150⁰C is improved by about 80% in Comparative Example 2, as compared with that of Comparative Example 1, and is improved by about 45% in Comparative Example 3, as compared with that of Comparative Example 1. In Example 1, however, the NOx adsorption amount at temperatures equal to or below 150⁰C is improved by about 100%, as compared with that of Comparative Example 1, and the degree of the improvement is greater than those of the other comparative examples. This is apparently because the NOx adsorption layer 2 as the lower layer is located under the NOx storage -reduction catalyst layer 3.

[0042] It is understood from FIG. 3 and FIG. 4 that the NOx adsorption amount of Comparative Example 2 in a high temperature range is substantially the same as that of Comparative Example 1, but the NOx conversion efficiency is reduced by about 20% in Comparative Example 2. This may be because the reducibility of NOx deteriorates (i.e., NOx is less likely to be reduced), due to the ceria's capability of absorbing and releasing oxygen. [0043] In Comparative Example 3, the NOx adsorption amount in a high temperature range is reduced by about 60%, as compared with that of Comparative Example 1, and the NOx conversion efficiency is reduced by about 50%, as compared with that of Comparative Example 1. This may be because the NOx storage material contained in the NOx storage-reduction catalyst layer as the lower layer is not effectively utilized, in addition to an influence of the ceria's capability of absorbing and releasing oxygen.

[0044] In Example 1, on the other hand, the NOx adsorption amount in a high temperature range is improved by about 30%, and the NOx conversion efficiency is also improved by about 10%, as compared with those of Comparative Example 1. This is apparently because the NOx adsorption layer 2 as the lower layer is located under the NOx storage-reduction catalyst layer 3. Namely, the arrangement in which the NOx adsorption layer containing ceria is located under the NOx storage-reduction catalyst layer removes an impediment to reduction of NOx due to the ceria's capability of absorbing and releasing oxygen, and permits NOx released from the NOx adsorption layer as the lower layer to be stored and reduced with improved efficiency.

[0045] Next, Test Example 2 will be described. Some specimens of catalysts were prepared in the same manner as in Example 1, except that the NOx adsorption layers of the respective catalysts were formed with different average thicknesses, i.e., Oμm, 5μm, lOμm, 15μm, 20μm, 30μm, 40μm, 50μm and 60μm. The average thickness of the NOx storage-reduction catalyst layer as the upper layer was fixed to 70μm.

[0046] For each of the catalysts, the amount of NOx adsorbed on the catalyst at 150⁰C when saturated with NOx, the amount of NOx stored after a rich spike at 400⁰C, and the NOx conversion efficiency (the average value in a 3-minite period) at 400⁰C were measured in the same manner as in Test Example 1, and the results of the measurements are indicated in FIG. 5 through FIG. 7.

[0047] It is apparent from FIG. 5 - FIG. 7 that the average thickness of the NOx adsorption layer is preferably lOμm or larger, and is particularly desirably 30μm or larger.

Claims

CLAIMS:

1. An exhaust gas purifying catalyst, comprising: a support substrate! a NOx adsorption layer that is formed on a surface of the support substrate, and includes a NOx adsorbent whose NOx adsorption amount when saturated at 200⁰C is equal to or larger than 0.1 mass%; and a NOx reduction catalyst layer formed on a surface of the NOx adsorption layer.

2. The exhaust gas purifying catalyst according to claim 1, characterized in that the NOx adsorbent comprises at least one selected from alumina, ceria, zirconia and magnesia.

3. The exhaust gas purifying catalyst according to claim 2, characterized in that the NOx adsorbent comprises ceria.

4. The exhaust gas purifying catalyst according to claim 3, characterized in that the NOx adsorbent includes one of lanthanides.

5. The exhaust gas purifying catalyst according to claim 4, characterized in that the lanthanides include at least one of lanthanum, praseodymium, and neodymium.

6. The exhaust gas purifying catalyst according to claim 4, characterized in that the NOx adsorbent contains 3 to 80 mass% of an oxide of the lanthanide.

7. The exhaust gas purifying catalyst according to claim 2, characterized in that the NOx adsorbent comprises a ceria-zirconia composite oxide.

8. The exhaust gas purifying catalyst according to any one of claims 1 through 7, characterized in that the NOx adsorption layer has a thickness of lOμm or larger.

9. The exhaust gas purifying catalyst according to claim 8, characterized in that the NOx adsorption layer has a thickness of 30μm or larger.

10. The exhaust gas purifying catalyst according to any one of claims 1 through 9, characterized in that the NOx adsorption layer contains precious metal that serves as a catalyst for oxidizing NO.

11. The exhaust gas purifying catalyst according to claim 10, characterized in that the precious metal comprises at least one of Pt (platinum), Pd (palladium), and Rh (rhodium).

12. The exhaust gas purifying catalyst according to any one of claims 1 through 10, characterized in that the NOx reduction catalyst layer is composed of a NOx storage-reduction catalyst.